Silver nitrate produced by a continuous evaporative crystallization process

Abstract: Silver nitrate crystals comprising a substantially non-platelet crystal morphology as well as an apparatus and process for preparing silver nitrate crystals by evaporative crystallization are disclosed. The non-platelet silver nitrate crystals have an aspect ratio in the range of from about 1:2:3 to about 1:1:1.

Description: Technical Field The present invention relates to silver nitrate crystals, improved, cost-effective process for the manufacture of silver nitrate. In particular, the present invention relates to an improved form of silver nitrate crystals and the preparation of crystalline silver nitrate by evaporative crystallization and compaction of the crystals into a freely flowable form. Prior Art Silver nitrate crystals are produced by crystallizing silver nitrate in a slurry in a crystallizer. Slurry containing crystals is then withdrawn from the crystallizer and introduced to a separator to separate silver nitrate crystals from the slurry. Silver nitrate crystals prepared by prior art processes have a platelet-type of crystal morphology that can render the crystals difficult to separate and dry. The separation and drying of such crystals can be time-consuming and costly, and crystals can tend to break and not separate out, further increasing process costs and inefficiency. In the process that is generally used for preparing silver nitrate, an aqueous silver nitrate solution is prepared and introduced to a cooling crystallizer. Cooling of the solution induces silver nitrate crystal growth. Solution containing silver nitrate crystals is then drawn from the crystallizer and the silver nitrate crystals are separated and dried. Prior art processes suffer from serious deficiencies that have hindered their industrial utility. For example, a growth crystallizer such as a continuous cooling crystallizer typically has a residence time of about 12 to 24 hours, because low supersaturation is required to avoid fouling of the heat transfer surfaces. At shorter residence times and higher supersaturation, product begins to build up on cool metal surfaces, leading to fouling and blockage of the heat exchanger. A commercial size silver nitrate cooling crystallizer may therefore have to be shut down frequently, e.g. every 24 hours, for steam cleaning and defouling. Also, the process is time consuming because of the high residence time. This means that for a desired output of product, a large inventory of solution and therefore of silver must be maintained in the crystallizer. The size and the cost of the apparatus and facilities therefore is also high. Another drawback is that silver nitrate crystals prepared by prior art processes do not exhibit uniform growth along the crystal axes, resulting in a product that is difficult to separate from solution and dry, necessitating a time-consuming and costly separation and drying process. The crystals have a size distribution that is broad, and a mean particle size that can vary extensively due to changing crystallizer conditions such as heat transfer surface fouling. Consequently, the crystal product can vary widely in moisture content, product flowability, and percentage of fines or dust, causing quality control problems with inconsistent product and increased exposure to workers of hazardous airborne dust. The silver nitrate product crystals also tend to fuse, such as when the product is packaged, and form into large chunks or blocks of product. The product is then difficult to handle since it is heavy and bulky. Problem to be Solved by the Invention It is the objective of the present invention to provide an industrially feasible and economically practical process for forming silver nitrate crystals having an improved crystal morphology. It is another objective of the present invention to provide a process for manufacturing silver nitrate that is capable of extended operation without the necessity of frequent shutdown and that is also capable of forming silver nitrate crystals having an improved crystal morphology. Disclosure of the Invention This invention provides silver nitrate crystals having a substantially non-platelet morphology as illustrated by FIGS. 4 AND 5. Typically, the crystals of the invention are non-platelet, as signified by the aspect ratio which is typically in the range of from about 1:2:3 to about 1:1:1, the latter defining a cubic structure. The crystals typically have a mean particle size in the range of about 200 µm to about 600 µm, and a size distribution of from about 70 µm to about 1000 µm. In accordance with this invention, there is also provided a process for continuously producing silver nitrate crystals from an aqueous silver nitrate solution according to claim 1 of the application. The aqueous silver nitrate solution is introduced to an evaporative crystallizer. The solution is heated and concentrated by evaporation in a crystallization zone of the crystallizer to form a slurry comprising silver nitrate crystals. The slurry in the crystallizer is agitated to promote uniform crystal growth. Some of the slurry is withdrawn from the crystallizer, and silver nitrate crystals are separated from the withdrawn slurry and dried. A partial vacuum can be maintained in the crystallizer to promote