Patent Application
20130047509
1. Field
Embodiments described herein generally relate to systems and methods for producing synthetic gas. More particularly, such embodiments of the present invention relate to systems and methods for producing synthetic gas using low grade coal or other carbonaceous feedstocks.
2. Description of the Related Art
Clean coal technology using gasification is a promising alternative to meet the global energy demand. Most existing coal gasification processes perform best on high rank (bituminous) coals and petroleum refinery waste products, but these processes are inefficient, unreliable, and expensive to operate when processing low grade coal. Low grade coal reserves including low rank and high ash coal remain underutilized as energy sources despite being available in abundance. Coal gasification coupled with methanation and carbon dioxide management offer an environmentally sound energy source. Synthetic or substitute natural gas (“SNG”) can provide a reliable supply of fuel. SNG, with the right equipment, can be produced proximate to a coal source. SNG can be transported from a production location into an already existing natural gas pipeline infrastructure, which makes the production of SNG economical in areas where it would otherwise be too expensive to mine and transport low grade coal.
Typical problems with SNG production include high auxiliary power and process water requirements. The large quantities of power and water needed to run the SNG production system can greatly escalate the cost of production and limit where SNG generation systems can be deployed.
There is a need, therefore, for more efficient systems and methods for producing SNG from coal that reduce the requirements for outside power and water.
Systems and methods for producing synthetic gas are provided. The method can include gasifying a feedstock within a gasifier to provide a raw syngas. The raw syngas can be processed within a purification system to provide a treated syngas, and the purification system can include a flash gas separator. The treated syngas and a first heat transfer medium can be converted into a synthetic gas, a second heat transfer medium, and a methanation condensate. The methanation condensate can be introduced to the flash gas separator.
The raw syngas via line 106 can be introduced to the syngas cooler 305 to provide a cooled syngas via line 116. Heat from the raw syngas introduced via line 106 to the syngas cooler 305 can be transferred to a heat transfer medium introduced via line 108 and/or 112. The heat transfer medium in line 108 and/or 112 can be process water, boiler feed water, superheated low pressure steam, superheated medium pressure steam, superheated high pressure steam, saturated low pressure steam, saturated medium pressure steam, saturated high pressure steam, and the like. Although not shown, the heat transfer medium in line 108 and/or 112 can include process steam or condensate from the syngas purification system 400.
Although not shown, the heat transfer medium via line 112 can be introduced or otherwise mixed with the heat transfer medium in line 108 to provide a heat transfer medium mixture or “mixture.” The mixture can be introduced as the heat transfer medium to the syngas cooler 305 to provide the superheated high pressure steam via line 110 and/or line 114. The mixture can also be recovered from the syngas cooler 305 via a single line (not shown).
The heat transfer medium in line 108, for example boiler feed water, can be heated within the syngas cooler 305 to provide superheated high pressure steam via line 110. The heat transfer medium in line 112 can be heated within the syngas cooler 305 to provide superheated high pressure steam or steam at a higher temperature and/or pressure than in line 112 via line 114. The steam via line 110 and/or line 114 can have a temperature of about 450° C. or more, about 550° C. or more, about 650° C. or more, or about 750° C. or more. The steam via line 110 and/or line 114 can have a pressure of about 4,000 kPa or more, about 8,000 kPa or more, about 11,000 kPa or more, about 15,000 kPa or more, about 17,000 kPa or more, about 19,000 kPa or more, about 21,000 kPa or more, or about 22,100 kPa or more.
At least a portion of the superheated high pressure steam via lines 110, 114 can be used to generate auxiliary power for the SNG system 100. At least a portion of the superheated high pressure steam via lines 110, 114 can be introduced to the gasifier 205. For example, the superheated high pressure steam via lines 110, 114 can be introduced to the gasifier 205 after a pressure let down, for example from a steam turbine.
The cooled syngas via line 116 from the syngas cooler 305 can be introduced to the purification system 400 to provide a treated/purified syngas via line 118. The syngas purification system 400 can remove particulates, ammonia, carbonyl sulfide, chlorides, mercury, and/or acid gases. The syngas purification system 400 can saturate the cooled syngas with water, shift convert carbon monoxide to carbon dioxide, or combinations thereof.
The syngas in line 118 can have a hydrogen concentration ranging from a low of about 20 mol %, about 30 mol %, about 40 mol %, or about 50 mol % to a high of about 60 mol %, about 70 mol %, about 80 mol %, or about 90 mol %, on a dry basis. For example, the syngas in line 118 can have a hydrogen concentration of about 25 mol % to about 85 mol %, about 35 mol % to about 75 mol %, about 45 mol % to about 65 mol %, or about 60 mol % to about 70 mol %, on a dry basis. The syngas in line 118 can have a carbon monoxide concentration ranging from a low of about 1 mol %, about 5 mol %, about 10 mol %, or about 15 mol % to a high of about 25 mol %, about 30 mol %, about 35 mol %, or about 40 mol %, on a dry basis. For example, the syngas in line 118 can have a carbon monoxide concentration of about 3 mol % to about 37 mol %, about 7 mol % to about 33 mol %, about 13 mol % to about 27 mol %, or about 17 mol % to about 23 mol %, on a dry basis. The syngas in line 118 can have a carbon dioxide concentration ranging from a low of about 0 mol %, about 5 mol %, about 10 mol %, or about 15 mol % to a high of about 20 mol %, about 25 mol %, or about 30 mol %, on a dry basis. For example, the syngas in line 118 can have a carbon dioxide concentration of about 0.1 mol % to about 30 mol %, about 0.5 mol % to about 20 mol %, about 1 mol % to about 15 mol %, or about 2 mol % to about 10 mol %, on a dry basis. The syngas in line 118 can have a methane concentration ranging from a low about 0 mol %, about 3 mol %, about 5 mol %, about 7 mol %, or about 9 mol % to a high of about 15 mol %, about 20 mol %, about 25 mol %, or about 30 mol %, on a dry basis. For example, the syngas in line 118 can have a methane concentration of about 2 mol % to about 19 mol %, about 4 mol % to about 17 mol %, about 6 mol % to about 15 mol %, or about 8 mol % to about 13 mol %, on a dry basis. The syngas in line 118 can have a nitrogen concentration of about 5 mol % or less, about 4 mol % or less, about 3 mol % or less, about 2 mol % or less, about 1 mol % or less, or about 0.5 mol % or less, on a dry basis. For example, the syngas in line 118 can have a nitrogen concentration of about 0.01 mol % to about 4.5 mol %, about 0.05 mol % to about 3.5 mol %, about 0.07 mol % to about 2.5 mol %, or about 0.1 mol % to about 1.5 mol %, on a dry basis. The syngas in line 118 can have an argon concentration of about 5 mol % or less, about 4 mol % or less, about 3 mol % or less, about 2 mol % or less, about 1 mol % or less, or about 0.5 mol % or less, on a dry basis. For example, the syngas in line 118 can have an argon concentration of about 0.01 mol % to about 3.5 mol %, about 0.02 mol % to about 2.5 mol %, or about 0.03 mol % to about 1.5 mol %, on a dry basis. The syngas in line 118 can have a water concentration of about 5 mol % or less, about 4 mol % or less, about 3 mol % or less, about 2 mol % or less, about 1 mol % or less, or about 0.5 mol % or less, on a wet basis. For example, the syngas in line 118 can have a water concentration of about 0.01 mol % to about 3.5 mol %, about 0.05 mol % to about 2.5 mol %, or about 0.1 mol % to about 1.5 mol %, on a wet basis.
The low concentration of inert gases, i.e., nitrogen and argon, can increase the heating value of the SNG provided via line 122 from the methanator 500. A higher methane concentration in the treated syngas via line 118 can be beneficial for SNG production, can provide a product value, for example a heating value, and can also reduce the product gas recycle requirements to quench the heat of reaction within the methanator 500. The methane concentration can also reduce auxiliary power consumption, capital costs, and operating costs of the SNG system.
The treated syngas via line 118 and a heat transfer medium (“first heat transfer medium”) via line 120 can be introduced to the methanator 500 to provide a methanated syngas or SNG via line 122 and a heated heat transfer medium (“second heat transfer medium”), e.g., steam, via line 124. The methanator 500 can be or include any device or system suitable for converting at least a portion of the hydrogen, carbon monoxide, and/or carbon dioxide to SNG. The SNG in line 122 can have a methane content ranging from a low of about 0.01 mol % to a high of 100 mol %. For example, the SNG in line 122 can have a methane content ranging from a low of about 65 mol %, about 75 mol %, or about 85 mol % to a high of about 90 mol %, about 95 mol %, or about 100 mol %. The methanator 500 can be operated at a temperature ranging from a low of about 150° C., about 425° C., about 450° C., or about 475° C. to a high of about 535° C., about 565′C, or about 590° C. The methanator 500 can also be operated at a temperature ranging from a low of about 590° C., about 620° C., or about 640° C. to a high of about 660° C., about 675° C., about 700° C., or about 1,000° C.
The methanation of the treated syngas in line 118 is an exothermic reaction that generates heat. At least a portion of the heat generated during methanation of the purified syngas can be transferred to the heat transfer medium introduced via line 120 to provide the steam via line 124. The heat transfer medium in line 120 can be process water, boiler feed water, and the like. For example, boiler feed water introduced via line 120 to the methanator 500 can be heated to provide low pressure steam, medium pressure steam, high pressure steam, saturated low pressure steam, saturated medium pressure steam, or saturated high pressure steam. At least a portion of the steam (“second heat transfer medium”) in line 124 can be introduced to the syngas cooler 305 as the heat transfer medium introduced via line 112. Another portion of the steam via line 124 can be provided to various process units within SNG generation system 100 (not shown). The steam in line 124 can have a temperature of about 250° C. or more, about 350° C. or more, about 450° C. or more, about 550° C. or more, about 650° C. or more, or about 750° C. or more. The steam in line 124 can be at a pressure of about 4,000 kPa or more, about 7,500 kPa or more, about 9,500 kPa or more, about 11,500 kPa or more, about 14,000 kPa or more, about 16,500 kPa or more, about 18,500 kPa or more, about 20,000 kPa or more, about 21,000 kPa or more, or about 22,100 kPa or more. For example, the steam in line 124 can be at a pressure of from about 4,000 kPa to about 14,000 kPa or from about 7,000 kPa to about 10,000 kPa. As described above, the steam (“second heat transfer medium”) via line 112 can absorb heat from the raw syngas via line 106 in the syngas cooler 305 to provide the steam (“third heat transfer medium”) via line 110 and/or 114.
The feedstock via line 102, oxidant via line 104, and steam via line 127 can be combined in the mixing zone 215 to provide a gas mixture. The feedstock via line 102 can include any suitable carbonaceous material. The carbonaceous material can include, but is not limited to, one or more carbon-containing materials whether solid, liquid, gas, or a combination thereof. The one or more carbon-containing materials can include, but are not limited to, coal, coke, petroleum coke, cracked residue, crude oil, whole crude oil, vacuum gas oil, heavy gas oil, residuum, atmospheric tower bottoms, vacuum tower bottoms, distillates, paraffins, aromatic rich material from solvent deasphalting units, aromatic hydrocarbons, asphaltenes, naphthenes, oil shales, oil sands, tars, bitumens, kerogen, waste oils, biomass (e.g., plant and/or animal matter or plant and/or animal derived matter), tar, low ash or no ash polymers, hydrocarbon-based polymeric materials, heavy hydrocarbon sludge and bottoms products from petroleum refineries and petrochemical plants such as hydrocarbon waxes, byproducts derived from manufacturing operations, discarded consumer products, such as carpet and/or plastic automotive parts/components including bumpers and dashboards, recycled plastics such as polypropylene, polyethylene, polystyrene, polyurethane, derivatives thereof, blends thereof, or any combination thereof. Accordingly, the process can be useful for accommodating mandates for proper disposal of previously manufactured materials.
