IMPROVED TRIPLE EFFECT ABSORPTION APPARATUS AND METHOD Background of the Invention In U. S. Patent Nos. 5,335,515 and 5,390,509 there are disclosed triple effect absorption cycle apparatus and systems incorporating one or more absorbers for directing an aqueous absorption fluid to first, second and third generators operating at successively higher temperatures. These triple effect apparatus include three condensers operating at successively higher temperatures and communicating with the generators. The three condensers are also interconnected whereby condensed refrigerant flows successively from the third condenser to the second condenser, then to the first condenser, and thereafter to one or more evaporators. The heat generated in the
condensers is used to drive the lower generators. The use of such apparatus in which a single refrigerant such as water is used throughout the system achieves substantial improvement over prior art systems which rely on heat transfer coupling of heat exchangers with no common mass flows.
As advantageous as the aforesaid triple effect apparatus are, vapor pressures of the absorption solution in the high temperature, third generator are usually above 25 psig, and are normally operated at between about 40 and about 80 psig, typically at about 60 psig. In many areas, present boiler codes require that absorption cycle apparatus boilers or generators operating above 15 psig must be monitored by an operator at all times during operation. Such requirement obviously is economically disadvantageous, and where costs and expenses of operation are of great importance, the use of apparatus having high generator pressure requirements is handicapped. It is to the elimination of such a disadvantage of the aforesaid triple effect apparatus and systems that the present invention Us directed.
Summarv of the Invention The present invention is directed to methods of operating the triple effect absorption cycle apparatus using a high temperature third generator operating at reduced pressures, preferably less than 15 psig. The triple effect apparatus used in the invention is disclosed in U. S. Patent No. 5,390,509 as well as 5,205,136, all of
which disclosures are incorporated herein by reference. The low pressure operation of the high temperature third stage generator is achieved, according to invention, by using relatively high metal salt concentrations in the absorption fluid in the third stage generator. The high concentration for strong solution in the third stage generator is achieved by using relatively low sorption fluid flow into the highest temperature generator and desorbing water vapor and allowing the salt concentration to substantially increase in the generator as compared to concentrations tjsed in prior art systems.
Brief Description of the Drawings Figs. 1 and 2 are schematic illustrations of triple effect absorption cycle apparatus which may be used and operated according to the invention.
Detailed Description of the Preferred Embodiments In Figs. 1 and 2 there are schematically illustrated tripled effect cycle apparatus, which illustrations are substantially identical to corresponding Figs. 1 and 2 in U. S. Patent No. 5,390,509. In each of the illustrated triple affect systems, a single absorber and evaporator are used. However, the invention is not limited to single absorber apparatus and two or three absorbers and two or three evaporators may be used. Thus, all of the apparatus shown and disclosed in the aforesaid U. S. Patent Nos. 5,335,515 and 5,390,509 may be used in the present invention.
Multiple absorber and evaporator units are advantageous if fluid crystallization limits endanger safe operation of the cycle in the liquid solution field. However, the single evaporator absorber systems are shown for relative simplicity for describing the present invention. The essential feature of the present invention is in operating the high otage generator, G3 at an internal absorption fluid vapor pressure below the pressure which requires operator observation by code. For example, where the local code requires the presence of an operator where generator pressures are 15 psig, according to the invention, the high stage generator G3 is operated below 15 psig. Of course, the lower stage generators G2 and G, will also be operated at pressures below the code operator requirements. The low pressure operation is achieved by substantially increasing the salt concentration in the absorption fluid of the
third stage generator. Typically, in using prior art systems as described in the aforesaid patents, the salt concentration in the absorption fluid in the high stage generator G3 is increased via desorption of water by between about 4% and about 6% of the relatively weak concentration supplie to the generator. Thus, in such typical prior art systems, the salt concentration in the absorption fluid leaving the high stage generator G3 is about 4% and about 6% higher than the salt concentration in the absorption fluid fed to the generator from an absorber, or from b lower stage generator. In the present invention, the salt concentration for the strong solution in the third generator is substantially increased to be capable of and sufficient to provide generator operating pressures below 25 psig.
Specific salt concentration increases are between about 10% and about 25%, and preferably between about 12 and about 20%, by weight, from the concentration of salt in the weaker solution introduced into the generator. Such salt concentration increases are achieved by utilizing relatively low flows of the absorption fluid into the generator.
The temperatures within the generators, and particularly high stage generator G3 will be substantially the same as described in the aforesaid patents. Typical third stage generator operating temperatures are between about 380°F and about 500°F, with optimum operating temperatures between about 400°F and about 450°F. Third stage generator G3 is preferably direct fired for economical reasons, using a burner and combustion air pre-heating capabilities and components, well known to those skilled in the art. However, where appropriate, indirect heating bf the high temperature generator G3 may be used with phase change or pumped fluid loop equipment. Any remaining energy or sensible heat below that required to heat the high temperature generator may be directed to one or both of the lower stage generators. Thus, where the third stage generator is direct fired, available hot gases of combustion may be directed to heat one or more of the lower stage generators.