evaporation and crystallization. An evaporative crystallizer having a solution level controller is provided for carrying out the process of claim 1 of the application. Means for heating and concentrating the aqueous silver nitrate solution in a crystallization zone of the crystallizer to form the slurry is also provided. The apparatus also comprises means for measuring the slurry density and for controlling the means for heating to maintain the slurry density within a desired range. The apparatus further comprises means for agitating the slurry and means for introducing a silver nitrate feed solution to the crystallizer. Means for maintaining a partial vacuum in the crystallizer can also be provided. Advantageous Effect of the Invention The silver nitrate crystals of the invention are prepared rapidly by evaporative crystallization. In other words, the residence time of material in the crystallizer is short, e.g. on the order of about 1 to 3 hours. The crystals can therefore be prepared efficiently and at a reasonable cost. The crystals are easily separated and dryed, which further adds to the speed and efficiency of their preparation. The crystals also exhibit good resistance to breakage during separation, which further improves the efficiency of their preparation since more crystals are effectively separated and therefore less are recycled to the crystallizer. The process of the invention is substantially free of the problem of heat exchange surface fouling and blockage. The invention can therefore be practiced under conditions that require just a short mean residence time of material in the crystallizer, for example on the order of about 1 to 3 hours, and substantially shorter than prior art mean residence times. A high output of silver nitrate crystal product can therefore be produced with relatively inexpensive, smaller equipment than are required by prior art systems. A further cost saving is achieved because the total plant silver inventory is much less than that of prior art systems due to the short residence time and high product throughput of the invention. For example, total silver inventory can be on the order of 80 percent less than a similar-scale prior art system, and can thus provide substantial savings in silver inventory costs. Also, fewer shutdowns may be necessary, resulting in a more efficient and cost-effective system. The invention also produces a silver nitrate crystal product having a crystal morphology that facilitates separation and drying. These and other aspects, objects, features and advantages of the present invention will be more clearly understood and appreciated from a review of the following detailed description of the preferred embodiments and appended claims, and by reference to the accompanying drawings. Brief Description of the Figures Figure 1 is a schematic representation of an apparatus of a continuous crystallization system to carry out the process of claim 1 of the apllication. Figure 2 is a graph showing the mean particle size and size distribution for the process of the invention and for a comparative process. Figure 3 is a photomicrograph at magnifications of 10X, 20X, and 30X of silver nitrate crystals prepared by batch mode evaporative crystallization. Figure 4 is a photomicrograph at magnifications of 10X, 20X, and 30X of silver nitrate crystals prepared by a pilot plant continuous evaporative crystallization process and apparatus. Figure 5 is a photomicrograph at magnifications of 10X, 20X, and 30X of silver nitrate crystals prepared by a pilot plant continuous evaporative crystallization process and apparatus. Figure 6 is a schematic representation of separation and compaction apparatus. Figure 7 is a front elevation schematic view of a roll compactor. Figure 8 is an enlarged, schematic representation of a compact of the invention. Figure 9 is a front elevation view showing detail of the compactor roller surface. Figure 10 is a graph of moisture content in the product versus the ratio of drying air flow rate to product flow rate. Figure 11 is a graph of product pH versus drying air flow rate. Figure 12 is a graph of product moisture content versus drying air flow rate. Figure 13 is a graph of compact density versus compaction pressure for compacted silver nitrate of the invention. Detailed Description of the Invention The preparation of the aqueous silver nitrate solution used as a starting material in the invention is well known and is described, for example, in U. S. Pat. No. 5,000,928. The equation for the reaction of silver with nitric acid can be expressed as follows: 4Ag + 6HNO 3 → 4AgNO 3 + NO + NO 2 + 3H 2 O After preparation, the silver nitrate solution can be purified prior to use as a starting material in the invention as is discussed further below. Purification of silver nitrate solutions is described, for example, in U.S. Pat. No.s 1,039,325, 2,581,519, 5,000,928, and Jap. Kokai No. 52[1977]-60294. Referring now to FIG. 1, silver nitrate solution is introduced as the feed solution to evaporative crystallizer 10 via line 12 and flow control valve 14, the level of solution in crystallizer 10 being shown schematically as the dotted line. For efficient operation of the crystallizer, the concentration of silver nitrate in the silver nitrate feed solution should be in the range of from