The coal can include, but is not limited to, high-sodium and/or low-sodium lignite, subbituminous, bituminous, anthracite, or any combination thereof. The hydrocarbon-based polymeric materials can include, for example, thermoplastics, elastomers, rubbers, including polypropylenes, polyethylenes, polystyrenes, including other polyolefins, polyurethane, homo polymers, copolymers, block copolymers, and blends thereof; polyethylene terephthalate (PET), poly blends, other polyolefins, poly-hydrocarbons containing oxygen, derivatives thereof, blends thereof, and combinations thereof.
Depending on the moisture concentration of the carbonaceous material, for example coal, the carbonaceous material can be dried prior to introduction to the gasifier 205. The carbonaceous material can be pulverized by milling units, such as one or more bowl mills, and heated to provide a carbonaceous material containing a reduced amount of moisture. For example, the carbonaceous material can be dried to provide a carbonaceous material containing less than about 50% moisture, less than about 30% moisture, less than about 20% moisture, less than about 15% moisture, or less. The carbonaceous material can be dried directly in the presence of a gas, for example nitrogen, or indirectly using any heat transfer medium via coils, plates, or other heat transfer equipment.
The feedstock introduced via line 102 can include nitrogen containing compounds. For example, the feedstock via line 102 can be coal or petroleum coke that contains about 0.5 mol %, about 1 mol %, about 1.5 mol %, about 2 mol % or more nitrogen in the feedstock based on ultimate analysis of the carbonaceous feedstock. At least a portion of the nitrogen contained in the feedstock introduced via line 102 can be converted to ammonia within the gasifier 205. In one or more embodiments, about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80% or more of the nitrogen in the feedstock can be converted to ammonia within the gasifier 205. For example, the amount of nitrogen in the feedstock converted within the gasifier 205 to ammonia can range from a low of about 20%, about 25%, about 30%, or about 35% to a high of about 70%, about 80%, about 90%, or about 100%.
The average particle diameter size of the feedstock via line 102 can be used as a control variable to optimize particulate density of the solids recycled to the mixing zone via the standpipe 250. The particle size of the feedstock introduced via line 102 can be varied to optimize the particulate mass circulation rate and to improve the flow characteristics of the gas-solid mixture within the mixing zone 215 and riser 220. The steam via line 127 can be supplied to the gasifier 205 both as a reactant and as a moderator to control the reaction temperature.
The oxidant introduced via line 104 can include, but is not limited to, air, oxygen, essentially oxygen, oxygen-enriched air, mixtures of oxygen and air, mixtures of oxygen and inert gas such as nitrogen and argon, and combinations thereof. As used herein, the term “essentially oxygen” refers to an oxygen feed containing 51% vol oxygen or more. As used herein, the term “oxygen-enriched air” refers to air containing greater than 21% vol oxygen. Oxygen-enriched air can be obtained, for example, from cryogenic distillation of air, pressure swing adsorption, membrane separation, or any combination thereof. The oxidant introduced via line 104 can be nitrogen-free or essentially nitrogen-free. By “essentially nitrogen-free,” it is meant that the oxidant in line 104 contains less than about 5% vol nitrogen, less than about 4% vol nitrogen, less than about 3% vol nitrogen, less than about 2% vol nitrogen, or less than about 1% vol nitrogen. The steam via line 127 can be any suitable type of steam, for example low pressure steam, medium pressure steam, high pressure steam, superheated low pressure steam, superheated medium pressure steam, or superheated high pressure steam.
The amount of oxidant introduced via line 104 to the mixing zone 215 can range from about 1% to about 90% of the stoichiometric oxygen required to oxidize the total amount of carbonaceous materials in the carbonaceous solids and/or the carbonaceous containing solids. The oxygen concentration within the gasifier 205 can range from a low of about 1%, about 3%, about 5%, or about 7% to a high of about 30%, about 40%, about 50%, or about 60% of the stoichiometric requirements based on the molar concentration of carbon in the gasifier 205. In one or more embodiments, the oxygen concentration within the gasifier 205 can range from a low of about 0.5%, about 2%, about 6%, or about 10% to a high of about 60%, about 70%, about 80%, or about 90% of the stoichiometric requirements based on the molar concentration of carbon in the gasifier 205.
One or more sorbents can also be introduced to the gasifier 205. The sorbents can capture contaminants from the syngas, such as sodium vapor in the gas phase within the gasifier 205. The sorbents can scavenge oxygen at a rate and level sufficient to delay or prevent oxygen from reaching a concentration that can result in undesirable side reactions with hydrogen (e.g., water) from the feedstock within the gasifier 205. The sorbents can be mixed or otherwise added to the one or more feedstocks. The sorbents can be used to dust or coat feedstock particles in the gasifier 205 to reduce the tendency for the particles to agglomerate. The sorbents can be ground to an average particle size of about 5 microns to about 100 microns, or about 10 microns to about 75 microns. Illustrative sorbents can include, but are not limited to, carbon rich ash, limestone, dolomite, kaolin, silica flour, and coke breeze. Residual sulfur released from the feedstock can be captured by native calcium in the feedstock or by a calcium-based sorbent to form calcium sulfide.
The gasifier 205 can be operated at a temperature range from a low of about 500° C., about 600° C., about 700° C., about 800° C., or about 900° C. to a high of about 1,000° C., about 1,100° C., about 1,200° C., about 1,500° C., or about 2,000° C. For example, the gasifier 205 can be have a temperature between about 870° C. to about 1,100° C., about 890° C. to about 940° C., or about 880° C. to about 1,050° C. Heat can be supplied by burning the carbon in the recirculated solids in a lower portion of the mixing zone 215 before the recirculated solids contact the entering feedstock.
The operating temperature of the gasifier 205 can be controlled, at least in part, by the recirculation rate and/or residence time of the solids within the riser 220; by reducing the temperature of the ash prior to recycling via line 255 to the mixing zone 215; by the addition of steam to the mixing zone 215; and/or by varying the amount of oxidant added to the mixing zone 215. The recirculating solids introduced via line 255 can serve to heat the incoming feedstock, which also can mitigate tar formation.
The residence time and temperature in the mixing zone 215 and the riser 220 can be sufficient for water-gas shift reaction to reach near-equilibrium conditions and to allow sufficient time for tar cracking. The residence time of the feedstock in the mixing zone 215 and riser 220 can be greater than about 2 seconds, greater than about 5 seconds, or greater than about 10 seconds.
The feedstock via line 102, oxidant via line 104, and steam via line 127 can be introduced sequentially or simultaneously into the mixing zone 215. The feedstock via line 102, oxidant via line 104, and steam via line 127 can be introduced separately into the mixing zone 215 (as shown) or mixed prior to introduction to the mixing zone 215 (not shown). The feedstock via line 102, oxidant via line 104, and steam via line 127 can be introduced continuously or intermittently depending on desired product types and grades of the raw syngas.
The mixing zone 215 can be operated at pressures from about 100 kPa to about 6,000 kPa to increase thermal output per unit reactor cross-sectional area and to enhance raw syngas energy output. For example, the mixing zone 215 can be operated at a pressure ranging from a low of about 600 kPa, about 650 kPa, or about 700 kPa to a high of about 2,250 kPa, about 3,250 kPa, or about 3,950 kPa or more. The mixing zone 215 can be operated at a temperature ranging from a low of about 250° C., about 400° C., or about 500° C. to a high of about 650° C., about 800° C., or about 1,000° C. For example, the mixing zone 215 can be operated at a temperature of from about 350° C. to about 950° C., about 475° C. to about 900° C., about 899° C. to about 927° C., or about 650° C. to about 875° C.
The gas mixture can flow through the mixing zone 215 into the riser 220 where additional residence time allows the gasification, steam/methane reforming, tar cracking, and/or water-gas shift reactions to occur. The riser 220 can operate at a higher temperature than the mixing zone 215. Suitable temperatures in the riser 220 can range from about 550° C. to about 2,100° C. For example, suitable temperatures within the riser 220 can range from a low of about 700° C., about 800° C., or about 900° C. to a high of about 1050° C., about 1150° C., about 1250° C., or more. The riser 220 can have a smaller diameter or cross-sectional area than the mixing zone 215, or the riser 220 can have the same diameter or cross-sectional area as the mixing zone 215. The superficial gas velocity in the riser 220 can range from about 3 m/s to about 27 m/s, about 6 m/s to about 24 m/s, about 9 ms to about 21 m/s, about 9 m/s to about 12 m/s, or about 11 m/s to about 18 m/s.
The gas mixture can exit the riser 220 and enter the disengagers 230, 240 where at least a portion of particulates can be separated from the gas and recycled back to the mixing zone 215 via one or more conduits including, but not limited to, a standpipe 250, and/or j-leg 255. The disengagers 230, 240 can be cyclones. The j-leg 255 can include a non-mechanical “j-valve,” “L-valve,” or other valve to increase the effective solids residence time, increase the carbon conversion, and minimize aeration requirements for recycling solids to the mixing zone 215. One or more particulate transfer devices 245, such as one or more loop seals, can be located downstream of the disengagers 230, 240 to collect the separated particulates.
The raw syngas in line 106 exiting the gasifier 205 can include, but is not limited to, hydrogen, carbon monoxide, carbon dioxide, methane, nitrogen, argon, or any combination thereof. The raw syngas in line 106 can have a hydrogen content ranging from a low of about 40 mol % to a high of about 80 mol %. The raw syngas in line 106 can have a carbon monoxide content ranging from a low of about 15 mol % to a high of about 25 mol %. The raw syngas in line 106 can have a carbon dioxide content ranging from a low of about 0 mol % to about 40 mol %. The raw syngas in line 106 can be have a methane content ranging from a low of about 0 mol %, about 5 mol %, or about 10 mol % to a high of about 20 mol %, about 30 mol %, or about 40 mol %. For example, the raw syngas in line 106 can have a methane content ranging from a low of about 3.5 mol %, about 4 mol %, about 4.5 mol %, or about 5 mol % to a high of about 8 mol %, about 8.5 mol %, about 9 mol %, or about 9.5 mol % or more. The raw syngas in line 106 can have a nitrogen content ranging from a low of about 0 mol %, about 1 mol %, or about 2 mol % to a high of about 3 mol %, about 6 mol %, or about 10 mol %. When air or excess air is introduced as an oxidant via line 104 to the gasifier 205, the nitrogen content in raw syngas in line 106 can range from about 10 mol % to about 50 mol % or more. When an essentially nitrogen-free oxidant is introduced via line 104 to the gasifier 205, the nitrogen content in the raw syngas in line 106 can range from about 0 mol % to about 4 mol %. The raw syngas in line 106 can have an argon content ranging from a low of about 0 mol %, about 0.5 mo %, or about 1 mol % to a high of about 1.5 mol %, about 2 mol %, or about 3 mol %. An essentially nitrogen-free oxidant introduced via line 104 can provide raw syngas via line 106 having a combined nitrogen and argon concentration ranging from a low of about 0.001 mol % to a high of about 3 mol %.
