COAL CHAR PASSIVATION PROCESS AND APPARATUS
20190071614 ยท 2019-03-07
Assignee
Inventors
- Franklin G. Rinker (Marco Island, FL, US)
- Deane Avent Horne (Toledo, OH, US)
- Timothy J. Kuhn (Toledo, OH, US)
- Robert W. Mueller (Louisville, KY, US)
- James Darrell Kinder (Charlestown, IN, US)
Cpc classification
C10L9/00
CHEMISTRY; METALLURGY
C10B51/00
CHEMISTRY; METALLURGY
International classification
C10B57/00
CHEMISTRY; METALLURGY
C10B51/00
CHEMISTRY; METALLURGY
Abstract
A continuous process and apparatus for treating dried coal and coal char to promote passivation of the reactive carbon particles by forming a protective oxide coating and simultaneously adding moisture to rehydrate said particles. The passivation process is conducted in a novel apparatus providing for the staged control of the reaction temperature and the staged introduction of both oxygen and moisture. The fluidized bed apparatus has internal in-bed cooling means embedded within the fluidized coal or coal char particles so as to remove the heat energy as it is released by virtue of the exothermic passivation reactions.
Claims
1. A fluidized passivation apparatus for passivating coal char, comprising a reaction chamber defining an interior and having a char inlet for receiving coal char into the interior and a char sump for allowing coal char to exit the interior; the reaction chamber further including at least one gas inlet for admitting an oxygen-containing fluidizing gas into the interior, at least one gas outlet for allowing exit of the fluidizing gas from the interior, and a gas recirculation system comprising a source of fluidizing gas, one or more conduits and a pump, the conduits and pump arranged and adapted to recirculate the fluidizing gas from the gas outlet to the gas inlet under conditions to cause a fluidized state in the coal char within the interior of the reaction chamber; at least one heat exchanger embedded within the interior of the reaction chamber, the heat exchanger having a coolant fluid inlet, a coolant fluid outlet and a plurality of contact surfaces for exchanging heat with coal char within the interior; and a humidifier connected to a source of water and adapted for humidifying the coal char.
2. The apparatus of claim 1 wherein there are a plurality of heat exchangers and a plurality of gas inlets.
3. The apparatus of claim 1, further comprising a cyclone in the gas recirculation system for removing entrained particulates from the gas stream and returning the particulates to the char.
4. The apparatus of claim 1 wherein the humidifier is configured to humidify the coal char by one or more of: (a) droplet spray onto char located in the interior of the reaction chamber; (b) droplet spray onto char at a location prior to its entry into the reaction chamber; (c) droplet spray into the interior of the fluidizing reaction chamber; and (d) droplet spray into the gas recirculation system so that the fluidizing gas is humidified.
5. The apparatus of claim 4 wherein the humidifier comprises a spray nozzle adapted to spray water into the interior of the reaction chamber.
6. The apparatus of claim 4 wherein the humidifier comprises a spray nozzle adapted to spray water into gas recirculation system.
7. The apparatus of claim 5 or claim 6 wherein the humidifier further comprises a source of compressed gas for atomizing the sprayed water.
8. The apparatus of claim 1, further comprising a source of oxygen for providing or supplementing the oxygen-containing fluidizing gas to passivate the coal char.
9. A method for passivating coal char using a fluidized passivation bed according to claim 1.
10. A method for passivating coal char using a fluidized bed reactor with an internal heat exchanger.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0022]
[0023]
[0024]
[0025]
[0026]
DETAILED DESCRIPTION OF THE INVENTION
[0027] Various embodiments are described herein in the context of methods and apparatus for passivating coal char. Those of ordinary skill in the art will realize that the following detailed description of the embodiments is illustrative only and not intended to be in any way limiting. Other embodiments will readily suggest themselves to such skilled persons having the benefit of this disclosure. Reference to an embodiment, aspect, or example herein indicate that the embodiments of the invention so described may include a particular feature, structure, or characteristic, but not every embodiment necessarily includes the particular feature, structure, or characteristic. Further, repeated use of the phrase in one embodiment does not necessarily refer to the same embodiment, although it may.
[0028] In the interest of clarity, not all of the routine features of the implementations or processes described herein are shown and described. It will, of course, be appreciated that in the development of any such actual implementation, numerous implementation-specific decisions will be made in order to achieve the developer's specific goals, such as compliance with application- and business-related constraints, and that these specific goals will vary from one implementation to another and from one developer to another. Moreover, it will be appreciated that such a development effort might be complex and time-consuming, but would nevertheless be a routine undertaking for those of ordinary skill in the art having the benefit of this disclosure.