about 60 to about 90 percent by weight. The temperature of the feed solution entering the crystallizer should be in the range of from about 20°C to about 85°C. The flow rate of feed solution to the crystallizer and/or the slurry discharge from the crystallizer can be established based on the desired production rate. Crystal growth is dependent on mean residence time in the crystallizer and other factors that are further discussed below. The evaporative crystallizer employed to carry out the process of the invention should be a well-mixed evaporative crystallizer, such as is described below, in Perry's Chemical Engineer's Handbook , 6th Ed., Section 19, Liquid-Solid Systems , "Crystallization Equipment", Miller et al, pp. 19-35 to 19-40 (hereinafter "Perry's"), incorporated herein by reference, and in Chemical Engineer's Handbook , 4th Ed., Section 17, "Crystallization", Perry et al, pp. 17-7 to 17-23 (hereinafter "Crystallization"). According to FIG. 1, the crystallizer 10 is a draft tube evaporative crystallizer comprising draft tube 16. Means for introducing the silver nitrate feed solution to crystallizer 10 can comprise any convenient system, e.g. a continuous silver nitrate feed solution production facility having an output pipeline serving as the input pipeline to crystallizer 10. Bladed agitator 20 is means for agitating the solution and the slurry along the flow path indicated by the direction arrows to promote the formation of a well-mixed slurry in a crystallization zone in and around draft tube 16. The solution level in the crystallizer should be maintained above draft tube 16 but by not more than about 2 inches (5 cm) to 6 inches (15 cm) to avoid leaving a poor slurry crystallization zone thereabove due to insufficient agitation and flow. At such a solution level, the crystallization zone effectively is the entire solution volume shown in crystallizer 10. Silver nitrate crystals typically form and grow while suspended in the crystallization zone. The well-mixed slurry promotes uniform silver nitrate crystal growth to achieve a desirable non-platelet crystal morphology as discussed below. Agitator 20, for example a bladed agitator, is turned by shaft 22 which in turn is driven by motor 24. The silver nitrate slurry is dense, and agitator 20, shaft 22, and motor 24 should be sized accordingly, based on factors such as desired agitation rate and maximum expected loading. One skilled in the art can readily select the appropriately sized and powered agitator system for the particular crystallizer system design. A crystallizer level controller system comprises level detector 26 that measures the level of solution in crystallizer 10 and provides a signal to level controller 28. Controller 28 provides an output signal to control valve 14, thereby automatically regulating the flow rate of feed solution to the crystallizer to maintain a desired level in the crystallizer. Means for heating and concentrating the solution in the crystallizer is steam jacket 30 to which steam, e.g. low pressure steam at about 3 psig (0.4 kPa) to 15 psig (2 kPa), is supplied via line 32 and flow control valve 34. The heating evaporates water from the supersaturated solution, causing silver nitrate to crystallize and precipitate. Crystallizer 10 can also be heated by any other convenient heat transfer means such as are well known in the art. A preferred slurry temperature is in the range of from about 100°F (38°C) to about 140°F (60°C). At higher slurry temperatures, crystal growth can become too rapid and undesirable amounts of fines can form. Preferably, a partial vacuum is provided and maintained in the vapor space in the crystallizer. The vacuum, for example, can be in the range of from about 23 mm Hg absolute to about 200 mm Hg absolute, with a preferred level of about 112 mm Hg absolute. The solution in the crystallizer is heated while vacuum is drawn. Means for maintaining a partial vacuum can comprise a cooling condenser having a vacuum source such as a vacuum pump to which the process gases, primarily water vapor, from the crystallizer vapor space can be exhausted. The heating under vacuum creates a concentrated, supersaturated slurry in which silver nitrate crystals are formed and grow Crystallization conditions such as slurry density and mean residence time are controlled in order to obtain a desired crystal habit and size. Crystal formation and its mechanisms are further described in "Crystallization" at pp. 17-11 to 17-15, incorporated herein by reference. Means for measuring the slurry density and for controlling the means for heating to maintain the slurry density within a desired range comprises differential pressure transmitter 36 and controller 38 that controls valve 34. Slurry density is measured by differential pressure transmitter 36 with diaphragm seals, which transmitter is a standard well-known device such as the Model 3051C manufactured by Rosemount, Inc. The concentration of solids in the slurry is related to slurry density by the equation Concentration of Solids = Slurry Density - Mother Liquor Density. Slurry density is proportional to the pressure differential across differential pressure transmitter 36. Transmitter 36 provides a signal representative of solids content to controller 38. Controller 38 then provides a control signal to