The syngas cooler 305 can include one or more heat exchangers or heat exchanging zones. As illustrated, the syngas cooler 305 can include three heat exchangers 310, 320, and 330 arranged in series. Any one or all of the heat exchangers 310, 320, 330 can be shell-and-tube type heat exchangers. The raw syngas via line 106 can be cooled in the first heat exchanger (“first zone”) 310 to provide a cooled raw syngas via line 315 having a temperature of from about 260° C. to about 820° C. The cooled raw syngas exiting the first heat exchanger 310 via line 315 can be further cooled in the second heat exchanger (“second zone”) 320 to provide a cooled raw syngas via line 325 having a temperature of from about 260° C. to about 704° C. The cooled raw syngas exiting the second heat exchanger 320 via line 325 can be further cooled in the third heat exchanger (“third zone”) 330 to provide a cooled raw syngas via line 116 having a temperature of from about 260° C. to about 430° C. Although not shown, the syngas cooler 305 can be or include a single boiler.
The heat transfer medium (e.g., boiler feed water) via line 108 can be heated within the third heat exchanger (“economizer”) 330 to provide the cooled syngas via line 116 and a condensate via line 338. The condensate 338 can be introduced (“flashed”) to one or more steam drums or separators 340 to separate the gas phase (“steam”) from the liquid phase (“condensate”). The condensate via line 346 from the separator 340 can be introduced to the first heat exchanger (“boiler”) 310 and indirectly heated against the syngas introduced via line 106 to provide at least partially vaporized steam which can be introduced to the separator 340 via line 344. Steam via line 342 can be introduced to the second heat exchanger (“superheater”) 320 and heated against the incoming syngas via line 315 to provide the superheated steam or superheated high pressure steam via line 114.
The superheated steam or superheated high pressure steam via line 114 can have a temperature of about 400° C. or more, about 450° C. or more, about 500° C. or more, about 550° C. or more, about 600° C. or more, about 650° C. or more, about 700° C. or more, or about 750° C. or more. The superheated steam or superheated high pressure steam via line 114 can have a pressure of about 4,000 kPa or more, about 8,000 kPa or more, about 11,000 kPa or more, about 15,000 kPa or more, about 17,000 kPa or more, about 19,000 kPa or more, about 21,000 kPa or more, or about 22,100 kPa or more. The steam via line 114 can be used to drive one or more steam turbines 360 that, in turn, drive one or more electric generators 380. The steam turbine 360 can provide a condensate via line 390 that can be introduced back into the syngas cooler 305. For example, the condensate via line 390 can be introduced to the economizer 330.
The cooled raw syngas via line 116 can exit the syngas cooler 305 and be introduced to the syngas purification system 400. The treated syngas via line 118 and the heat transfer medium, (e.g., boiler feed water) via line 120 can be introduced to the methanator 500 to provide the SNG via line 122 and the heated heat transfer medium or steam via line 124. At least a portion of the steam in line 124 can be introduced back into the syngas cooler 305 via line 112. For example, the steam via line 112 can be introduced to the boiler 310, the superheater 320, the economizer 330, and/or the separator 340.
The oxidant via line 104, the feedstock via line 102, and the steam via line 127 can be introduced to the gasifier 205 to provide the raw syngas via line 106. The oxidant via line 104 can be pure oxygen, nearly pure oxygen, essentially oxygen, or oxygen-enriched air. Further, the oxidant via line 104 can be a nitrogen-lean, oxygen-rich feed, thereby minimizing the nitrogen concentration in the syngas provided via line 106 to the syngas cooler 305. The use of a pure or nearly pure oxygen feed allows the gasifier 205 to produce a syngas that can be essentially nitrogen-free, e.g., containing less than 0.5 mol % nitrogen/argon. The air separation unit 222 can provide from about 10%, about 30%, about 50%, about 70%, about 90%, or about 100% of the total oxidant introduced to the gasifier 205.
The air separation unit 222 can supply the oxidant via line 104 at a pressure ranging from about 2,000 kPa to 10,000 kPa or more. For example, the air separation unit 222 can supply oxidant of about 99.5% purity at a pressure of about 1,000 kPa greater than the pressure within the gasifier 205. The flow of oxidant can be controlled to limit the amount of carbon combustion that takes place within the gasifier 205 and to maintain the temperature within the gasifier 205. The oxidant can enter the gasifier 205 at a ratio (weight of oxygen to weight of feedstock on a dry and mineral matter free basis) ranging from about 0.1:1 to about 1.2:1. For example, the ratio of oxidant to the feedstock can be about 0.66:1 to about 0.75:1.
As discussed and described above with reference to
The cooled syngas can be introduced via line 116 to the particulate control device 410. The particulate control device 410 can include one or more separation devices, such as high temperature particulate filters. The particulate control device 410 can provide a filtered syngas with a particulate concentration below the detectable limit of about 0.1 ppmw. An illustrative particulate control device can include, but is not limited to, sintered metal filters (for example, iron aluminide filter material), metal filter candles, and/or ceramic filter candles. The particulate control device 410 can eliminate the need for a water scrubber due to the efficacy of removing particulates from the syngas. The elimination of a water scrubber can allow for the elimination of dirty water or grey water systems, which can reduce the process water consumption and associated waste water discharge.
The solid particulates can be purged from the system via line 412, or they can be recycled to the gasifier 205 (not shown). The filtered syngas via line 414 leaving the particulate control device 410 can be divided, and at least a portion of the syngas can be introduced to the saturator 420 via line 415, and another portion can introduced to the carbonyl sulfide (“COS”) hydrolysis device 480 via line 416. Heat can be recovered from the cooled syngas in line 416. For example, the cooled syngas in line 416 can be exposed to a heat exchanger or a series of heat exchangers (not shown). The portions of cooled syngas introduced to the saturator 420 via line 415 and to the COS hydrolysis device 480 via line 416 can be based, at least in part, on the desired ratio of hydrogen to carbon monoxide and/or carbon dioxide at the inlet of the methanation device 500. Although not shown, in one or more embodiments the filtered syngas via line 414 can be introduced serially to both the saturator 420 and the COS hydrolysis device 480.
The saturator 420 can be used to increase the moisture content of the filtered syngas in line 415 before the syngas is introduced to the gas shift device 430 via line 424. Process condensate generated by other devices in the SNG system 300 can be introduced via line 442 to the saturator 420. Illustrative condensates can include process condensate from the ammonia scrubber 490, process condensate from the syngas cooler 305, process condensate from the gas cooler 440, process condensate from methanator 500, or a combination thereof. Make-up water, such as demineralized water, can also be supplied via line 418 to the saturator 420 to maintain a proper water balance.
The saturator 420 can have a heat requirement, and about 70 percent to 75 percent of the heat requirement can be sensible heat provided by the cooled syngas in line 415, as well as medium to low grade heat available from other portions of the SNG system 300. About 25 percent to 30 percent of the heat requirement can be supplied by indirect steam reboiling. The indirect steam reboiling can use medium pressure steam. For example, the steam can have a pressure ranging from about 4,000 kPa to about 4,580 kPa. In one or more embodiments, the saturator 420 does not have a live steam addition. The absence of live steam addition to the saturator 420 can minimize the overall required water make-up and reduce saturator blow down via line 422.
Saturated syngas can be introduced via line 424 to the gas shift device 430. The gas shift device 430 can include a system of parallel single-stage or two-stage gas shift catalytic beds. The saturated syngas in line 424 can be preheated before entering the gas shift device 430. For example, the temperature of the saturated syngas in line 424 can range from about 200° C. to about 295° C., from about 190° C. to about 290° C., or from about 290° C. to about 300° C. or more. The saturated syngas can enter the gas shift device 430 with a steam-to-dry gas molar ratio ranging from about 0.8:1 to about 1.2:1 or higher. The saturated syngas in line 424 can include carbonyl sulfide, which can be at least partially hydrolyzed to hydrogen sulfide by the gas shift device 430.
The gas shift device 430 can be used to convert the saturated syngas to provide a shifted syngas via line 432. The gas shift device 430 can include one or more shift converters to adjust the hydrogen to carbon monoxide ratio of the syngas by converting carbon monoxide to carbon dioxide. The gas shift device 430 can include, but is not limited to, single stage adiabatic fixed bed reactors, multiple-stage adiabatic fixed bed reactors with interstage cooling, steam generation or cold quench reactors, tubular fixed bed reactors with steam generation or cooling, fluidized bed reactors, or any combination thereof.
A cobalt-molybdenum catalyst can be incorporated into the gas shift device 430. The cobalt-molybdenum catalyst can operate at a temperature of about 290° C. in the presence of hydrogen sulfide, such as about 100 ppmw hydrogen sulfide. If the cobalt-molybdenum catalyst is used to perform a sour shift, subsequent downstream removal of sulfur can be accomplished using any sulfur removal method and/or technique.
The gas shift device 430 can include two reactors arranged in series. A first reactor can be operated at high temperature of from about 260° C. to about 400° C. to convert a majority of the carbon monoxide present in the saturated syngas in line 424 to carbon dioxide at a relatively high reaction rate using a catalyst which can be, but is not limited to, copper-zinc-aluminum, iron oxide, zinc ferrite, magnetite, chromium oxides, derivatives thereof, or any combination thereof. A second reactor can be operated at a relatively low temperature of about 150° C. to about 200° C. to maximize the conversion of carbon monoxide to carbon dioxide and hydrogen. The second reactor can use a catalyst that includes, but is not limited to, copper, zinc, copper promoted chromium, derivatives thereof, or any combination thereof. The gas shift device 430 can recover heat from the shifted syngas. The recovered heat can be used to preheat the saturated syngas in line 424 before it enters the gas shift device 430. The recovered heat can also pre-heat feed gas to the shift reactors, pre-heat recycled condensate, preheat make-up water introduced to the SNG system 300, produce medium pressure steam, provide at least a portion of the heat duty for the syngas saturator 420, provide at least a portion of the heat duty for the acid gas removal device 460, and/or provide at least a portion of the heat to dry the carbonaceous feedstock and/or other systems within the SNG system 300.
After the saturated syngas is shifted forming a shifted syngas, the shifted syngas can be introduced via line 432 to the gas cooler 440. The gas cooler 440 can be an indirect heat exchanger. The gas cooler 440 can recover at least a portion of heat from the shifted syngas in line 432 and produce cooled shift converted syngas and a condensate. The cooled shift converted syngas can leave the gas cooler 440 via line 449. The condensate from the gas cooler 440 can be introduced via line 442 to the saturator 420 after passing through the flash gas separator 446.
The COS hydrolysis device 480 can convert carbonyl sulfide in the cooled syngas in line 416 to hydrogen sulfide. The COS hydrolysis device 480 can include a number of parallel carbonyl sulfide reactors. For example, the COS hydrolysis device 480 can have about two or more, three or more, four or more, five or more, or ten or more parallel carbonyl sulfide reactors. The filtered syngas in line 416 can enter the COS hydrolysis device 480, pass over the parallel carbonyl sulfide reactors, and hydrogen sulfide syngas can exit the COS hydrolysis device 480 via line 482. The hydrogen sulfide syngas in line 482 can have a carbonyl sulfide concentration of about 1 ppmv or less. The heat in the hydrogen sulfide syngas in line 482 can be recovered and used to preheat boiler feedwater, to dry the carbonaceous feedstock, as a heat source in other portions of the SNG system 300, or any combination thereof. A heat exchanger (not shown) can be used to recover the heat from the hydrogen sulfide syngas in line 482. Illustrative heat exchangers can include a shell and tube heat exchanger, a concentric flow heat exchanger, or any other heat exchanging device. After the heat is recovered from the hydrogen sulfide syngas in line 482, the hydrogen sulfide syngas in line 482 can be introduced to the ammonia scrubbing device 490.