[0029] It is to be understood that the ranges and limits mentioned herein include all ranges located within the prescribed limits (i.e., subranges). For instance, a range from about 100 to about 200 also includes ranges from 110 to 150, 170 to 190, 153 to 162, and 145.3 to 149.6. Further, a limit of up to about 7 also includes a limit of up to about 5, up to 3, and up to about 4.5, as well as ranges within the limit, such as from about 1 to about 5, and from about 3.2 to about 6.5.
[0030] Pyrolysis Process Overview
[0031]
[0032] The pyrolysis process produces three products, water vapor, effluent or evolved gases, and coal char. As shown in
[0033] Note that some portion of the volatiles driven from the coal may be reused as sweep gas (path 60) for heating the coal during pyrolysis. Some components of the coal volatiles do not condense at ambient temperatures and remain in a gaseous state known as syngas. Syngas may be burned off as a flare 700 or, preferably re-used as a fuel for the boiler (path 62). Alternatively, the boiler 1400 may be fueled by any other source of fuel 710, such as diesel fuel. The CDL and volatile process stream is shown in
[0034] Solid coal products are shown in
[0035] Passivation Reactor
[0036] Passivation requires oxygen adsorption or uptake (aka chemisorption) by the char particles in the range of about 0.2% to about 0.7% by weight, or from about 0.3% to about 0.6% by weight, nominally about 0.5% by weight. Excessive oxygen uptake reduces the calorific value of the resultant char. Passivation also requires moisture or water uptake by the char particles in the range of about 3% to about 7% by weight, or from about 5% to about 6% by weight, nominally about 5.5% by weight.
[0037] Fluidized bed reactors are well known and operate on the principle that particulate matter can be made to behave like a fluid when subjected to a stream of gas flowing under a sufficient pressure. While the particles are behaving like a fluid, the surface area of the particles is more exposed, enabling faster chemical and physico-chemical reactions. Fluidized bed reactors have been utilized in the drying and heating processes of pyrolysis, but to our knowledge, no fluidized bed reactors with internal heat exchangers have been utilized in a char passivation process. Suitable fluidized bed reactors are commercially available from Carrier Vibrating Equipment Company, Louisville, Ky.
[0038] Advantages of the present invention include smaller char particle sizes, which enable for the first time the use of fluidized bed reactors with internal heat exchangers for passivation, and increased surface area for a given mass of particle, which facilitates the kinetics of the chemical and physical reactions of passivation. These features contribute to much faster passivation times and lower particle residence times. For example, particle residence times in a continuous process may be on the order of about 60 minutes or less, about 45 minutes or less, or about 30 minutes or less. In some embodiments, the residence time is 60 minutes, 20 minutes. In other embodiments, the residence time is 30 minutes, about 10 minutes
[0039]
[0040] The spray nozzle is fed by a source of water 28 (optionally filtered at 11) and optionally with a source of compressed air 32 for creating a spray or atomized spray of water from the spray head or nozzle 2c into the reaction chamber 2. The nozzle 2c is one mechanism for humidifying the char; an alternative method of humidification is described later in connection with the gas recirculation system 42. The fluidized passivator bed system 40 may utilize either one of the alternative humidification methods alone, or may use both in combination. If a spray nozzle 2c is utilized for humidification, it may be desirable to locate it near the coal inlet, and to avoid placing a heat exchanger (13, see later) directly beneath the spray nozzle 2c.
[0041] The reaction chamber 2 also has at least one gas inlet 24 for admitting a fluidizing gas into the interior 22, and at least one gas outlet 26 for exiting a fluidizing gas. The gas inlet 24 and the gas outlet 26 may also be viewed as part of a gas recirculation system 42, which circulates the gas from the gas outlet 26 back to the gas inlet 24. The gas recirculation system 42 also comprises various conduits or conducting paths (e.g. paths 3 and 9) and a fan or pump 14 for pressurizing the gas and driving it forward through conduit 9 into the reaction chamber 2. The gas inlet 24 is typically at the bottom of the reaction chamber 2, which allows the downward force of gravity to balance against the upward force of the gas stream to keep the particles fluidized in vertical motion. Meanwhile, continuous entry of new char material at char inlet 2a and removal of passivated char at sump/exit 2b produces a generally lateral flow from inlet to exit (from left to right in
[0042] The fluidizing gas may be any gas capable of fluidizing the char particles. In one embodiment the fluidizing gas is oxygen-depleted air; while in another embodiment, the fluidizing gas is a non-oxidative gas, such as nitrogen, carbon dioxide, or a combination of the above. However, as explained herein, the chemisorption of oxygen onto or into the char particles is an important component to the passivation process, so if an inert or non-oxidative gas is used, it is desirable to include a source of oxygen-containing gas as a makeup, as described below. Conversely, if too much oxygen is present, the char may adsorb too much oxygen, so pure air, at 23% by weight oxygen, is generally not used, except for initial start-up following a nitrogen purge. Thereafter, fluidizing air that is oxygen-depleted is used. An oxygen-depleted gas or fluid is one in which the oxygen content is less than about 15% by weight. In some embodiments, the fluidizing gas is depleted of oxygen by passing it through the charwhich adsorbs some of the oxygen, and then recycling it as a fluidizing gas.
