Abstract:
A recycling apparatus for spent protective atmosphere gas contaminated with fouling organic decomposition byproduct materials. The recycling apparatus includes a compressor having an inlet connected to a spent protective atmosphere gas supply line, and a solvent supply configured to supply solvent to a gas passage at or upstream of the compressor. The recycling apparatus also includes a first chamber connected to an outlet of the compressor, where the first chamber is configured to receive compressed gas from the compressor and to collect a mixture including the solvent and any contaminants entrapped or dissolved in the solvent.

Description:
CROSS-REFERENCE TO RELATED APPLICATION 
       [0001]    The present application is related to U.S. Provisional Application Ser. No. 60/839,427, entitled “IMPROVED METHOD AND APPARATUS FOR PROTECTIVE ATMOSPHERE RECYCLING,” filed Aug. 23, 2006, which is incorporated herein by reference in its entirety. 
     
     BACKGROUND OF THE INVENTION 
       [0002]    1. Field of the Invention 
         [0003]    The present invention relates to processing and recycling of spent protective atmosphere gas contaminated with fouling organic decomposition byproduct materials during thermal processing. 
         [0004]    2. Discussion of the Background 
         [0005]    Protective atmosphere gas used in heat treatment or other thermal processing has long been discarded after use in industries where the components being treated are coated or bound with organic species. Examples include batch annealing of metal coated with residual rolling oils and reduction and/or sintering of metal powders or fibers combined with organic binders. The spent atmosphere gases, usually at low pressure, have been considered too prone to formation of fouling deposits to be compressed, let-alone otherwise purified and recycled. This is true even when total impurities are extremely low. 
         [0006]    The inventors of the present invention have discovered that these fouling tendencies usually arise from the formation of poly-cyclic aromatic hydrocarbons (PAH&#39;s) during the thermal processing step. Most compounds of this type form solid deposits at standard conditions. These solids are prone to further thermal dehydrogenation, with an eventual tendency to form a range of adherent solids referred to as “varnish,” “tar,” or “coke.” These fouling tendencies are especially strong when gas mixtures containing these compounds are compressed, for two reasons. First, increasing the total pressure of the mixture increases the thermodynamic tendency towards solid formation during interstage cooling, as the partial pressure of the contaminants is increased. And second, the high temperatures experienced in many compression cycles can accelerate the formation of thermal decomposition products such as varnish, tar and coke. If these are formed in critical moving parts, such as compressor valves, then malfunction will be greatly accelerated. 
       SUMMARY OF THE INVENTION 
       [0007]    In an effort to eliminate the above problems, the inventors have devised a method and apparatus for the recycling of spent atmosphere gases that advantageously reduce the net consumption of atmosphere gas. Thus, the present invention advantageously provides a method and apparatus to facilitate the processing of atmosphere gases contaminated with fouling organic decomposition byproduct materials. 
         [0008]    Accordingly, the present invention advantageously provides methods of operating thermal treatment equipment employing protective atmospheres to treat materials including organic coatings or binders to avoid the formation of fouling deposits in a gas recycling apparatus. 
         [0009]    The present invention further advantageously provides a method and apparatus for removing vaporized decomposition byproducts from spent atmosphere gas prior to compression in a gas recycle apparatus. 
         [0010]    The present invention also advantageously provides a method and apparatus for compressing spent atmosphere gases contaminated with decomposition byproducts from organic coatings or binders that prevents the formation of fouling deposits. 
         [0011]    In addition, the present invention advantageously provides a method and apparatus for cooling compressed, spent atmosphere gases contaminated with decomposition byproducts from organic coatings or binders without fouling. 
         [0012]    The present invention also advantageously provides a method for recycling spent atmosphere gases contaminated with decomposition byproducts from organic coatings or binders that captures the byproduct species without exhausting them into the environment. 
         [0013]    The present invention further advantageously provides a method and apparatus for recycling spent atmosphere gases contaminated with decomposition byproducts from organic coatings or binders that employs at least one stage of positive-displacement compression. 
         [0014]    Additionally, the present invention advantageously provides a method and apparatus for recycling spent atmosphere gases contaminated with decomposition byproducts from organic coatings or binders that employs at least one stage of oil-lubricated positive-displacement compression. 
         [0015]    Furthermore, the present invention advantageously provides a method and apparatus for recycling spent atmosphere gases contaminated with decomposition byproducts from organic coatings or binders that employs at least one stage of oil-lubricated positive-displacement compression, where the oil used to lubricate the mechanical running gear maintains its original lubricating properties. 
     