The ammonia scrubbing device 490 can use water introduced via line 488 to remove ammonia from the hydrogen sulfide syngas in line 482. The water via line 488 can be recycle water from other parts of the SNG generation system 300 or can be make-up water supplied from an external source. The water supplied to the ammonia scrubber 490 via line 488 can also include water produced during the drying of the carbonaceous feedstock. The water via line 488 can be provided at a temperature ranging from about 50° C. to about 64° C. For example, the water can have a temperature of about 54° C. The water can remove at least a portion of any fluorides and/or chlorides in the syngas. Accordingly, waste water having ammonia, fluorides, and/or chlorides can be discharged from the ammonia scrubber 490 and introduced via line 492 to the gas cooler 440 where it can be combined with the condensate to provide a combined condensate. The combined condensate can be provided via line 444 to the flash gas separator 446. The combined condensate in line 444 can be pre-heated before entering the flash gas separator 446. The combined condensate in line 444 can have a pressure ranging from about 2,548 kPa to about 5,922 kPa. The combined condensate in line 444 can be flashed in the flash gas separator 446 to provide a flashed gas and a condensate. The flashed gas can include ammonia. The flashed gas can be recycled back to the gasifier 205 via line 448 and converted therein to nitrogen and hydrogen. The condensate can be recycled to the saturator 420 via line 442.
The ammonia scrubbing device 490 can also output a scrubbed syngas via line 494. A portion of the scrubbed syngas in line 494 can be recycled back to the gasifier 205 via line 496. Another portion of the scrubbed syngas in line 494 can be combined with the cooled shifted syngas in line 449 to provide a mixed syngas via line 497. The mixed syngas in line 497 can be pre-heated and introduced to the mercury removal device 450. The mixed syngas in line 497 can have a temperature ranging from about 60° C. to about 71° C., about 20° C. to 80° C., or about 60° C. to about 90° C.
The mercury removal device 450 can include, but is not limited to, activated carbon beds that can adsorb a substantial amount, if not all, of the mercury present in the processed syngas. The processed syngas recovered from the mercury removal device 450 via line 452 can be introduced to the acid gas removal device 460.
The acid gas removal device 460 can remove carbon dioxide from the processed syngas. The acid gas removal device 460 can include, but is not limited to, a physical solvent-based two stage acid gas removal system. The physical solvents can include, but are not limited to, Selexol™ (dimethyl ethers of polyethylene glycol) Rectisol® (cold methanol), or combinations thereof. One or more amine solvents such as methyl-diethanolamine (MDEA) can be used to remove at least a portion of any acid gas, e.g., carbon dioxide, from the processed syngas to provide the treated syngas via line 118. The treated syngas can be introduced via line 118 to the methanator 500. The treated syngas in line 118 can have a carbon dioxide content from a low of about 0 mol % to a high of about 40 mol %. The treated syngas in line 118 can have a total sulfur content of about 0.1 ppmv or less.
The carbon dioxide can be recovered as a low-pressure carbon dioxide rich stream via line 464. The carbon dioxide content in line 464 can be about 95 mol % carbon dioxide or more. The low-pressure carbon dioxide stream can have a hydrogen sulfide content of less than 20 ppmv. The low-pressure carbon dioxide stream can be introduced via line 464 to the carbon handling compression unit 470. The low-pressure carbon dioxide stream in line 464 can be exposed to one or more compression trains, and the carbon dioxide can leave the carbon handling compression unit 470 via line 472 as a dense-phase fluid at a pressure ranging from about 13,890 kPa to about 22,165 kPa. The carbon dioxide via line 472 can be used for enhanced oil recovery, or it can be sequestered. In one or more embodiments, the carbon dioxide stream in line 472 can conform to carbon dioxide pipeline specifications. The carbon handling compression unit 470 can be a four stage compressor or any other compressor. An illustrative compressor can include a four stage intercooled centrifugal compressor with electric drives.
The acid gas removal device 460 can also remove sulfur from the processed gas. The sulfur can be concentrated as a hydrogen sulfide rich stream. The hydrogen sulfide rich stream can be introduced via line 462 to the sulfur recovery unit 466 for sulfur recovery. As an example, the sulfur recovery unit 466 can be an oxygen fired Claus unit. When the hydrogen sulfide stream in line 462 is combusted in the sulfur recovery unit 466, a tail gas can be produced. The tail gas can be compressed and recycled via line 468 upstream of the acid removal device 460.
A portion of the treated gas in line 118 can be removed via line 499 and used as a fuel gas. The fuel gas can be combusted to provide power for the SNG system 300. The remaining treated syngas in line 118 can be introduced to the methanator 500. The treated syngas can have a nitrogen content of 0 mol % to about 50 mol % and an argon content ranging from about 0 mol % to about 5 mol %.
The heat transfer medium via line 120 can be introduced to the methanator 500, as discussed and described above with reference to
The methanation condensate in line 509 can also have a carbon monoxide content ranging from a low of 0 mol %, about 0.1 mol %, or about 0.5 mol % to a high of about 1 mol %, about 2 mol %, or about 5 mol %. The methanation condensate in line 509 can have a carbon dioxide content ranging from a low of 0 mol %, about 0.1 mol %, or about 0.5 mol % to a high of about 1 mol %, about 2 mol %, or about 5 mol %. The methanation condensate in line 509 can have a hydrogen content ranging from a low of 0 mol %, about 0.01 mol %, or about 0.1 mol % to a high of about 0.5 mol %, about 1 mol %, or about 2 mol %. The methanation condensate in line 509 can have a methane content ranging from a low of 0 mol %, about 0.01 mol %, or about 0.1 mol % to a high of about 0.5 mol %, about 1 mol %, or about 2 mol %. The methanation condensate in line 509 can also have a nitrogen content ranging from a low of 0 mol %, about 0.001 mol %, or about 0.01 mol % to a high of about 0.05 mol %, about 0.1 mol %, or about 0.5 mol % and an argon content ranging from a low of 0 mol %, about 0.001 mol %, or about 0.01 mol % to a high of about 0.05 mol %, about 0.1 mol %, or about 0.5 mol %. The methanation condensate in line 509 can further have a hydrogen sulfide content ranging from a low of 0 mol %, about 0.001 mol %, or about 0.01 mol % to a high of about 0.05 mol %, about 0.1 mol %, or about 0.2 mol %, a COS content ranging from a low of 0 mol %, about 0.001 mol %, or about 0.01 mol % to a high of about 0.05 mol %, about 0.1 mol %, or about 0.2 mol %, and an ethane content ranging from a low of 0 mol %, about 0.001 mol %, or about 0.01 mol % to a high of about 0.05 mol %, about 0.1 mol %, or about 0.5 mol %.
In one or more embodiments, the methanation condensate in line 509 can be recycled back to the gas cooler 440, saturator 420, or other portions of the SNG system 300. The methanator 500 can also provide high pressure steam via line 124 to the syngas cooler 305. The syngas cooler 305 can superheat the high pressure steam to provide superheated high pressure steam via line 110, as discussed and described above. The superheated high pressure steam can be introduced to one or more steam turbine generators to produce electricity for the SNG system 300.
The methanation condensate in line 509 can be at a temperature ranging from a low of about 0° C. to a high of about 200° C. For example, the methanation condensate in line 509 can be at a temperature of about 1° C. to about 150° C., about 5° C. to about 100° C., about 15° C. to about 75° C., about 20° C. to about 60° C., or about 30° C. to about 50° C. when introduced to the saturator 420.
The methanation condensate in line 509 can be at a pressure ranging from a low of about 500 kPa to a high of about 15,000 kPa. For example, the methanation condensate in line 509 can be at a pressure of about 1,000 kPa to about 12,000 kPa, about 2.000 kPa to about 10,000 kPa, or about 4,000 kPa to about 8,000 kPa when introduced to the saturator 420.
The temperature of the saturated syngas in line 424 exiting the saturator 420 can range from about 200° C. to about 295° C., from about 190° C. to about 290° C., or from about 290° C. to about 300° C. or more. The saturated syngas in line 424 can have a steam-to-dry gas molar ratio ranging from about 0.8:1 to about 1.2:1 or higher. The saturated syngas in line 424 can include carbonyl sulfide, which can be at least partially hydrolyzed to hydrogen sulfide by the gas shift device 430.
The methanator 500 can include one, two, three, four, five, six, or more methanator reactors. For example, the methanator 500 can include three reactors arranged in parallel and a fourth reactor can be in series with three parallel reactors (not shown). The three parallel reactors can provide a portion of the total SNG introduced to the fourth reactor. The three reactors can also have a recycle stream, which can recycle a portion of the SNG back to the inlet of each of the three reactors. SNG can be provided from the fourth reactor via line 122 to the SNG drying and compression device 502.
The methanator 500 can also include various heat exchangers and mixing equipment to ensure that a proper temperature is maintained in each of the methanator reactors. The reactors can include a methanation catalyst such as nickel, ruthenium, another common methanation catalyst material, or combinations thereof. The methanator 500 can be maintained at a temperature from about 150° C. to about 1,000° C. The methanator 500 can provide SNG via line 122 to the SNG drying and compression device 502.
The SNG drying and compression device 502 can dehydrate the SNG in line 122 to about 3.5 kilograms of water per million standard cubic meters (Mscm) or lower. The dehydration can be performed in a conventional tri-ethylene glycol unit. After dehydration the SNG in line 122 can be compressed, cooled, and introduced via line 504 to an end user or a pipeline. The SNG in line 504 can have a pressure ranging from about 1,379 kPa to about 12,411 kPa and a temperature of about 20° C. to about 75° C. In one or more embodiments, the SNG in line 122 can be compressed, and after compression the SNG in line 122 can be dehydrated.
In order to provide a better understanding of the foregoing discussion, the following non-limiting prophetic examples are offered. Although the prophetic examples may be directed to specific embodiments, they are not to be viewed as limiting the invention in any specific respect. All parts, proportions, and percentages are by weight unless otherwise indicated.
Embodiments of the present invention can be further described with the following simulated processes. One or more of the above described systems can theoretically be used with Wyoming Powder River Basin (“WPRB”) coal. The WPRB coal was given a composition as shown in Table 1 below.
The simulated composition of the raw syngas via line 106 from the gasifier 205 was calculated to have a composition as shown in Table 2.
Based on simulated process conditions, when the syngas provided from the gasification of the WPRB coal is processed in accordance to one or more embodiments discussed and described above, the treated syngas via line 118 introduced to the methanator 500 can have the composition shown in Table 3.
The calculated feed requirements and some of the byproduct production for generating SNG from WPRB coal using a process according to one or more of the embodiments discussed and described above can be as shown in Table 4. The feed requirements and byproduct (carbon dioxide) generation were calculated using the assumption of a production of about 4.3 million standard cubic meters per day (Mscmd) of SNG with a heating value of about 36 MJ/scm.
AR is the calculated coal feed rate in tonnes per day as received, which had moisture content for WPRB coal of 27.21 wt %. AF is the calculated coal feed rate as the coal is introduced to the gasifier 205, which had moisture content for PRB coal of 17.89 wt %. The oxygen per tonne of coal was calculated on moisture and ash free basis. The calculated make-up water for the SNG system, which uses syngas derived from WPRB coal, is about 1.14 cubic meters per minute (CMPM). Fuel gas is treated syngas, in excess of the treated syngas needed to meet the target SNG production of 4.3 Mscmd, which can be used as fuel for the SNG system 300. In addition to the byproduct carbon dioxide listed in Table 4, other byproducts produced using WPRB coal were calculated to include sulfur at a rate of about 33 tonne/day and ash at a rate of about 814 tonne/day.
One or more of the above described systems theoretically can be used with North Dakota Lignite Coal. The North Dakota Lignite Coal was given a composition as shown below in Table 5 below.
