Closed system refrigeration using a turboexpander
BACKGROUND OF THE INVENTION 
     1. Field of the invention 
     The present invention relates to improved closed cycle refrigeration systems, particularly for removing excessive hydrocarbons or other chemicals from air-vapor mixtures by condensation. 
     2. Related information 
     Environmental concerns have led to a requirement for the reduction of chemical vapors, particularly hydrocarbons emitted into the atmosphere from every possible source. One of the sources targeted are bulk loading and unloading terminals. In these terminals a vapor recovery system is used to gather the air containing hydrocarbons or other vapors which are emitted during loading and unloading operations. The vapors are commonly separated from the air by refrigeration of the air-vapor mixture to cryogenic temperatures. The refrigeration systems can reduce &#34;condensable&#34; hydrocarbons or other condensable materials in the vented air to acceptable levels, i.e., loss than 80 mg/l. 
     The cryogenic temperatures required, i.e., about -100° F., necessitate efficient refrigeration to achieve the separation. Since the total amount of refrigeration, expressed in tons (1 ton=12,000 BTU removed), is small when compared to large scale plants, such as ice plants and gas liquefaction plants, less efficient closed refrigeration cycles can be used with the common fluorocarbon refrigerants such as Freon 12. 
     With less efficient refrigerants, greater circulation and more compression power is required. Cascade refrigeration, using two refrigerants--one to cool the other--is an alternative. The most commonly used closed refrigeration cycle in these smaller scale plants is the compression of the refrigerant followed by cooling at the higher pressure and expansion across a Joules-Thomson expansion valve, the cycle being used to cool both refrigerants in the cascade refrigeration system. However, with the advent of concerns about damage to the atmosphere attributed to the fluorocarbons, these are being banned or expected to be banned in commercial operations. 
     A turboexpander may be used when the refrigerant is at a &#34;free&#34; higher pressure. The most common use of the turboexpander is in the natural gas processing industry. More specifically it is used in the demethanizer separation column when there is a free pressure drop, that is, the entering gas from the well or pipeline is at a pressure above that necessary for the separation. Generally the entering gas mixture is first pre-cooled by heat exchange with the exiting methane from the tower and the condensed liquids separated in a separator. The gas, containing mostly methane, is expanded across a turbine to the tower operating pressure and thus chilled. An enlarged top portion of the column acts as a separator for the expanded gas. To achieve an essentially isentropic expansion of the gas the turbine is coupled to a drive shaft which may have a brake applied or drive a compressor which partially compresses the product methane toward the desired pipeline pressure. The brake is required to vary the load on the turboexpander and match it with the compressor load. A situation where the mass flow in both the turboexpander and compressor is proportional is desirable for control purposes. Although the demethanizer is the most common application of the industrial turboexpander, its use in a closed refrigeration system has been proposed in &#34;Introduction To Chemical Engineering Thermodynamics&#34;, Smith and Van Hess, Second Edition, McGraw-Hill Book Company, Inc. , New York, 1959, pp.301-303. 
     Adaptation of the turboexpander to the closed cycle system of refrigeration for smaller scale plants could achieve greater efficiency and allow use of less efficient refrigerants. 
     SUMMARY OF THE INVENTION 
     Briefly the present invention utilizes a turboexpander in place of the Joules-Thomson expansion valve in a conventional refrigeration system to achieve higher efficiency. The turboexpander replaces the Joules-Thomson expansion valve, which is essentially adiabatic, with a turbine which takes work out of the expansion making it essentially isentropic. The isentropic expansion allows for a lower temperature of the expanded refrigerant at the same pressure reduction. More specifically the refrigeration is used in removing condensable hydrocarbons or chemicals from air which has been contaminated during loading and unloading at bulk plants. The more efficient turboexpansion cycle allows the use of saturated aliphatic hydrocarbons, such as ethane, propane or butane, as refrigerant, the use of which would be precluded from normal Joules-Thomson expansion cycles. Preferably the refrigerant is ammonia, nitrogen or a saturated lower aliphatic hydrocarbon, more preferably having C 2  to C 6  carbons. 