As shown in Figs. 1 and 2, as well as described in substantial detail in the aforesaid U. S. Patent
Nos. 5,335,515 and 5,309,509, the disclosures of which are incorporated herein by reference, the fluid circuit for directing the aqueous absorption fluid between one or more absorbers and the three generators may be in series, parallel and reverse fluid flow, as well as combinations of two or more of these different flows. As such, any one or more of the absorbers may feed more than one generator with the same fluid, and the flow sized or metered for proper heat balance. Thus, usually the mass or volume flows from different absorbers to different generators are not the same or even, and when using junctions for combining fluids, the specific flows to a specific generator can 5be selected and regulated as desired. Particularly, according to the invention, it is important to regulate, control or
meter the flow to the third stage generator G3, in order to achieve low flow rates and allow the concentration of the salt within the absorption fluid to substantially increase. Thus, observing Fig. 1, flow splitting junctions 13 and 15, which preferably include appropriate pipe size restrictions or metering valves for selecting the mass or volume of fluid flows to the lower stage generators G2 and G, as well as to high temperature generator G3. Similarly, in Fig. 2, junctions 27 and 28, as well as 26 and 29 may be provided with pipes of suitable size, restrictions or metering valves for ultimately selecting the appropriate flow of absorption fluid to generator G3 in order to carry out the present invention.
A preferred triple effect system according to the invention utilizes a parallel flow cycle arrangement, such as illustrated in Fig. 1, although again, the number of absorbers andlor evaporators are not limited to the single absorber systems shown. Such parallel flow systems may also be combined with series andlor reverse flow directing fluid loops, such as further described in the aforesaid and incorporated patents. Preferably, the flow to the third stage generator G3 is below about 20% (mass or volume) of the total system weak solution flow, i. e., the portion of the fluid from the absorber in a single absorber system to G3, or the weak solution absorber, designated A3 in a three absorber system or A2 or the portion from A2 to G3 in a two absorber system. More preferably, the weak tsolution flow to the third stage generator is tess than about 15% of the total weak solution flow in the system.
The solutions making up the absorption fluids in a system according the present invention are aqueous solutions of a metal salt which may be an alkali, alkaline or transition metal halide, or an alkali metal hydroxide.
The halide is preferably bromide or chloride, and the preferred metal is lithium. Thus, the preferred salts are lithium bromide or lithium chloride, or mixtures thereof, with lithium bromide being most preferred. Such lithium halide salts
are concentrated to at least 66.5%, by weight in the highest stage generator G3 to achieve the required low vapor pressure according to the invention. Preferred strong solution lithium halide concentrations in the third stage generator are between about 67% and about 76%, by weight. The other metal halides within the aforesaid list are also used in the same vapor pressure suppression range. However, the specific concentrations of any specific salt or salt mixture to be used may be determined by measuring the concentration at the third generator outlet flow at the desired low pressure.
Other metal salts include alkali metal hydroxides or mixtures of such hydroxides, with sodium hydroxide andlor potassium hydroxide, cesium hydroxide, rubidium hydroxide and their mixtures preferred. The strong solution concentration of the hydroxides for achieving the desired low solution vapor pressures in the high stage generator are between about 70% and about 88%, by weight. However, again, specific concentrations to achieve the desired 5third stage low pressure operations may be readily determined.
Where the metal halide salts are used, it is advantageous to incorporate a hydroxide, for example, an alkali netal hydroxide such as lithium hydroxide or sodium hydroxide for pH control of the fluid for reducing corrosion roblems. It is particularly important to use a corrosion inhibitor in the high stage generator, because of the temperature of the solution. Molybdate, silicate, tungstate, borate, nitrate or combinations of two or more such : orrosion inhibitors may be used. The use of such corrosion inhibitors are well known to those skilled in the art.
Where lithium halide aqueous absorption fluid is used, it may also be desirable to use a crystallization inhibitor additive. Such additives include ethanolamine and ethylene diamine, and their use is known to those skilled in the art.
By way of example, a triple effect absorption system shown in Fig. 1 is operated using an aqueous lithium bromide absorption fluid. The temperature of the weak absorption solution entering the third stage generator G3 is 312.0°F and the lithium bromide concentration is 54.36%, by weight. The solution leaving the generator G3 has a temperature of 426.4°F and a lithium bromide concentration of 71.75%, by weight. During the process, the maximum pressure in generator G3 is 11.73 psig. In the system, the concentration of lithium bromide from generator G2 is 57.35% and from generator G, is 57.19%.
In operating a reverse flow cycle apparatus of Fig. 2, the concentration of lithium bromide in the aqueous absorption solution directed into generator G3 is 58.37% and after refrigerant desorption, the fluid directed from the generator is concentrated at 70.93% lithium bromide, by weight. The operating temperature of the weak solution directed into generator G3 was 352.7°F and the concentrated solution flowing from the generator has a temperature of 424.5°F. During the triple effect cycle operation, the maximum absorption fluid vapor pressure in the high stage generator G3 is 13.60 psig. Lithium bromide concentration in the solution entering generator G2 is 56.27%, and leaving the generator at 58.37%, by weight. The absorption solution entering generator G, has a salt concentration of 55.13%, and leaving the generator at 56.27%, by weight.
As previously described, the invention is in operating the high stage generator G3 of a triple effect absorption cycle apparatus at pressures of less than 25 psig, preferably less than 20 psig, and more preferably less 5than 15 psig. However, the intent is to avoid the requirement of a manned operator or observer present during the system operation as required by a code for generator pressures at or in excess of the code requirements.