The simulated composition of the raw syngas via line 106 from the gasifier 205 was calculated to have a composition as shown in Table 6.
Based on simulated process conditions, when the raw syngas via line 106 from the gasification of the North Dakota Lignite is processed in accordance to one or more embodiments discussed and described above, the treated syngas via line 118 introduced the methanator 500 can have the composition shown in Table 7.
The calculated feed requirements and some of the byproducts produced during the production of the SNG from North Dakota Lignite Coal can be as shown in Table 8. The values in Table 8 were based on the use of three gasifiers 205. The feed requirements and byproduct generation were calculated assuming a production of about 4.3 Mscmd of SNG with a heating value of about 36 MJ/scm.
AR is the calculated coal feed rate in tonnes per day as received, which had moisture content for the North Dakota lignite of 29.82 wt %. AF is the calculated coal feed rate as the coal is introduced to the gasifier 205, which had a moisture content for the North Dakota Lignite of 17.89 wt %. The oxygen per tonne of coal is calculated on a moisture and ash free basis. The calculated make-up water for the SNG system, which uses syngas derived from the North Dakota Lignite, is about 0.267 CMPM. In addition to the byproduct (carbon dioxide) listed in Table 8, other byproducts produced using North Dakota lignite were calculated to include sulfur at a rate of about 79 tonne/day and ash at a rate of about 1,521 tonne/day.
Simulated Auxiliary Power Requirements
The following section discusses the SNG facility's auxiliary power load requirements, power generation concepts, and options to meet the balance of power demand. The outside battery limit (“OSBL”) steam and power systems include the steam generation system and the electric power generation system. The inside battery limit (“ISBL”) process units produce substantial amounts of steam from waste heat recovery, which can be used to make electric power in one or more steam turbine generators (“STGs”). The specific configuration can depend on decisions regarding the electric power balance. For example, if sufficient electric power is reliably available at a competitive price from the local utility grid, the balance of the power demand can be purchased. However, if sufficient electric power is not reliably available, the SNG facility can be operated, electrically, in “island mode” and can generate all electrical power on-site. The island mode is possible with the SNG system because the SNG system is more efficient than other SNG systems. The basic design options considered include:
Tables 9 and 10 summarize the basic performance parameters for the steam and power generation systems for the WPRB and North Dakota lignite cases.
WPRB Case Description
For the simulated WPRB coal case, there is a surplus of syngas (fuel gas) produced based on a target SNG production rate of 4.3 Mscmd. In the Base Case option, this surplus syngas is used as boiler fuel to produce more electric power via the STGs, and the balance of the electric power can be purchased off-site. In Options 1 & 2, the balance of power is generated on-site. With a fixed amount of syngas produced from the gasifiers, using syngas as fuel can reduce the net production of SNG in Option 1, as indicated. In Option 2, a small surplus of syngas is available after meeting the power generation requirements (i.e., Table 9 shows slightly more power generation than load for Option 2). This is due to the higher efficiency of Option 2 vs. Option 1. The excess syngas can be used to increase SNG production marginally, or the cogen cycle can be de-tuned to keep the syngas requirement in balance. For example, the load on one or more GTGs can be reduced and duct firing for one or more HRSGs can be increased.
North Dakota Lignite Case Description
For the North Dakota lignite case, in the Base Case option, the balance of electric power is purchased from off-site. In Options 1 & 2, the balance of power is generated on-site. Since no additional fuel gas is available, the extra fuel requirement for Options 1 & 2 is shown as an equivalent reduction in SNG production.
The treated syngas via line 118 can be introduced to the methanation system 500 to produce the SNG via line 122. The syngas in line 118 can have a temperature ranging from a low of about 0° C., about 5° C., about 10° C., about 15° C., about 20° C., or about 25° C. to a high of about 40° C., about 50° C., about 70° C., about 90° C., or about 100° C. For example, the syngas in line 118 can have a temperature of about 12° C. to about 43° C., about 18° C. to about 37° C., or about 22° C. to about 33′C.
The pressure of the syngas within the methanation system 500 can range from about 500 kilopascals (“kPa”) to about 10,000 kPa. For example, the pressure of the syngas can range from a low of about 700 kPa, about 1,000 kPa, about 1,700 kPa, or about 2,500 kPa to a high of about 3,500 kPa, about 4,500 kPa, about 6,500 kPa, or about 8,500 kPa. In another example, the pressure of the syngas can range from about 2,600 kPa to about 3,000 kPa, about 2,650 kPa to about 2,900 kPa, or about 2,700 kPa to about 2,850 kPa.
The syngas via line 118 can be introduced to the guard bed 505 to produce a purified or sulfur-lean syngas via line 507. For example, the guard bed 505 can remove sulfur and sulfur containing compounds, e.g., hydrogen sulfide, from the syngas via line 118. The guard bed 505 can be, but is not limited to, a particulate bed, for example, a zinc oxide (ZnO) bed.
The purified syngas in line 507 can also include, but is not limited to, methane, carbon monoxide, carbon dioxide, hydrogen, nitrogen, argon, sulfur, sulfur containing compounds, or any combination thereof. The purified syngas in line 507 can have less than about 50 ppm, less than about 25 ppm, less than about 10 ppm, less than about 7 ppm, less than about 5 ppm, less than about 3 ppm, less than about 1 ppm, or less than about 0.5 ppm of sulfur and/or sulfur containing compounds, and can otherwise have similar concentrations to the syngas in line 118.
The purified syngas via line 507 can be heated in the first heat exchanger or preheater 510 to produce a first heated syngas via line 511. The first heated syngas via line 511 can be at a temperature ranging from a low of about 50° C., about 100° C., or about 150° C. to a high of about 200° C., about 250° C., or about 375° C. For example, the first heated syngas via line 511 can be at a temperature of about 75° C. to about 150° C., about 100° C. to about 200° C., about 125° C. to about 175° C., about 140° C. to about 240° C., or about 90° C. to about 150° C.
The first heated syngas via line 511 can be introduced to and further heated within the second heat exchanger 515 to produce a second heated syngas via line 516. The second heated syngas via line 516 can be at a temperature ranging from a low of about 175° C., about 200° C., about 210° C., or about 220° C. to a high of about 240° C., about 250° C., about 275° C., or about 300° C. For example, the second heated syngas via line 516 can be at a temperature ranging from about 195° C. to about 265° C., about 205° C. to about 255° C., or about 215° C. to about 245° C.
The second heated syngas in line 516 can be divided via one or more manifolds or splitters 598 into two or more portions. For example, as shown in
The first syngas via line 517, second syngas via line 518, and third syngas via line 519 can have a methane concentration ranging from a low of about 1 mol %, about 3 mol %, about 5 mol %, or about 7 mol % to a high of about 11 mol %, about 13 mol %, about 15 mol %, about 20 mol %, or about 25 mol %. For example, the first syngas via line 517, second syngas via line 518, and third syngas via line 519 can have a methane concentration ranging from about 1 mol % to about 20 mol %, about 5 mol % to about 15 mol %, about 7 mol % to about 13 mol %, or about 9 mol % to about 11 mol %.
The first syngas via line 517 can be introduced to the one or more first methanators 520 to produce a first effluent via line 521. The first effluent in line 521 can include, but is not limited to, methane, water, hydrogen, carbon monoxide, carbon dioxide, nitrogen, argon, or any combination thereof. The first effluent in line 521 can have a methane concentration ranging from a low of about 30 mol %, about 40 mol %, or about 50 mol % to a high of about 60 mol %, about 70 mol %, or about 80 mol %, on a wet basis. For example, the first effluent in line 521 can have a methane concentration of about 35 mol % to about 75 mol %, about 45 mol % to about 65 mol %, or about 55 mol % to about 60 mol %, on a wet basis. The first effluent in line 521 can have a water concentration ranging from a low of about 10 mol %, about 20 mol %, or about 30 mol % to a high of about 40 mol %, about 50 mol %, or about 60 mol %, on a wet basis. For example, the first effluent in line 521 can have a water concentration of about 15 mol % to about 55 mol % or about 25 mol % to about 45 mol %, on a wet basis. The first effluent in line 521 can have a hydrogen concentration ranging from a low of about 0.1 mol %, about 0.5 mol %, about 1 mol %, or about 2 mol % to a high of about 4 mol %, about 6 mol %, about 8 mol %, or about 10 mol %, on a wet basis. For example, the first effluent in line 521 can have a hydrogen concentration of about 0.3 mol % to about 9 mol %, about 0.75 mol % to about 7 mol %, or about 1.5 mol % to about 5 mol %, on a wet basis. The first effluent in line 521 can have a carbon dioxide concentration of about 5 mol % or less, about 4 mol % or less, about 3 mol % or less, about 2 mol % or less, or about 1 mol % or less, on a wet basis. For example, the first effluent in line 521 can have a carbon dioxide concentration of about 0.1 mol % to about 4.5 mol %, about 0.2 mol % to about 3.5 mol %, about 0.3 mol % to about 2.5 mol %, or about 0.4 mol % to about 1.5 mol %, on a wet basis. The first effluent in line 521 can have a carbon monoxide concentration of about 5 mol % or less, about 3 mol % or less, about 2 mol % or less, about 1 mol % or less, about 0.5 mol % or less, about 0.1 mol % or less, about 0.05 mol % or less, or about 0.01 mol % or less, on a wet basis. For example, the first effluent in line 521 can have a carbon monoxide concentration of about 0.001 mol % to about 0.7 mol %, about 0.002 mol % to about 0.3 mol %, or about 0.003 mol % to about 0.2 mol %, on a wet basis. The first effluent in line 521 can have a nitrogen concentration of about 5 mol % or less, about 4 mol % or less, about 3 mol % or less, about 2 mol % or less, about 1 mol % or less, or about 0.5 mol % or less, on a wet basis. For example, the first effluent in line 521 can have a nitrogen concentration of about 0.01 mol % to about 3.5 mol %, about 0.05 mol % to about 2.5 mol %, about 0.07 mol % to about 1.5 mol %, or about 0.1 mol % to about 0.5 mol %, on a wet basis. The first effluent in line 521 can have an argon concentration of about 5 mol % or less, about 4 mol % or less, about 3 mol % or less, about 2 mol % or less, about 1 mol % or less, or about 0.5 mol % or less, on a wet basis. For example, the first effluent in line 521 can have an argon concentration of about 0.01 mol % to about 3.5 mol %, about 0.03 mol % to about 2.5 mol %, about 0.05 mol % to about 1.5 mol %, or about 0.07 mol % to about 0.3 mol %, on a wet basis.
The first effluent in line 521 can be at a temperature ranging from a low of about 300° C., about 350° C., about 375° C., or about 400° C. to a high of about 450° C., about 500° C., about 600° C., about 700° C., about 800° C., or about 850° C. For example, the first effluent in line 521 can be at a temperature ranging from about 375° C. to about 440° C., about 400° C. to about 600° C., about 450° C. to about 700° C., about 500° C. to about 800° C., or about 390° C. to about 430° C.
The first effluent via line 521 can be introduced to the third heat exchanger or heat recovery unit 525 to produce a first cooled effluent via line 527. The first cooled effluent in line 527 can be at a temperature ranging from a low of about 190° C., about 200° C., about 210° C., or about 220° C. to a high of about 250° C., about 275° C., about 325° C., or about 375° C. For example, the first cooled effluent in line 527 can be at a temperature ranging from about 205° C. to about 265° C., about 220° C. to about 300° C., about 215° C. to about 245° C., about 260° C. to about 340° C., or about 275° C. to about 360° C.