[0043] By weight, the oxygen content of the fluidizing gas should be at least 5% but less than about 15%. In some embodiments, the oxygen content of the fluidizing gas should be between about 7% and about 12% by weight. In embodiments where the spray nozzle 2c is used for humidification and the spray is atomized, the oxygen content of the atomizing gas should also be considered as a source of oxygen in the passivation reactor 2.
[0044] Optionally, the gas recirculation system 42 comprises a separator, such as cyclone separator 4. The cyclone separator 4 receives at a tangential inlet the fluidizing gas exiting the reaction chamber interior 22. This exiting gas may include some entrained particulates. Cyclone 4 spins the gas to allow the particulates to drop out of the entraining gas. The particulates are collected and, via rotary valve 5, are readmitted to the reaction chamber 2, preferably near the char sump 2b. Suitable cyclone separators are available from suppliers such as Ducon, 5 Penn Plaza, New York, N.Y.; Fisher-Klosterman, Louisville, Ky.; or Heumann Environmental, Jeffersonville, Ind. For example, some Heurmann units are designed to remove 95% of the minus 5 micron particulates carried in the fluidizing gas stream. Gas, free of entrained particulates, exits the top of the cyclone.
[0045] Optionally, the gas recirculation system 42 comprises a humidifier 6, which may optionally take the form of an additional cyclone device. The humidifier 6 receives at a tangential inlet the fluidizing gas exiting the separation cyclone 4 (or exiting the reaction chamber interior 22 if cyclone 4 is absent). Water from a source of water 28 optionally filtered (at 7), optionally atomized by a source of compressed gas 32 before being sprayed into the humidifier 6 to re-humidify the fluidizing gas before it is returned via conduits and pump 14 to the gas inlet 24 of the reaction chamber 2.
[0046] For control purposes, the gas recirculation system 42 may further comprise monitors or sensors for measuring concentration or level (A), temperature (T), pressure (P), and/or flow velocity (F), as well as valves or controllers that are responsive to these measurements. For example,
[0047] Finally, the gas recirculation system 42 may further comprise a source of an oxygen-containing makeup gas, such as air 12 (or pure oxygen), having oxygen as a component. As has been explained, the chemisorptions of oxygen onto or into the char particles is an important component to the passivation process. An oxygen sensor (A) monitors the oxygen levels in the fluidizing gas and, in response, a controller (AIC) operates a valve (AVC) to admit more of the oxygen-containing gas 12.
[0048] Still referring to
[0049] While the heat exchangers 13 are embedded within the reaction chamber 2, the coolant fluid system 44 is completely distinct from gas recirculation system 42 and the two never mix directly. After leaving the last heat exchanger 13, the coolant fluid exits the chamber 2 via conduit 11 and flows to a coolant return area 48. It will be noted that the coolant return area 48 may be looped back to the coolant supply area 46 via a conventional cooling tower (not shown), thus closing the coolant flow circuit. In this way, heat contained in the warm, pyrolized char and created by the exothermic chemisorption is extracted from the char as it is being fluidized. The increased surface area of the fluidized particulates and of the heat exchanger units embedded in the reaction bed allow for an extremely efficient cooling and passivation process. This in turn allows for a continuous process that can be operated more rapidly and with more control.
[0050] This careful control of reaction conditions is important for another reason. For the passivation process to proceed within a definite time period conducive to a continuous process, the temperature in the active fluidized bed is to be controlled to nominal 125 F., plus or minus about 10 F. (about 52 C. 6 C.) In various embodiments, the passivation temperature is carefully maintained from about 110 F. to about 140 F. (about 43 C. to about 60 C.), or from about 115 F. to about 135 F. (about 46 C. to about 57 C.), or from about 120 F. to about 130 F. (about 49 C. to about 54.5 C.).
[0051] Suitable fluidized bed reactors with heat exchanging coolant fluid systems are commercially available from Carrier Vibrating Equipment Company, Louisville, Ky.
[0052] Data from testing demonstrated that the exothermic heat release for the chemisorption and rehydration is in the order of 172,473 Btu (181,960 kJ) per metric ton of char prepared from a sub-bituminous coal. The char typically has a specific heat absorption rate of 0.35 Btu per pound degree F. (1.47 kJ per kg C.). In view of this exothermic heat release, it can easily be determined that the uncontrolled temperature increase could be as much as 225 degrees F. (about 125 C.). As such, the heat release, if uncontrolled, would increase the temperature of the dried coal char particles to temperature levels far in excess of those whence the rehydration moisture would adhere to the particles. The excess heat generated would have two negative effects. First, it would tend to evaporate the water before it could effectively hydrate the char. Second, it would cause over adsorption of oxygen, beyond desirable passivation levels, thereby reducing the calorific value of the char.