control valve 34 to adjust steam flow and thereby control the heating rate in the crystallizer. The slurry density is thus maintained at a desired level by controlling the heating of the slurry to thereby control evaporation from the slurry. In a preferred embodiment, slurry density is maintained in the range of from about 2.7 g/cc to about 3.2 g/cc, corresponding to about 18 to 45 weight percent silver nitrate, respectively. Alternatively, slurry density can be monitored manually and the crystallizer heating can be controlled manually, although automatic control as described is preferred. The term "mean residence time" can be defined as the average time a unit of material, e.g. silver nitrate, remains in the crystallizer after introduction. The mean particle size and size distribution of crystals in the slurry is primarily determined by the mean residence time and the agitating regime in the crystallizer. For steady state conditions, mean residence time can be defined by the equation Mean Residence Time = Vol s /v ws where Vol s is the volume of slurry in the crystallizer and v ws is the volumetric rate of withdrawing slurry from the crystallizer, with other parameters, e.g. slurry density and feed solution plus recycled solution flow to the crystallizer, being substantially constant. The smaller the mean particle size of the crystals, the more difficult it is to separate the crystals from the withdrawn portion of the slurry. Therefore, it is desirable to obtain crystals in the slurry having a mean particle size and size distribution capable of cost-effective separation, a factor which can influence the selection of minimum residence time. The upper limit on residence time is mainly determinable in regard to process efficiency, because crystal breakage tends to limit further process gains in crystal growth and size for long residence times in the apparatus of the invention. One skilled in the art can readily select the residence time for a particular system design and separator and for a desired product characteristic and output. For the preferred embodiment of the invention described herein for the stated operating parameters, e.g. feed concentration, feed temperature, and vacuum, a preferred residence time is in the range of from about 60 minutes to about 180 minutes. FIG. 2 shows the smaller mean particle size and size distribution of silver nitrate crystals formed by the process of the invention as compared to that formed by cooling crystallization. The size distribution and mean particle size of the crystals in the slurry are dependent on crystallization process conditions and on the crystallizer apparatus employed. Typically, the silver nitrate crystals of the invention have a size distribution in the range of from about 70µm up to about 1000 µm and a mean particle size of from about 200 µm to about 600 µm. It has also been surprisingly found that, with the appropriate selection of residence time for a given set of process parameters, a form of silver nitrate crystal can be obtained that can be separated from the slurry and dried with less difficulty than with other known processes, as discussed further in the Examples. FIG. 3 shows silver nitrate crystals formed by a different process and apparatus. As shown in FIGS. 4 and 5, the process and apparatus of the invention produce silver nitrate crystals having more uniform growth along each axis than the silver nitrate crystals of FIG. 3. Prior art processes produce silver nitrate crystals having irregular crystal sizes and morphologies, and such crystals have a tendency to form agglomerates of platelet-like crystal structures. In comparison, the silver nitrate crystals of the invention have a more regular size and morphology and are more cubic than prior art crystals. The terms "more cubic" or "cubical" are meant to include orthorhombic crystals, that is, crystals having a polyhedron structure having x, y, and z axes, and each such pair of axes having about a 90 degree angle therebetween. Crystallization process parameters such as flow rates and residence time can be established to produce a slurry containing the cubic silver nitrate crystals of the invention. A preferred cubic silver nitrate crystal of the invention has an aspect ratio of between about 1:2:3 to 1:1:1, where aspect ratio is defined as the ratio of the x, y, and z orthorhombic crystal axes. As discussed in the Examples below, the cubic silver nitrate of the invention is more easily deliquored, i.e. separated from the slurry, than irregular or platelet silver nitrate crystals, and therefore the process of the invention requires less time and can employ smaller, simpler apparatus to produce a given quantity of usable product than other processes. "Crystallization", pp. 17-7 to 17-8, incorporated herein by reference, further describes and defines the various crystallographic systems. Means for withdrawing slurry comprising silver nitrate crystals from crystallizer 10, and for providing slurry to a separator for separation of crystals, is provided by variable speed pump 70 and line 72. Slurry flow rate is measured by flow monitor 74 that provides a representative signal to controller 76 for controlling the speed of pump 70 and thereby controlling the withdrawal of slurry from crystallizer 10 at a selected rate. At steady state