The first cooled effluent via line 527 can be combined with the second syngas in line 518 to produce a first mixed effluent via line 528. The first mixed effluent in line 528 can have a methane concentration ranging from a low of about 15 mol %, about 25 mol %, about 35 mol %, or about 45 mol % to a high of about 55 mol %, about 60 mol %, about 65 mol %, or about 70 mol %, on a wet basis. For example, the first mixed effluent in line 528 can have a methane concentration of about 10 mol % to about 67 mol %, about 20 mol % to about 63 mol %, or about 30 mol % to about 57 mol %, on a wet basis. The first mixed effluent in line 528 can have a water concentration ranging from a low of about 10 mol %, about 20 mol %, or about 30 mol % to a high of about 40 mol %, about 50 mol %, or about 60 mol %, on a wet basis. For example, the first mixed effluent in line 528 can have a water concentration of about 15 mol % to about 55 mol % or about 25 mol % to about 45 mol %, on a wet basis. The first mixed effluent in line 528 can have a hydrogen concentration ranging from a low of about 4 mol %, about 6 mol %, about 8 mol %, about 10 mol %, or about 12 mol % to a high of about 13 mol %, about 15 mol %, about 17 mol %, about 19 mol %, or about 21 mol %, on a wet basis. For example, the first mixed effluent in line 528 can have a hydrogen concentration of about 5 mol % to about 20 mol %, about 7 mol % to about 18 mol %, about 9 mol % to about 16 mol %, or about 11 mol % to about 14 mol %, on a wet basis. The first mixed effluent in line 528 can have a carbon monoxide concentration ranging from a low of about 0.5 mol %, about 1 mol %, about 2 mol %, or about 3 mol % to a high of about 4 mol %, about 6 mol %, about 8 mol %, or about 10 mol %, on a wet basis. For example, the first mixed effluent in line 528 can have a carbon monoxide concentration of about 0.75 mol % to about 9 mol %, about 1.5 mol % to about 7 mol %, or about 2.5 mol % to about 5 mol %, on a wet basis. The first mixed effluent in line 528 can have a carbon dioxide concentration of about 5 mol % or less, about 4 mol % or less, about 3 mol % or less, about 2 mol % or less, or about 1 mol % or less, on a wet basis. For example, the first mixed effluent in line 528 can have a carbon dioxide concentration of about 0.1 mol % to about 4.5 mol %, about 0.2 mol % to about 3.5 mol %, about 0.3 mol % to about 2.5 mol %, or about 0.4 mol % to about 1.5 mol %, on a wet basis. The first mixed effluent in line 528 can have a nitrogen concentration of about 5 mol % or less, about 4 mol % or less, about 3 mol % or less, about 2 mol % or less, about 1 mol % or less, or about 0.5 mol % or less, on a wet basis. For example, the first mixed effluent in line 528 can have a nitrogen concentration of about 0.01 mol % to about 3.5 mol %, about 0.05 mol % to about 2.5 mol %, about 0.07 mol % to about 1.5 mol % or about 0.1 mol % to about 0.5 mol %, on a wet basis. The first mixed effluent via line 528 can have an argon concentration of about 5 mol % or less, about 4 mol % or less, about 3 mol % or less, about 2 mol % or less, about 1 mol % or less, or about 0.5 mol % or less, on a wet basis. For example, the first mixed effluent in line 528 can have an argon concentration of about 0.01 mol % to about 3.5 mol %, about 0.03 mol % to about 2.5 mol %, about 0.05 mol % to about 1.5 mol %, or about 0.07 mol % to about 0.3 mol %, on a wet basis.
The first mixed effluent in line 528 can be at a temperature that falls within the ranges provided for the first cooled effluent in line 527. The first mixed effluent via line 528 can be introduced to the one or more second methanators 530 to produce a second effluent via line 531. The second effluent in line 531 can include amounts of methane, water, hydrogen, carbon monoxide, carbon dioxide, nitrogen, and argon that fall within the ranges provided for the first effluent in line 521. The second effluent in line 531 can be at a temperature that falls within the ranges provided for the first effluent in line 521.
The second effluent via line 531 can be introduced to the fourth heat exchanger or heat recovery unit 535 to produce a second cooled effluent via line 537. The second cooled effluent in line 537 can be at a temperature that falls within the ranges provided for the first cooled effluent in line 527. The second cooled effluent in line 537 can be combined with the third syngas in line 519 to produce a second mixed effluent via line 538. The second mixed effluent in line 538 can include amounts of methane, water, hydrogen, carbon monoxide, carbon dioxide, nitrogen, and argon that fall within the ranges provided for the first mixed effluent in line 528. The second mixed effluent in line 538 can be at a temperature that falls within the ranges provided for the first cooled effluent in line 527.
The second mixed effluent via line 538 can be introduced to the one or more third methanators 540 to produce a third effluent via line 541. The third effluent in line 541 can include amounts of methane, water, hydrogen, carbon monoxide, carbon dioxide, nitrogen, and argon that fall within the ranges provided for the first effluent in line 521. The third effluent in line 541 can be at a temperature that falls within the ranges provided for the first effluent in line 521. The third effluent via line 541 can be introduced to the fifth heat exchanger or heat recovery unit 545 to produce a third cooled effluent via line 547. The third cooled effluent in line 547 can be at a temperature that falls within the ranges provided for the first cooled effluent in line 527.
At least a portion of the third cooled effluent via line 547 can flow back through the second heat exchanger 515 to produce a fourth cooled effluent via line 522. The second heat exchanger 515 can transfer heat from the third cooled effluent in line 547 to the first heated syngas in line 511 to produce the second heated syngas via line 516. The fourth cooled effluent in line 522 can be at a temperature ranging from a low of about 50° C., about 100° C., or about 150° C. to a high of about 300° C., about 400° C., or about 500° C.
The fourth cooled effluent via line 522 can be introduced to the sixth heat exchanger 550 to produce a fifth cooled effluent via line 551. The sixth heat exchanger 550 can transfer heat from the fourth cooled effluent via line 522 to a heat transfer medium (not shown), e.g., boiler feed water. The fifth cooled effluent in line 551 can be at a temperature ranging from a low of about 5° C., about 15° C., or about 25° C. to a high of about 50° C., about 75° C., or about 100° C. For example, the fifth cooled effluent in line 551 can be at a temperature of about 17° C. to about 53° C., about 23° C. to about 47° C., or about 27° C. to about 43° C.
The fifth cooled effluent in line 551 can be introduced to the first vapor-liquid separator 555 to produce a first separated effluent via line 557 and a first condensate via line 556. The first separated effluent via line 557 can have a methane concentration ranging from a low of about 90 mol %, about 92 mol %, or about 94 mol % to a high of about 95 mol %, about 97 mol %, or about 99 mol %, on a wet basis. For example, the first separated effluent via line 557 can have a methane concentration of about 91 mol % to about 99 mol %, about 93 mol % to about 97 mol %, or about 94.5 mol % to about 96 mol %, on a wet basis. The first separated effluent via line 557 can have a hydrogen concentration ranging from a low of about 0.001 mol %, about 1 mol %, about 2 mol %, or about 3 mol % to a high of about 4 mol %, about 5 mol %, about 6 mol %, or about 7 mol %, on a wet basis. For example, the first separated effluent via line 557 can have a hydrogen concentration of about 0.5 mol % to about 6.5 mol %, about 1.5 mol % to about 5.5 mol %, or about 2.5 mol % to about 4.5 mol %, on a wet basis. The first separated effluent via line 557 can have a carbon dioxide concentration ranging from a low of about 0.001 mol %, about 0.3 mol %, about 0.5 mol %, or about 0.7 mol % to a high of about 0.9 mol %, about 1.1 mol %, about 1.3 mol %, or about 1.5 mol %, on a wet basis. For example, the first separated effluent via line 557 can have a carbon dioxide concentration of about 0.2 mol % to about 1.4 mol %, about 0.4 mol % to about 1.2 mol %, or about 0.6 mol % to about 1 mol %, on a wet basis. The first separated effluent via line 557 can have a water concentration ranging from a low of about 0.001 mol %, about 0.2 mol %, about 0.4 mol %, or about 0.6 mol % to a high of about 0.7 mol %, about 0.9 mol %, about 1.1 mol %, or about 1.3 mol %, on a wet basis. For example, the first separated effluent via line 557 can have a water concentration of about 0.1 mol % to about 1.2 mol %, about 0.3 mol % to about 1 mol %, or about 0.5 mol % to about 0.8 mol %, on a wet basis. The first separated effluent via line 557 can have a nitrogen concentration ranging from a low of about 0.5 mol % or less, about 0.4 mol % or less, or about 0.3 mol % or less, on a wet basis. For example, the first separated effluent via line 557 can have a nitrogen concentration of about 0.1 mol % to about 0.45 mol % or about 0.2 mol % to about 0.35 mol %, on a wet basis. The first separated effluent via line 557 can have an argon concentration ranging from a low of about 0.5 mol % or less, about 0.4 mol % or less, about 0.3 mol % or less, or about 0.2 mol % or less, on a wet basis. For example, the first separated effluent via line 557 can have an argon concentration of about 0.01 mol % to about 0.45 mol %, about 0.05 mol % to about 0.35 mol %, or about 0.1 mol % to about 0.25 mol %, on a wet basis. The first separated effluent via line 557 can have a carbon monoxide concentration ranging from a low of about 10 mol % or less, about 5 mol % or less, about 1 mol % or less, or about 0.1 mol % or less, on a wet basis. For example, the first separated effluent via line 557 can have a carbon monoxide concentration of about 0.004 mol % to about 0.1 mol %, or about 0.5 mol % to about 1.0 mol %, or about 2.0 mol % to about 3.0 mol %.
The first condensate in line 556 can include, but is not limited to, water. For example, the first condensate in line 556 can have a water concentration of about 95 mol % or more, about 98 mol % or more, 99 mol % or more, or 100 mol %.
The first separated effluent via line 557 can be introduced to the fourth heat exchanger 558 to produce a heated effluent via line 559. The fourth heat exchanger 558 can transfer heat from a heat transfer medium (not shown), e.g., boiler feed water, to the first separated effluent in line 557. The heated effluent in line 559 can be at a temperature ranging from a low of about 100° C., about 150° C., about 200° C., or about 250° C. to a high of about 300° C., about 350° C., about 375° C., or about 400° C. For example, the heated effluent in line 559 can be at a temperature ranging from about 210° C. to about 310° C., about 240° C. to about 280° C., or about 250° C. to about 270° C.