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         [0016]    A more complete appreciation of the invention and many of the attendant advantages thereof will become readily apparent with reference to the following detailed description, particularly when considered in conjunction with the accompanying drawings, in which: 
           [0017]      FIG. 1  depicts a schematic view of a compression system for contaminated gas; 
           [0018]      FIG. 2  depicts a schematic view of a compression system with compressor lubrication according to the present invention; 
           [0019]      FIG. 3  is a chart showing solubility limits of hydrocarbon contaminants in two different compressor lubricants at room temperature; 
           [0020]      FIG. 4  depicts a schematic view of a compression system according to the present invention with a gas buffer placed below a gas cooler; 
           [0021]      FIG. 5  depicts a schematic view of a compression system according to the present invention with a unitized gas buffer apparatus; and 
           [0022]      FIG. 6  depicts a schematic view of a compression system according to the present invention with a unitized gas buffer apparatus with recycle of waste liquids to the system inlet, solvent injection means, and waste liquid pumping means. 
       
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
       [0023]    Embodiments of the present invention will be described hereinafter with reference to the accompanying drawings. In the following description, the constituent elements having substantially the same function and arrangement are denoted by the same reference numerals, and repetitive descriptions will be made only when necessary. 
         [0024]      FIG. 1  depicts a schematic view of a compression system that inducts a gas stream  1 , which can be cooled in a heat exchanger or cooler  2  to a desired suction temperature. The cooled gas then passes to a pulsation buffering vessel or chamber  3  that minimizes fluctuations in pressure caused by suction of a gas compressor  4 . The compressor  4  can be a positive displacement or dynamic compressor, using one or more reciprocating pistons, rotary screws or lobes, oscillating scrolls, a centrifugal or axial compressor, or any other type of compressor. The compressor  4  discharge is connected to a pulsation dampener or chamber  7 , before entering a cooler  8 , where it is cooled to a desired temperature before moving to a final vessel or chamber  9 . 
         [0025]    The compressed, cooled gas  10  exits the vessel  9  for use or for further processing. For example, the vessel  9  can serve as a pulsation dampener prior to further stages of compression, as in a multiple-stage reciprocating piston compressor. The vessel  9  can also serve as a liquid and/or solid particle separation vessel. To this end, the vessel  9  can be provided with internal baffles, filter elements, packed-media, a cyclone section, or other means to effect droplet separation. Likewise, the suction buffing vessel  3  can also serve as a separation device before the compressor  4 . In order to evacuate separated material from vessels  3  and  9 , they are provided with drains with drain valves  5  and  11 , respectively. The drain valves can be manual valves or automated valves. The drain valves can also be actuated by level sensors  6  and  12 , which can be of any level sensor type, such as radar, capacitance, thermal conductivity, ultrasonic, mechanical float, or optical, as suits the material being collected. In lieu of the level sensors  6  and  12 , the drain valves  5  and  111  can be automated based on timers, on number of compressor rotations, or on other means. The method of automation does not limit the present invention in any way. 
         [0026]    Table 1 below shows representative compositions of contaminants condensed from heat treating atmosphere gas at 0° C. All of these compounds are polyaromatic hydrocarbons, and all are solids at room temperature. These compounds, as well as other hydrocarbons, water vapor, and solids may be present in the inlet atmosphere stream  1  in concentrations in excess of 1,000 parts per million. Such concentrations can result in rapid fouling of coolers  2  and  8 , which results in undesirable downtime for maintenance. Even if the concentrations, temperature, and pressure are such that fouling does not occur in heat exchanger  2  or vessel  3 , the higher total gas pressure in heat exchanger  8  and vessel  9  could result in the formation of fouling deposits. Likewise, if the product gas  10  is compressed in subsequent stages of compression, as may be desirable to affect the best purification of the gas, then subsequent stages may experience fouling. 
         [0000]    
       