conditions in the continuous process of the invention, the rate of feed and makeup solution to the crystallizer should be about equal to the rate of slurry withdrawal and exhaust of vapors to the condenser. Crystallization of the silver nitrate and separation of the crystals as described herein produces silver nitrate product having a very substantial improvement in purity compared to the feed solution. Impurities are concentrated in the solution remaining in the crystallizer and in the liquor remaining from the separation step, producing a very pure silver nitrate crystalline product. The silver nitrate crystal product can typically exhibit an increase in purity in the range of about 30 to 100 times the purity of the feed solution as calculated by weight percent of the impurities present in the product and the feed solution. The pH of the crystal product is typically in the range of from about 3.5 to about 5.5, depending on the moisture and acid content in the product. Generally, pH increases as the moisture content decreases because the acid content in the product also decreases, and therefore the product also has a higher purity. The slurry withdrawn from crystallizer 10 is introduced to a separator, centrifuge 78, to separate silver nitrate crystals from the slurry. Centrifuge 78 separates silver nitrate crystals from the slurry, leaving a residue liquor that is recycled to crystallizer 10 via dissolver 82. FIG. 6 further illustrates details of centrifuge 78. Centrifuge 78 is a rotary screen centrifuge, e.g. a Model GTLII manufactured by Heinkel Corp., with screen 84 shown in phantom. Other separators useful in the invention include continuous pusher centrifuges such as the Kraus-Maffei SZ30 and SB250 series units. The rotary screen centrifuge is a preferred separator, and particularly preferred is one having a high ratio of rated capacity to product throughput. The screen hole size can be readily selected depending on the size of the crystals desired to be separated from the slurry. In the well-known manner, the slurry is introduced to the intake of centrifuge 78 and is rotationally accelerated against screen 84, separating the slurry into a liquor and fines component which passes through screen 84 and a solids component comprising silver nitrate crystals which are stopped by screen 84 and discharged therefrom. The next step in the process of the invention is drying the separated crystals. Control of moisture content is important in the preparation of silver nitrate. It is desirable to provide a consistent product for the eventual end-use, such as the preparation of photographic silver halide emulsions. At higher moisture levels, crystals can stick to surfaces, resulting in poor flowability from the separator and difficulty in handling. Some moisture content may be desirable, however, in order to prepare product having a desired pH value, and product pH can be dependent on moisture content as discussed in the Examples below. A preferred moisture content in the separated, uncompacted silver nitrate crystals is in the range of from about 0.001 percent to about 0.2 percent by weight, and 0.05 percent by weight is particularly preferred. Surprisingly, it has been discovered that the invention provides a drier, more consistent product than do prior art processes and apparatus. Unlike the prior art, the invention does not require large, costly dryers. the rotary screen centrifuge 78 is also a dryer, as it provides a drying function in addition to its above-described separating function. The inherent drying capability of centrifuge 78 can be supplemented by the introduction of an airstream to provide further drying of the crystals, as shown in FIG. 6. Line 86 is means for providing an airstream to the discharge end of centrifuge 78 to provide further drying of the crystals. The flow rate of air through line 86 to centrifuge 78 can be set so as to sufficiently dry the crystals a desired amount for a specified mass flow rate of separated, dried crystals. The moisture content of the separated crystal product depends on factors such as the speed of the centrifuge, the crystal habit, air addition rate, slurry flow rate, slurry temperature, and the hole size of the centrifuge screen. One skilled in the art can readily select the operating parameters to obtain a desired product moisture level in the practice of the invention. Extent of drying is determined by the ratio of the drying air flow rate to the crystal product flow rate. A preferred ratio of drying air flow rate to the dried crystal flow rate is in the range of from about 0.75 CFH of air/lb/hr of crystals (0.047 m 3 / hr of air/kg/min of crystals) to about 1.5 CFH of air/lb/hr of crystals (0.047 m 3 / hr of air/kg/min of crystals), to obtain product moisture contents of from about 0.1 percent to about 0.001 percent by weight, respectively. Separation and drying can be carried out on a slurry at any convenient slurry temperature, and is particularly good at elevated slurry temperatures, e.g. in the range of from about 45°C to about 55°C. At lower slurry temperatures, the moisture content in the crystal product can increase. At higher slurry temperatures, the slurry can be more difficult to handle because the pipelines have an increased tendency to plug up. The appropriate separator can be