The heated effluent via line 559 can be introduced to the one or more fourth methanators 560 to produce a fourth effluent via line 561. The fourth effluent in line 561 can include, but is not limited to, methane, water, nitrogen, hydrogen, argon, carbon dioxide, carbon monoxide, or any combination thereof. The fourth effluent in line 561 can have a methane concentration ranging from a low of about 85 mol %, about 90 mol %, about 93 mol % to a high of about 97 mol %, about 98 mol %, about 99 mol %, or about 99.5 mol %, on a wet basis. For example, the fourth effluent in line 561 can have a methane concentration ranging from about 94.5 mol % to about 99.5 mol % or about 95.5 mol % to about 98.5 mol %, on a wet basis. The fourth effluent in line 561 can have a water concentration ranging from a low of about 0.001 mol %, about 1 mol %, about 1.5 mol %, or about 2 mol % to a high of about 2.5 mol %, about 3.5 mol %, about 4.5 mol %, or about 5.5 mol %, on a wet basis. For example, the fourth effluent in line 561 can have a water concentration ranging from about 0.5 mol % to about 5 mol %, about 1.25 mol % to about 4 mol %, or about 1.8 mol % to about 3 mol %, on a wet basis. The fourth effluent in line 561 can have a nitrogen concentration of about 0.5 mol % or less, about 0.4 mol % or less, or about 0.3 mol % or less, on a wet basis. For example, the fourth effluent in line 561 can have a nitrogen concentration of about 0.1 mol % to about 0.45 mol % or about 0.2 mol % to about 0.35 mol %, on a wet basis. The fourth effluent in line 561 can have a hydrogen concentration of about 0.4 mol % or less, about 0.3 mol % or less, or about 0.2 mol % or less, on a wet basis. For example, the fourth effluent in line 561 can have a hydrogen concentration of about 0.01 mol % to about 035 mol %, about 0.05 mol % to about 0.25 mol %, or about 0.1 mol % to about 0.15 mol %, on a wet basis. The fourth effluent in line 561 can have an argon concentration of about 0.4 mol % or less, about 0.3 mol % or less, or about 0.2 mol % or less, on a wet basis. For example, the fourth effluent in line 561 can have an argon concentration of about 0.01 mol % to about 0.35 mol %, about 0.05 mol % to about 0.25 mol %, or about 0.1 mol % to about 0.15 mol %, on a wet basis. The fourth effluent in line 561 can have a carbon dioxide concentration of about 0.1 mol % or less, about 0.08 mol % or less, about 0.06 mol % or less, or about 0.05 mol % or less, on a wet basis. The fourth effluent in line 561 can have a carbon monoxide concentration of about 5 mol % or less, 1 mol % or less, 0.1 mol % or less, or about 0.005% or less, on a wet basis.
The fourth effluent in line 561 can be at a temperature ranging from a low of about 200° C., about 225° C., about 250° C., or about 275° C. to a high of about 300° C., about 350° C., about 400° C., about 450° C., or about 500° C. For example, the fourth effluent in line 561 can be at a temperature ranging from about 240° C. to about 340° C., about 260° C. to about 310° C., or about 275° C. to about 295° C.
The fourth effluent via line 561 can be introduced to the eighth heat exchanger 585 to produce a sixth cooled effluent via line 589. The eighth heat exchanger 585 can be or include, but is not limited to, a U-tube exchanger, a shell-and-tube exchanger, a plate and frame exchanger, a spiral wound exchanger, a fin-fan exchanger, an evaporative cooler, or any combination thereof. As discussed in more detail below, the fourth effluent in line 561 can be cooled within the eighth heat exchanger 585 by transferring heat from a heat transfer medium introduced via line 120. The sixth cooled effluent in line 589 can be at a temperature ranging from a low of about 100° C., about 150° C., about 175° C., or about 200° C. to a high of about 250° C., about 300° C., about 350° C., or about 400° C.
The sixth cooled effluent via line 589 can be introduced to the first heat exchanger 510 to produce a seventh cooled effluent via line 513. The seventh cooled effluent in line 513 can be at a temperature ranging from a low of about 5° C., about 15° C., or about 25° C. to a high of about 50° C., about 75° C., or about 100° C. For example, the seventh cooled effluent in line 513 can be at a temperature of about 17° C. to about 53° C., about 23° C. to about 47° C., or about 27° C. to about 43° C.
The seventh cooled effluent via line 513 can be introduced to the second vapor-liquid separator 565 to produce a second separated effluent via line 567 and a second condensate via line 569. The second separated effluent in line 567 can include amounts of methane, water, hydrogen, carbon monoxide, carbon dioxide, nitrogen, and argon that fall within the ranges provided for the fourth effluent in line 561. The second separated effluent in line 567 can be at a temperature ranging from a low of about 5° C., about 15° C., or about 25° C. to a high of about 50° C., about 75° C., or about 100° C. For example, the second separated effluent in line 567 can be at a temperature of about 17° C. to about 53° C., about 23° C. to about 47° C., or about 27° C. to about 43° C.
The first and second vapor-liquid separators 555, 565 can at least partially separate the gas phase from the liquid phase. The first and second vapor-liquid separators 555, 565 can include vertical vessels in which gravity can cause the liquid to settle to the bottom of the vessels, where it can be withdrawn, e.g., as the first and second condensate via lines 556, 569. Suitable vapor-liquid separators can include, but are not limited to, flash drums, knock-out drums, compressor suction drums, compressor inlet drums, demisters, combinations thereof, or the like. Vapor in the vessels can travel upward at a design velocity, which can minimize the entrainment of any liquid droplets in the vapor as it exits the top of the vessels.
The second separated effluent via line 567 can be introduced to the first compressor 570 to produce a compressed effluent via line 571. The compressor 570 can increase the pressure of the second separated effluent to meet pipeline or other requirements.
The compressed effluent via line 571 can be introduced to the drier 575 to removed at least a portion of the remaining moisture therein and produce a dried effluent via line 577 and a third condensate or water vapor via line 579. At least one of the first condensate via line 556, the second condensate via line 569, and the third condensate via line 579 can at least partially make up the methanation condensate via line 509 (
The dried effluent via line 577 can be introduced to the seventh heat exchanger or cooler 580 to produce the SNG via line 122. As shown, the seventh heat exchanger 580 can include one or more air coolers. It will be appreciated, however, that any one or more of a number of types of coolers can be implemented. For example, the seventh heat exchanger 580 can include, but is not limited to, one or more U-tube heat exchangers, one or more shell-and-tube heat exchangers, one or more plate and frame heat exchangers, one or more spiral wound heat exchangers, one or more fin-fan heat exchangers, one or more evaporative coolers, or any combination thereof.
The SNG product in line 122 can include methane, water, nitrogen, hydrogen, argon, carbon dioxide, carbon monoxide, or any combination thereof. The SNG product in line 122 can have a methane concentration ranging from a low of about 75 mol %, about 80 mol %, about 85 mol %, or about 90 mol %, to a high of about 95 mol %, about 97 mol %, about 98 mol %, about 99 mol %, or about 100 mol %, on a wet basis. The methanation system 500 can convert from about 80% to about 100% of the carbon monoxide and carbon dioxide in the syngas introduced via line 118 to methane. For example, the amount of the carbon monoxide and carbon dioxide contained in the syngas in line 118 that can be converted to SNG can be about 90% or more, about 93% or more, about 95% or more, about 97% or more, about 98% or more, or about 99% or more.
Referring back to the third cooled effluent via line 547, a portion can be recycled to the first syngas in line 517 and/or fed to the first methanator 520. For example, a portion of the third cooled effluent in line 547 or “recycle effluent” can be introduced via line 548 to the ninth heat exchanger 590 to produce an eighth cooled effluent or a cooled recycle effluent via line 593. The amount of the third cooled effluent in line 547 that can be recycled to the syngas in line 517 and/or directly to the first methanator 520 can range from a low of about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, or about 70% to a high of about 80%, about 90%, or about 98%. For example, about 50% to about 90%, about 55% to about 85%, about 70% to about 80%, or about 72% to about 78% of the third cooled effluent in line 547 can be recycled and/or introduced via line 548 to the ninth heat exchanger 590. The cooled recycle effluent in line 593 can be at a temperature ranging from a low of about 50° C., about 100° C., or about 150° C. to a high of about 200° C., about 250° C., or about 300° C.
The cooled recycle effluent via line 593 can be introduced to the second compressor 597 to produce a compressed recycle effluent via line 599. The compressed recycle effluent in line 599 can be at a pressure of about 500 kPa to about 14,000 kPa. For example, the compressed recycle effluent in line 599 can be at a pressure ranging from a low of about 700 kPa, about 1,000 kPa, about 2,000 kPa, or about 3,500 kPa to a high of about 4,500 kPa, about 5,500 kPa, about 7,500 kPa, or about 9,500 kPa. The compressed recycle effluent in line 599 can be at a temperature ranging from a low of about 175° C., about 200° C., about 210° C., or about 220° C. to a high of about 240° C., about 250° C., about 275° C., or about 300° C. For example, the compressed recycle effluent in line 599 can be at a temperature ranging from about 195° C. to about 265° C., about 205° C. to about 255° C., or about 215° C. to about 245° C. The compressed recycle effluent via line 599 can be mixed or combined with the first syngas in line 517 to produce a mixture and/or introduced directly to the first methanator 520.
The heat transfer medium via line 120 can be introduced to the eighth heat exchanger 585 to produce a first heated heat transfer medium via line 587. For example, the eighth heat exchanger 585 can transfer heat from the fourth effluent via line 561 to the heat transfer medium via line 120 to produce the first heated heat transfer medium via line 587.
The first heated heat transfer medium via line 587 can be introduced to the ninth heat exchanger 590 to provide a second heated heat transfer medium via line 591. For example, the ninth heat exchanger 590 can transfer heat from the recycle effluent in line 548 to the first heated heat transfer medium in line 587 to produce the second heated heat transfer medium via line 591. In another example, the ninth heat exchanger 590 can transfer heat to the recycle effluent in line 548 from the first heated heat transfer medium in line 587.
The heat transfer medium in line 120, the first heated heat transfer medium in line 587, and the second heated heat transfer medium in line 591 can be at a pressure ranging from a low of about 500 kPa, about 1,000 kPa, about 2,500 kPa, about 4,000 kPa, or about 6,000 kPa to a high of about 10,000 kPa, about 12,000 kPa, about 14,000 kPa, about 16,000 kPa, or about 18,000 kPa. The heat transfer medium in line 120, the first heated heat transfer medium in line 587, and the second heated heat transfer medium in line 591 can be at a temperature ranging from a low of about 90, about 125° C., or about 150° C. to a high of about 250° C., about 275° C., about 300° C., or about 325° C. The heat transfer mediums in lines 120, 587, and 591 can be or include liquid phase heat transfer mediums. For example, if the heat transfer medium in line 120 is or includes boiler feed water, the boiler feed water in lines 120, 587, and 591 can be about 90% liquid, about 95% liquid, about 97% liquid, about 98% liquid, about 99% liquid, or about 100% liquid phase.
The second heated heat transfer medium via line 591 can be introduced to the heat transfer medium collector/separator 595 to produce a heat recovery medium via lines 524, 534, and 544 for the heat exchangers 525, 535, 545. A heated heat transfer medium via line 124 can also be recovered from the heat transfer medium collector/separator 595. Although not shown, the heat transfer medium collector/separator 595 can include a plurality of discrete or separate vessels or other apparatus. For example, the heat transfer medium collector/separator 595 can include two, three, four, five, six, seven, eight, nine, ten, or more vessels or other apparatus. The heat transfer medium collector/separator 595 can separate a gaseous phase heat transfer medium from liquid phase heat transfer medium. For example, when the heat transfer medium in line 591 is water and/or a water/steam mixture, the steam within the heat transfer medium collector/separator 595 can be recovered as the heated heat transfer medium via line 124. When the heat transfer medium is water, the heat transfer medium collector/separator 595 can also be referred to as a “steam drum” or “steam collector/separator.”
The heated heat transfer medium via line 124, e.g., saturated steam or superheated steam, can be introduced to the syngas cooler 305 (
The first heat recovery medium via line 524 can be introduced from the heat transfer medium collector/separator 595 to the third heat exchanger 525 to produce a first heated heat recovery medium stream via line 529. The third heat exchanger 525 can transfer heat from the first effluent in line 521 to the first heat recovery medium to produce the first cooled effluent via line 527 and the first heated heat transfer recovery via line 529.
The second heat recovery medium via line 534 can be introduced from the heat transfer medium collector/separator 595 to the fourth heat exchanger 535 to produce a second heated heat recovery medium via line 539. The fourth heat exchanger 535 can transfer heat from the second effluent in line 531 to the second heat recovery medium to produce the second cooled effluent via line 537 and the second heated heat recovery medium via line 539.