[0053] Experience indicates that the passivation reactions proceed rapidly when the solid particles are initially injected into the fluidized bed reaction unit. The rate of chemisorption and rehydration diminishes as the passivation process proceeds. Therefore, as shown in
[0054] The internal heat exchangers 113 are designed to independently control the temperature in each lateral section even as the heat release varies from the entry end (near 2c) to the exit end (near 2b) of the fluidized bed processing chamber. The coolant passes internally thru the internal embedded coils at flow rates controlled so as to remove the differing exothermic heat generation levels at successive stages along the reaction passageway. Thus, coolant may flow faster at the entry end so as to more rapidly remove the heat generated by the early, initial stage exothermic reaction, and more slowly near the exit end where the exothermic reaction has slowed. Likewise, the oxygen input/output concentration levels and the moisture input/output concentration levels can be staged so as to meet the varying demand levels as the passivation process matures in passing laterally (from left to right in
[0055] As discussed above, fluidization causes the fine particles to move both vertically and horizontally, and continuous injection of fresh particles at the inlet end causes the particles to pass horizontally through the reaction chamber. The retention time can be controlled by increasing or decreasing the influx of untreated or active char particles and by moderately modulating the gas flow rate. Of necessity, the dried coal or coal char particles must have been carefully sized to facilitate fluidization and to expose the necessary surface area to facilitate the passivation reactions within a finite reaction chamber.
[0056]
EXAMPLE 1
[0057] A coal pyrolysis and char passivation apparatus is set up substantially as described herein in connection with
[0058] Assuming an internal coolant fluid is used, it is possible to calculate the required flow rate based reasonable assumptions. Assuming a coolant having a heat capacity of 0.5 Btu/lb (0.12 kJ/kg), and assuming a temperature change of 50 F. (28 C.), e.g. from about 85 F. (29.4 C.) inlet to about 135 F. (57.2 C.) outlet temperature, to maintain the reaction chamber at about 125 F. (51.7 C.), implies that the coolant fluid is capable of removing 25 Btu/lb (58.2 kJ/kg) coolant. If 6,118,479 Btu (6,454,996 kJ) per hour need to be removed, the coolant must flow at about 244,759 lbs (111,020 kg) per hour in order to remove the anticipated exothermic heat load.
EXAMPLE 2
[0059] An embodiment of the invention using an external humidifier to inject moisture into the fluidizing gas is evaluated, using a fluidized reactor bed that is 7.5 ft (2.29 m) wide, 30 ft (9.14 m) long and having 66 inches (1.68 m) of fluidized depth. Nitrogen is used as the fluidizing gas at a design velocity of 86 ft/min, which equates to a flow rate of 19,350 SCFM or 86,500 lb (39,236 kg) dry gas/hr. Oxygen is admitted as required to facilitate the ongoing chemisorptions process. Assuming a char flow of about 32.25 metric tons/hour as in Example 1, and a 5.5% target moisture, implies that about 3910 lbs (1775 kg)/hr of water are necessary to passivate the char. Rounding to 4000 lbs (or about 1800 kg) per hr for a safety factor, means that the vapor content of the Nitrogen fluidizing gas must be 4000/(86,500+4,000) [or 1800/(39.236+1800)]=4.4% or 4.5% absolute humidity. At a typical average temperature of about 115 F. (46 C.), this represents a relative humidity of about 36%, which is easily attainable.
EXAMPLE 3
[0060] An embodiment of the invention using an atomized spray nozzle to supply moisture directly into the reaction chamber is evaluated, using a fluidized reactor bed that is 7.5 ft (2.29 m) wide, 30 ft (9.14 m) long and having 66 inches (1.68 m) of fluidized depth. The reaction chamber is fitted with eight internal mix atomizing nozzles (e.g. Spraying Systems models 1//2JSU89) for providing humidification. The water requirement of about 3950 lbs/hr (1792 kg/hr) is calculated and rounded as in Example 2, implying a water flow rate of 28,145 gallons/hr or 470 gallons/min (1779 L/min). The example considers both nitrogen and air as atomizing gases.
[0061] It is important to note that in this spray humidifier embodiment, the humidifying water is admitted to the reaction chamber in the physical form of a very fine mist or alternatively as water vapor.
[0062] While the invention has been described with reference to various and preferred embodiments, it should be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the essential scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof.
[0063] The entire content of all US patents and patent applications and any other publication mentioned specifically in this application is hereby incorporated by reference.
[0064] Therefore, it is intended that the invention not be limited to the particular embodiment disclosed herein contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the claims.