selected based on factors such as slurry and crystal characteristics and the like. For example, the rotary screen hole size can be selected based on the mean particle size and size distribution of the crystals in the slurry to be being separated. In a preferred embodiment, the aqueous slurry comprises silver nitrate crystals having a mean particle size in the range of from about 200 µm to about 600 µm, and the screen has holes sized to separate and dry crystals having a size of about 50 µm and up. Silver nitrate crystals can accumulate over time on screen 84, which can adversely affect the rotational stability of centrifuge 78 and cause unacceptable vibration levels. Accordingly, means for cleaning screen 84 is provided, comprising a controlled, intermittent introduction of hot water to centrifuge 78. The hot water should have a sufficient flow rate for a sufficient time to substantially flush and clean screen 84. For example, a flow rate of about 5 gallons per minute (19 l/min), for a time of about 10 seconds, at a water temperature of about 50°C can provide adequate cleaning without substantial interruption of the continuous separation and drying of the silver nitrate crystals. During continuous operations, a preferred time interval between cleanings is about 1.5 hours. A standard vibration sensor 86 is mounted on centrifuge 78 to monitor the vibration level. The invention also includes a novel way of treating the silver nitrate crystal product to facilitate subsequent use and handling of the product. As discussed above, the silver nitrate crystals produced in the process of the invention have a substantially cubic morphology compared to the complex aggregate or platelet-type structure of crystals produced by other processes. The crystal product can also have a mean particle size and size distribution smaller than that produced by prior art processes. As described above, these characteristics lend some advantages to the crystal product of the invention. An accompanying disadvantage, however, is that the smaller crystals may have a greater tendency to fuse, creating large chunks of material that are difficult to handle and use. Accordingly, in another aspect of the invention, after separation and drying, the silver nitrate crystal product is compacted to form a plurality of small, flowable, compacted silver nitrate bodies. Each compacted silver nitrate body has a compacted surface and density sufficient to allow the body to freely disengage from surface contact with other similar bodies so that the body is freely flowable despite the contact with the other such bodies. Referring now to FIGS. 6 and 7, in order to form the compacts, the separated, dried crystals drop from screen 84 into solids discharge chamber 88. Chamber 88 should be polished, and have a discharge diameter of about 4 inches (102 mm) or larger and a cone angle of about 40 degrees to substantially prevent or minimize bridging and clogging of the crystals therein. The crystals discharge from chamber 88 into feed tube 90. Feed tube 90 is seamless and without surface projections to avoid bridging of the crystals and blockage of crystal flow in feed tube 90. Chamber 88 has first end 92 engaged with the discharge end of centrifuge 78 and second end 94 engaged with first end 96 of feed tube 90. Second end 98 of feed tube 90 is engaged with compactor 100. The invention encompasses any well-known compactor, such as a tablet press, pellet press, rotary pan sphereinizer, or a roll compactor. The rotary pan sphereinizer produces compacts having a high moisture content and therefore increased drying of the product is necessary. The pellet press uses lubricating materials that may contaminate the product and can be inconvenient or impractical for a continuous process producing a large quantity of a highly purified product. A roll compactor is preferred, since it does not have the aforementioned problems, it is capable of providing a continuous, large throughput of uncontaminated product, and is economical to use. Roll compactors are described in Roll Pressing , W. Pietsch, Powder Advisory Centre, P. O. Box 78, London NW11 OPG, England (2nd Ed. 1987) (hereinafter "Pietsch"), incorporated herein by reference. Roll compactors comprise one of two typical designs, cantilevered and mill shaft. The mill shaft design can accommodate higher compaction pressures and roll forces and have a higher capacity than a comparably sized cantilevered roll compactor, and is preferred for compacting the dense silver nitrate crystals of the invention. A representative roll compactor useful in the invention is the Model 4B4LX10 Chilsonator, manufactured by The Fitzpatrick Company. Compactor 100, as shown in FIGS. 7 and 8, is a roll compactor. Compactor 100 comprises fixed, drive roll 102 rotatably mounted within housing 104, and movable, idler roll 106 rotatably mounted within housing 104 and slidably mounted on opposing walls 108 and 110 of housing 104 by bearing blocks 112 and 114, respectively. Rolls 102 and 106 are mounted such that their axes of rotation are substantially parallel during compaction. Movable roll 106 is an idler roll that is gear-driven by a standard gear mechanism (not illustrated) driven by roll 102. Roll 102 is associated with standard drive means (not illustrated). The actuator of hydraulic