     Basically the process of the present invention comprises: 
     (a) compressing a refrigerant gas at temperature T 1  and pressure of P 1  to a temperature T 2  and pressure P 2  in a first compressor; 
     (b) cooling said compressed refrigerant gas to a temperature of T 5 , T 5  &gt;T 1 , in a condenser such that substantially all of said refrigerant gas is condensed to a refrigerant liquid; 
     (c) expanding said refrigerated liquid to a pressure of P 7 , P 7  &lt;P 6 , across a turboexpander, said turboexpander driving a second compressor to remove work and providing an essentially isentropic expansion of said refrigerant liquid to a refrigerant gas and cooling said refrigerant gas to a cryogenic temperature of T 7 , T 7  &lt;T 6  ; 
     (d) indirectly exchanging heat from said mixture at a temperature of T 8  to said refrigerant gas in a vapor chiller to increase the temperature of said refrigerant gas to about T 10  and cooling said mixture to a temperature of T 9 , T 8  &lt;T 10 , thereby condensing substantially all of said hydrocarbons in said mixture; 
     (e) compressing said refrigerant gas at a temperature T 3  and pressure P 3  to a pressure of P 4  and temperature T 4  in said second compressor, P 1  &lt;P 2  &lt;P 4 , and returning said refrigerant to the inlet of said first compressor for recycle; 
     (f) venting said air less substantially all of said hydrocarbons to the atmosphere; and 
     (g) recovering said condensed hydrocarbons. 
    
    
     BRIEF DESCRIPTION OF THE DRAWING 
     The FIGURE depicts a simplified flow diagram of the present invention as used in vapor removal from air. 
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 
     In one embodiment of the present invention ethane is used as the refrigerant in a closed loop compression, turboexpander cycle to cool air containing hydrocarbons and condense the hydrocarbons for removal. The FIGURE depicts a flow diagram of this application with dashed lines surrounding the refrigeration cycle, 
     The air-hydrocarbon vapor mixture containing water is collected in header 1 and passed through flow lines 1a or 1b to one of two dehydrators 110a or 110b to remove the water from the vapor. The water must be removed to prevent freezing and plugging of the lines at the temperatures used. The dehydrators 110a and 110b contain a common gas desiccant such as a molecular sieve and are arranged for parallel flow so that the sieve in one may be regenerated while the other is in service. Water is removed from the dehydrators to disposal line 16. 
     The now dry vapor mixture at substantially atmospheric pressure and temperature is next passed to a precooler 200 via flow line 2 where it is cooled to a temperature T 8  of about 0° F. by indirect heat exchange with the cold vented air. The vapor mixture is then chilled to a temperature T 9  of about -130° F. in vapor chiller 180 wherein about 90+ percent of the condensable hydrocarbons are liquified by indirect heat exchange with the cold refrigerant gas from the refrigerant section. The liquid vapors, containing essentially no water, are recovered in separator 190 and sent to storage through flow line 5 by pump 210. Check valve 220 in flow line 6 prevents backflow of vapors and vapor lock of pump 210. Meter 230 is provided to monitor the flow rate of recovered vapors. 
     The air effluent from the separator 190 is passed via line 17 first to vapor precooler 200 to absorb additional heat from the vapor mixture by indirect heat exchange therewith. The air at temperature T 12  of about 60° F. may then be vented to the atmosphere via line 7 containing less than about 35 mg/l of condensable hydrocarbons which is well within current EPA limits. 