         
               
               
             
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                   
                 TABLE 1 
               
             
             
               
                   
                   
               
               
                   
                 Amount detected (in μg) for an injection of 1.0 μl of sample 
               
             
          
           
               
                   
                   
                   
                   
                   
                   
                   
                   
                 Chrysene/ 
                   
                   
               
               
                 Sample 
                 Naph- 
                   
                   
                 Fluor- 
                 Anthracene/ 
                   
                 Py- 
                 Benza[a]- 
                 Benzo- 
               
               
                 # 
                 thalene 
                 Acenaphthylene 
                 Acenaphthene 
                 ene 
                 Phenanthrene 
                 Fluoranthene 
                 rene 
                 Anthracene 
                 fluroanthenes 
                 Benzo[a[pyrene 
               
               
                   
               
             
          
           
               
                 1 
                 0.289 
                 0.016 
                 0.010 
                 0.096 
                 0.439 
                 0.200 
                 0.174 
                 0.008 
                 0.010 
                 — 
               
               
                 2 
                 0.037 
                 — 
                 0.027 
                 0.028 
                 0.054 
                 — 
                 0.003 
                 — 
                 — 
                 — 
               
               
                 3 
                 11.24 
                 0.873 
                 0.171 
                 0.837 
                 2.264 
                 0.508 
                 0.329 
                 0.128 
                 0.034 
                 0.030 
               
               
                 4 
                 7.271 
                 0.424 
                 0.148 
                 0.453 
                 0.537 
                 0.128 
                 0.105 
                 0.006 
                 — 
                 — 
               
               
                 5 
                 0.060 
                 — 
                 — 
                 1.805 
                 0.802 
                 0.197 
                 0.089 
                 — 
                 — 
                 — 
               
               
                 6 
                 — 
                 — 
                 — 
                 1.017 
                 3.040 
                 0.520 
                 0.238 
                 0.074 
                 — 
                 — 
               
               
                 7 
                 — 
                 — 
                 0.024 
                 2.596 
                 1.133 
                 0.190 
                 0.108 
                 — 
                 — 
                 — 
               
               
                   
               
             
          
         
       
     