The third heat recovery medium via line 544 can be introduced from the heat transfer medium collector/separator 595 to the fifth heat exchanger 545 to produce a third heated heat recovery medium via line 549. The fifth heat exchanger 545 can transfer heat from the third effluent in line 541 to the third heat recovery medium in line 544 to produce the third cooled effluent via line 547 and the third heated heat recovery medium via line 549.
The first, second, and third heated heat recovery mediums via lines 529, 539, and/or 549 can be or include saturated steam. For example, the first, second, and third heated heat recovery mediums in lines 529, 539, and/or 549 can be or include saturated steam in an amount ranging from a low of about 5 wt %, about 15 wt %, about 25 wt %, or about 35 wt % to a high of about 60 wt %, about 70 wt %, about 80 wt %, about 90 wt %, or about 95 wt %. The first, second, and third heated heat recovery mediums in lines 529, 539, and/or 549 can be at a temperature ranging from a low of about 172° C., about 220° C., or about 260° C. to a high of about 275° C., about 310° C., or about 343° C. The first, second, and third heated heat recovery mediums via lines 529, 539, and 549 can be recycled back to the heat transfer medium collector/separator 595.
The heat exchangers 525, 535, 545 can be, but are not limited to, U-tube exchangers, shell-and-tube exchangers, plate and frame exchangers, spiral wound exchangers, fin-fan exchangers, evaporative coolers, or any combination thereof.
The methanators 520, 530, 540, 560 can include one or more of physical, mechanical, electrical, and/or chemical systems to react carbon monoxide and/or carbon dioxide with hydrogen to produce methane and water. The methanators 520, 530, 540, 560 can each include one or more reactors. In at least one embodiment, the methanators 520, 530, 540, 560 can include two or more reactors operating in series or in parallel. For example, at least one of the methanators 520, 530, 540, 560 can include two catalytic reactors operating in parallel. In one or more embodiments, the first methanator 520, the second methanator 530, and the third methanator 540 can each include two reactors operated in parallel, and the fourth methanator 560 can include a single reactor.
The first methanator 520 can include a first catalyst, the second methanator 530 can include a second catalyst, the third methanator 540 can include a third catalyst, and the fourth methanator 560 can include a fourth catalyst. The first, second, and third catalysts can each be different than the fourth catalyst. The first, second, and third catalysts can be the same type of catalyst, or two or more of the first, second, and third catalysts can be different types of catalysts with respect to one another. In at least one embodiment, the first syngas in line 517, the first mixture in line 528, and the second mixture in line 538 can be methanated in the presence of the first catalyst, the second catalyst, and the third catalyst, respectively, and the heated effluent in line 559 can be methanated in the presence of the fourth catalyst, where the first, second, and third catalysts are different from the fourth catalyst.
Suitable catalysts can include, but are not limited to, nickel, rare earth promoted nickel, derivatives thereof, or combinations thereof. Other suitable catalysts can include, but are not limited to, cobalt, iron, ruthenium, “noble” Group VIII metals, molybdenum, tungsten, derivatives thereof, or combinations thereof. For example, the first, second, and third catalysts in the first, second, and third methanators 520, 530, and 540, respectively, can each be nickel oxide and the fourth catalyst in the fourth methanator 540 can be ruthenium.
The catalyst can vary in size and shape, as desired. For example, the catalyst can be shaped as rings, toroids, cylinders, rods, pellets, ellipsoids, spheres, tri-lobes, cubes, pyramids, cones, stars, daisies, combinations thereof, or the like. The catalyst may or may not be grooved and/or notched. In at least one embodiment, the catalyst used can be, but is not limited to, 6×6×2 mm ring shaped and/or 6-3 mm spherical shaped structures. For example, the 6×6×2 mm ring shaped catalyst structure can be used in the first methanator 520, the second methanator 530, and the third methanator 540, and the 6-3 mm spherical shaped structure can be used in the fourth methanator 560.
Embodiments of the present invention can be further described with the following prophetic example. The following simulation uses a methanation system similar to the methanation system 500 discussed and described above. The simulation, however, uses only one heat exchanger prior to splitting the effluent between the first three methanators 520, 530, 540 and uses only one heat exchanger after recycling the cooled effluent from the fifth heat exchanger 545 and before vapor-liquid separation via the vapor-liquid separator 555. The simulation also does not include further processing, e.g., cooling, separation, compression, and drying, of the effluent from the fourth methanator 560.
In this simulated example, a total of four methanation reactors are used, e.g., methanators 520, 530, 540, 560. The first three methanators operate with a recycle stream exiting the third methanator back to the first methanator to dilute the incoming carbon monoxide concentration. A fresh feed stream from an upstream gasification and purification system is split into three portions with each portion introduced directly into the inlet of the first three methanators. A SNG—1000 catalyst in a 6×6×2 mm ring shape is used because of high moisture content in these first three methanation stages, as it is more tolerant to high moisture conditions and high temperatures. The fourth methanator, e.g., methanator 560, treats the portion of the flow exiting the third methanator that was not recycled back to the front end for dilution. This results in about 25% of a wet gas volume exiting the third methanator. Cooling and water separation steps are inserted into the process before the fourth methanator, and a feed or effluent to the final methanator is reheated to 260° C. (500° F.). For the dryer methanation process in the fourth methanator uses a Meth-134 catalyst in a 6-3 mm spherical shape.
Table 11 summarizes the simulated methanator configuration and design.
Tables 12-14 summarize the simulated results for the example. The stream numbers correspond to the line numbers depicted in
Embodiments described herein further relate to any one or more of the following paragraphs:
1. A method for producing a synthetic gas, comprising: gasifying a feedstock within a gasifier to provide a raw syngas; processing the raw syngas within a purification system to provide a treated syngas, wherein the purification system comprises a flash gas separator; converting the treated syngas and a first heat transfer medium into a synthetic gas, a second heat transfer medium, and a methanation condensate; and introducing the methanation condensate to the flash gas separator.
2. The method of paragraph 1, wherein converting the treated syngas further comprises: splitting the treated syngas into a first treated syngas, a second treated syngas, and a third treated syngas; converting the first treated syngas into a first effluent in a first methanator; mixing the first effluent and the second treated syngas to provide a first mixed effluent; converting the first mixed effluent into a second effluent in a second methanator; mixing the second effluent and the third treated syngas to provide a second mixed effluent; and converting the second mixed effluent into a third effluent in a third methanator.
3. The method of paragraph 2, further comprising removing a first condensate from the third effluent in a first separator to provide a first separated effluent.
4. The method of paragraph 3, further comprising converting the first separated effluent into a fourth effluent in a fourth methanator.
5. The method of paragraph 4, further comprising transferring heat from the fourth effluent to the first heat transfer medium to provide a cooled effluent.
6. The method of paragraph 5, further comprising removing a second condensate from the cooled effluent to provide a second separated effluent.
7. The method of paragraph 6, further comprising compressing the second separated effluent to provide a compressed effluent.
8. The method of paragraph 7, further comprising removing a third condensate from the compressed effluent to provide the synthetic gas.
9. The method of paragraph 8, wherein at least one of the first, second, and third condensates at least partially comprises at least a portion of the methanation condensate.
10. A method for producing a synthetic gas, comprising: gasifying a carbonaceous feedstock in the presence of an oxidant within a gasifier to provide a raw syngas: cooling the raw syngas within a cooler to provide a cooled syngas; processing the cooled syngas within a purification system to provide a treated syngas, wherein the purification system comprises a flash gas separator and a saturator; introducing the treated syngas and a first heat transfer medium to a methanator to provide a synthetic gas, a second heat transfer medium, and a first condensate; introducing the first condensate to the flash gas separator to provide a flashed gas and a second condensate; introducing the flashed gas to the gasifier; and introducing the second condensate to the saturator.
11. The method of paragraph 10, wherein processing the cooled syngas within the purification system further comprises increasing a moisture content of at least a portion of the cooled syngas with the saturator to provide a saturated syngas.
12. The method of paragraph 11, further comprising: introducing the saturated syngas to a gas shift device to provide a shifted syngas; introducing the shifted syngas to a syngas cooler to provided a cooled shifted syngas and a third condensate; and introducing the third condensate to the flash gas separator.
13. The method according to any one of paragraphs 10 to 12, wherein processing the cooled syngas within the purification system further comprises: introducing at least a portion of the cooled syngas to a hydrolysis device to provide a hydrogen sulfide syngas; and removing ammonia from the hydrogen sulfide syngas with an ammonia scrubber to provide a scrubbed syngas and waste water.
14. The method of paragraph 13, further comprising: introducing the waste water to a syngas cooler to provide a third condensate; and introducing the third condensate to the flash gas separator.
15. A system for producing a synthetic gas, comprising: a gasifier adapted to gasify a feedstock to provide a raw syngas; a purification system coupled to the gasifier and adapted to convert the raw syngas into a treated syngas, wherein the purification system comprises a flash gas separator; and a methanator coupled to the purification system and adapted to convert the treated syngas and a first heat transfer medium into a synthetic gas, a second heat transfer medium, and a methanation condensate, wherein the methanation condensate is introduced to the flash gas separator.
16. The system of paragraph 15, wherein the methanator further comprises: a first methanator coupled to the purification system and adapted to convert a first portion of the treated syngas into a first effluent, wherein the first effluent is mixed with a second portion of the treated syngas to provide a first mixed effluent; a second methanator coupled to the first methanator and adapted to convert the first mixed effluent into a second effluent, wherein the second effluent is mixed with a third portion of the treated syngas to provide a second mixed effluent; and a third methanator coupled to the second methanator and adapted to convert the second mixed effluent into a third effluent.
17. The system of paragraph 16, further comprising a first separator coupled to the third methanator and adapted to remove a first condensate from the third effluent to provide a first separated effluent.
18. The system of paragraph 17, further comprising a fourth methanator coupled to the first separator and adapted to convert the first separated effluent into a fourth effluent.
19. The system of paragraph 18, further comprising a second separator coupled to the fourth methanator and adapted to remove a second condensate from the fourth effluent to provide a second separated effluent.
20. The system of paragraph 19, wherein at least one of the first and second condensates at least partially comprises the methanation condensate.
Certain embodiments and features have been described using a set of numerical upper limits and a set of numerical lower limits. It should be appreciated that ranges from any lower limit to any upper limit are contemplated unless otherwise indicated. Certain lower limits, upper limits and ranges appear in one or more claims below. All numerical values are “about” or “approximately” the indicated value, and take into account numerical error and variations that would be expected by a person having ordinary skill in the art.
Various terms have been defined above. To the extent a term used in a claim is not defined above, it should be given the broadest definition persons in the pertinent art have given that term as reflected in at least one printed publication or issued patent. Furthermore, all patents, test procedures, and other documents cited in this application are fully incorporated by reference to the extent such disclosure is not inconsistent with this application and for all jurisdictions in which such incorporation is permitted.
While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
This application is a continuation-in-part of U.S. patent application Ser. No. 13/091,980, filed on Apr. 21, 2011, and published as U.S. Publication No. 2012/0101323, which is a continuation of U.S. patent application Ser. No. 12/437,999, filed on May 8, 2009, and issued as U.S. Pat. No. 7,955,403, which claims priority to U.S. Provisional Patent Application having Ser. No. 61/081,304, filed on Jul. 16, 2008. This application also claims the benefit of U.S. patent application Ser. No. 13/335,314, filed on Dec. 22, 2011, which is incorporated by reference herein. The content of each is incorporated by reference herein to the extent consistent with the present disclosure.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 13091980 | Apr 2011 | US |
| Child | 13663902 | US |