     Now turning to the refrigeration cycle, cooling is provided for vapor chiller 180 by the compression-turboexpansion cycle of refrigerant gas, such as ethane. The refrigerant gas is first compressed in recompressor 120 to a temperature T 2  of about 170° F. and a pressure P 2  of about 100 psig. The refrigerant gas is then carried by flow line 9 to aerial condenser 130 where it is cooled to temperature T 3  of about 110° F. at constant pressure, the refrigerant gas is then compressed in a second stage recompressor 140 to a temperature T 4  of about 200° F. to a pressure P 4  of about 450 psig. The refrigerant gas is then carried by flow line 11 to aerial condenser 150 where it is cooled to temperature T 5  to about 110° F. at constant pressure, thereby condensing substantially all of the refrigerant to a liquid. The refrigerant is partially cooled by the returning refrigerant gas via line 15, by indirect heat exchanged in heat exchanger 160° to about 0° F. The refrigerant liquid is then passed via flow line 13 to the inlet side of turboexpander 170 where the refrigerant is expanded essentially isentropically to pressure P 7  of about 10 psig and thereby cooled to a cryogenic temperature T 7  of less than -100° F. The exiting low pressure refrigerant gas is used to chill the air-vapor mixture via line 14 by indirect heat exchange in vapor chiller 180. The transfer of heat to the refrigerant in chiller 180 raises the temperature of the refrigerant gas to temperature T 10  , about -100° F. It is then passed via line 15 to heat exchanger 160 to remove any liquid by indirect contact with the liquid refrigerant in line 12 which is at T 1  60° F. and P 1  10 psig prior to partially recompressing it to a pressure P 2  of about 100 psig in compressor 120 driven by turboexpander 170. The partially recompressed refrigerant gas is then passed to the suction side of second stage recompressor 140 (driven by motor 141) via flow line 10 where the cycle begins anew. 
     The turboexpander is able through substantially isentropic expansion, which produces work, to cool the refrigerant gas to a cryogenic temperature more easily than a simple Joules-Thomson expansion. Thus the use of the turboexpander will allow a gas to be cooled to -100° F. using less horsepower than would be required in a conventional cascade type refrigeration system. Additionally, the closed loop system provides the same mass flow through both expander 170 and compressor 120 alleviating loading and control problems. 
     Generally the process of the present invention comprises: 
     (a) compressing a refrigerant gas from temperature T 1  and pressure P 1  to temperature T 2  and pressure P 2  in a first stage of compression (120), 
     (b) cooling said compressed refrigerant gas to temperature T 3  and pressure P 3  in a first condenser (130), 
     (c) compressing said refrigerant gas from said temperature T 3  and pressure P 3  to temperature T 4  and pressure P 4  in a second stage of compression (140), 
     (d) cooling said compressed refrigerant gas to temperature T 5  and pressure P 5  in a second condenser (150), such that substantially all of said gas is condensed to a refrigerant liquid, 
     (e) expanding said refrigerant liquid to a pressure of P 7 , and temperature of T 7 , across a turboexpander (170), driving the first stage compressor (120) to remove work and providing an essentially isentropic expansion of said refrigerant liquid to a cryogenic refrigerant gas, 
     (f) indirectly exchanging heat from a air-vapor mixture at temperature T 8  with refrigerant at temperature T 7  (T 8  &gt;T 7 ) in a chiller (180), cooling said air-vapor mixture to a temperature of T 9 , thereby, condensing substantially all of said hydrocarbons or chemical vapors in said mixture, 
     (g) recompressing said refrigerant gas at temperature T 1  and pressure P 1  in said first stage compressor (120), 
     (h) venting said air less substantially all of said hydrocarbons or other chemical vapors to the atmosphere and 
     (i) recovering said condensed vapors. 
     Preferably, said air-vapor mixture at temperature T 9  with entrained condensed hydrocarbon or chemical vapors passes to a separator (190) in which the condensed vapors are accumulated, said air emissions vent through the inlet interchanger (200) exchanging heat from the inlet air-vapor mixture at temperature T 11 , prior to venting to atmosphere and the accumulated condensed hydrocarbon or chemical vapors from the separator (190) are discharged to storage. 
     In addition it is preferably to indirectly exchange heat from said refrigerant liquid at said temperature of T 5  and pressure P 5  with said refrigerant gas at temperature T 10  and pressure P 10  in an interchanger (160), thereby cooling said refrigerant liquid to temperature T 6  and pressure P 6  and warming said refrigerant gas to temperature T 1  and pressure P 1 . 
     The temperatures and pressures are given for a particular system as an exemplification and for illustration purposes and are not intended to limit the scope of the invention which is defined by the appended claims.