         [0027]      FIG. 2  shows an alternative compression scheme according to the present invention, wherein the compressor  4  is provided with a supply of solvent  21 , which in this case is lubricant, via a pump  22 . Because a liquid mixture can now collect in the discharge pulsation dampener vessel  7 , the vessel  7  is provided with a drain with a drain valve  23 . The drain valve  23  can be manually actuated or automatically actuated (e.g. by use of a level switch  24 , or by other means), as described above. The addition of lubricant  21  advantageously serves to enhance the sealing and wear life of the compressor  4 . 
         [0028]    The inventors have determined that the chemical composition and addition rate of the lubricant  21  can advantageously be selected in order to segregate the contaminants in the feedstock stream  1  into a liquid mixture of the solvent and any contaminants entrapped or dissolved in the solvent, which can be collected in chambers  7  and  9  and discharged via the valves  23  and  11 , respectively. The lubricant can be the same lubricant used to lubricate the compressor  4  itself. Because dissolved hydrocarbon, water and solid contaminants could alter the properties of the lubricant, it is preferred that a lubricant supply is employed that is separate from the lubricant supply for the mechanical components of the compressor. The use of a separate oil supply in compressors, especially positive displacement compressors, is widely practiced. For example, rotary vane, rotary screw, oscillating scroll, rotary lobe and reciprocating piston compressors are all known to be operated with one lubricant supply for the gas passages and a second supply for the mechanical apparatus. 
         [0029]      FIG. 3  shows the limits of solubility of representative contaminant hydrocarbons in two different compressor lubricants at room temperature. The lower melting point contaminants such as naphthalene have higher solubility limits in room temperature lubricant that the higher ones. Further, in this example, the lower viscosity lubricant advantageously dissolved a greater proportion of contaminants. Because different gas streams may carry different contaminants, it is not possible to identify a preferred lubricant for all cases; however, it is clearly important to establish the solubility limits to ensure that the lubricant chosen has an adequate ability to dissolve the contaminants in question at the temperatures of interest. All of the contaminants illustrated in  FIG. 3  dissolved completely in both lubricants at 100° C. at the 1 g/10 mL concentration level. Therefore, the local prevention of fouling within the compression system according to the present invention can be affected by the relative amounts of lubricant and contaminant flow, the temperature of the lubricant and contaminant mixture, the local concentration of the contaminant, and the chemical composition of the lubricant. 
         [0030]      FIG. 4  illustrates another embodiment of the compression system of the present invention where the compressor discharge buffer  7  of  FIGS. 1 and 2  is replaced by a lower buffer chamber  31 . The lower buffer chamber  31  is placed partially or wholly below the cooler  33 , which is arranged so that condensing liquid is drained into the buffer  31  chamber. The cooler  33  is connected with an upper buffer chamber  32 , which is partially or wholly above buffer chamber  31  and is in fluid communication with the discharge of cooler  33 . In this embodiment, compounds having a lower saturation temperature than that otherwise present in the compressor  4  discharge continually drain, or reflux, into the lower buffer chamber  31 . This materially reduces the temperature in the buffer chamber  31 , but also results in continual cleaning of solid deposits from the surfaces of the cooler  33  and the buffer chamber  31 . This results in a lower overall concentration of high saturation temperature compounds in the liquid mixture collected in the buffer chamber  31  to be drained through a drain with a drain valve  34 , which can be actuated by level sensor  36 , or other means. Although it is conceivable under some circumstances that no liquid would accumulate in the upper buffer chamber  32 , provision for liquid accumulation and removal can be provided via a drain with a drain valve  35  and level sensor  37 . As shown in  FIG. 4 , the functional elements of this embodiment can be combined into a single mechanical assembly  30 . Alternatively, the apparatus can be constructed in plural subassemblies. 
         [0031]      FIG. 5  shows an alternative embodiment of the system in  FIG. 4  where the buffer assembly  30  is a single apparatus. In this embodiment, the cooler  33  is provided with a tube that has an inlet in fluid communication with the lower buffer chamber  31  and a discharge  38  that is in fluid communication with the upper buffer chamber  32 . In this embodiment, the cooler  33  is a removable, U-tube bundle type cooler with a cooling fluid admitted through valve  40 , and passing through flow indicator  41 . The temperature of the gas  10  discharged from the upper chamber  32  can be advantageously used to control the flowrate through the valve  40 . This control can be done manually or automatically, via an electronic controller, or via a mechanical controller, such as a thermostatic valve. The buffer assembly  30  is advantageously provided with a droplet coalescing means  43  to prevent the carryover of liquid or solid contaminants in the gas stream  10 . The droplet coalescing can be accomplished via a packed bed, cartridge filter, or other means known to one skilled in the art. Although the upper and lower chambers  32  and  31  are shown as having the same diameter in  FIG. 5 , these chambers can be provided with different diameters. Furthermore, these chambers can alternatively each be provided with separate pressure boundaries, whereas  FIG. 5  illustrates a single, shared pressure boundary separating the chambers. 
         [0032]    The previous figures illustrate embodiments of the present invention that are useful when the feedgas  1  is not contaminated with species that form fouling deposits at the pressure and temperature existing in cooler  2 .  FIG. 6  shows an embodiment of the present invention that is advantageous for situations where fouling in cooler  2  or in inlet buffer vessel  3  is possible. In this embodiment, the mixture of condensed lubricant and contaminant streams from valves  34  and  35  are supplied to the vessel  3 , for example, the mixture can be returned to the inlet of the cooler  2  at point  50  (as depicted in  FIG. 6 ) which then travels to the vessel  3 , or alternatively the mixture can be returned to the vessel  3  directly, to the pipework conveying the gas  1  to the vessel  3  at a location upstream of the vessel  3  (either upstream or downstream of the cooler  2 , if such a cooler is present), or even to the pipework at a location downstream of vessel  3  such that gravity is then used to feed the mixture to the vessel  3 . Because the liquids from valves  34  and  35  are mixed with the lubricant, they have a lower molecular weight, saturation temperature, and melting point than the components that would form deposits at the low temperatures and pressures characteristic of cooler  2  and vessel  3 . Thus, these liquids can be used to dissolve the deposits. If additional stages of compression are provided for gas  10  as contemplated in the present invention, the liquids captured in buffer assemblies  30  associated with those additional stages of compression could also be returned to location  50 . These liquids would be successively lower in molecular weight than the liquids from valves  35  and  34 . In the limit of many stages of compression, the returned liquids would be essentially only lubricant. 
         [0033]    In order to provide for disposal of the mixture liquid from vessel  3  in a distant tank, or in situation where the gas pressure in vessel  3  is insufficient to effect flow through valve  5 , it can be advantageous to provide a pump  51 . The pump  51  could be provided with a back pressure valve  52  to facilitate continuous operation to prevent cooling and solidification of the mixture liquid in the pump  51 . The valve  5  would still be used to remove liquid from the system, and could still be actuated by the level sensor  6 , as shown. 
         [0034]    If the recycling of mixture from the valves  34  and  35  is not desired, or if the mixture is still difficult to handle or causes fouling, a port  55  in the vessel  3  can be used for the injection of solvent. Such solvent injection could also be practiced at an injection point that is upstream of cooler  2 . The use of a solvent facilitates handling of contaminants at concentrations otherwise too high for dilution in the compressor lubricant, or to economize on the use of compressor lubricant. Alternatively, solvent injection could be used in lieu of compressor lubrication. For dissolving hydrocarbon contaminants such as those in Table 1, solvents such as alcohols, ethers, light hydrocarbons, di-methyl chloride, gasoline and diesel may all serve as solvents. The inventors anticipate that other impurities can be readily dissolved in other solvents. The use of any solvent useful for dissolving the contaminants present is contemplated by the present invention. In one embodiment of the present invention, a coalescing means  56  is provided downstream of the solvent injection point  55  but in fluid communication with vessel  3 , such that the condensed liquid can drain into vessel  3 . This advantageously provides intimate contact between the gas  1  and the solvent injected through point  55 , thus maximizing the removal of contaminants. 
         [0035]    In a further embodiment of the present invention, the cooler  2  can be a direct-contact cooler. For hydrocarbon contaminants, a direct contact cooler using a cooling medium in which the contaminants have minimal solubility is preferred. An example of such a cooling medium is water. When a direct contact water cooler  2  is used, the immiscible hydrocarbon contaminants can be readily separated, and the coolant can be recycled indefinitely. The direct contact cooler  2  can be used with recycled lubricant being injected at point  50 , with lubricant reinjection directly into inlet vessel  3 , or without lubricant recycle. Different gas compositions, pressures and temperatures can make any of these routes desirable, such that none is inherently preferable. 
         [0036]    It should be noted that the exemplary embodiments depicted and described herein set forth the preferred embodiments of the present invention, and are not meant to limit the scope of the claims hereto in any way. 
         [0037]    Numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that, within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.