piston 116 is connected to plate 112 to provide a force to movable roll 106 during compacting. Machined spacer plate 118 establishes a minimum gap between the edges of rolls 102 and 106 in order to ensure and maintain a desired minimum flow of material through the nip and past the rolls while permitting a sufficient flow rate of material therethrough to minimize webbing between individual compacts. It is important to minimize webbing to minimize the amount of fines in the compacted product. Because roll 106 is slidably mounted on housing 104, the roll gap can be adjusted and roll 106 has some freedom of movement during compaction. The roll gap thus affects the percentage of fines in the compacted product. The roll gap should be small when using a roller design having a pocketed surface to limit webbing around the compact to an acceptable amount. Increased webbing can lead to increased fines, which can cause additional exposure to workers handling the compacted silver nitrate product. A preferred minimum spacer setting and minimum roll gap is about 0.002 inches (0.05 mm). The size and density of a compact of silver nitrate depends on factors such as the type of compactor used and the compacting force employed. The density of uncompacted silver nitrate crystals can typically be about 2.25 g/cc to about 2.30 g/cc. The density of a coherent, hard compact of silver nitrate is generally in the range of from about 3.5 g/cc to about the theoretical density of silver nitrate, which is 4.35 g/cc. Surprisingly, it has been found that the process of the invention provide a coherent, hard compact that can be prepared from uncompacted silver nitrate crystals that are either wet or dry, and without necessitating the addition to the uncompacted powder of a binder, e.g. polyvinyl alcohol. The fact that a binder is unnecessary is a significant aspect of the invention, because a binder can contaminate the silver nitrate and make it impracticable to use in applications requiring high-purity silver nitrate. Examples requiring the use of highly-pure silver nitrate include catalysis, and the preparation of photographic emulsions. FIG. 8 illustrates a compacted body, or "compact", of silver nitrate such as is formed by compactor 100. The size of the compact is a function of the roll surface cavity design as illustrated in FIG. 9. The density of a compact is a function of the roll force, which is proportional to the compaction pressure. Compaction pressures in the range of from about 500 psi (72 kPa) to about 80,000 psi (11,600 kPa) form a usable silver nitrate compact of the invention, although the integrity of the compact is better at a higher compaction pressure and less fines may be generated. Material fed into the roll gap is subject to a compaction force proportionate to the roll force, although a precise compaction pressure is difficult to measure. In the described embodiment, using a roll compactor having about a 4 inch (102 mm) wide compacting zone between two 10 inch (25.4 cm) diameter rolls, a preferred roll force is in the range of from about 16,000 pounds (7,270 kg) to about 40,000 pounds (18,200 kg) to produce good compaction pressures. The separated, dried silver nitrate crystals are typically fairly dense. As the roll force is increased there is a point at which the crystals approach maximum compaction. "Compaction ratio" is the ratio of the density of the silver nitrate compact to the density of the uncompacted silver nitrate crystals. Typically, the compaction ratio for silver nitrate has a maximum value of about 2 and is approached in the described embodiment at a roll force of about 32,000 pounds (14,545 kg). The density of a compact of silver nitrate is typically in the range of from about 3.5 g/cc to about 4.35 g/cc for a roll force of from about 16,000 pounds (7,270 kg) to about 40,000 pounds (18,200 kg), respectively. Roll speed can be selected so as to optimize product throughput while maintaining compact coherency. The maximum speed should therefore not exceed that at which a starved feed condition occurs. A minimum speed should be established such that a sufficient throughput is achieved and such that product bridging can be substantially avoided. "Bridging" is the fusing together of crystals. One skilled in the art can readily select and maintain appropriate minimum and maximum operating roll speeds, and the roll speed can also be controlled automatically as is further described herein. It is desirable to maintain a substantially continuous feed of crystals to compactor 100 in carrying out the continuous process of the invention, but if the level of silver nitrate crystals is above feed tube 90, bridging of the crystals can occur between centrifuge 78 and compactor 100, slowing the flow of crystals. Accordingly, there is provided an optical level monitor comprising light source 120 and detector 122 which are each positioned such that feed tube 90 is positioned therebetween. Feed tube 90 is fabricated of clear teflon or other translucent material to allow detector 122 to monitor the level of crystals in feed tube 90. Detector 122 provides an output signal to controller 124, and controller 124 computes a correction value and provides a control signal to adjust the speed of compactor 100, thereby maintaining the desired level of crystals in feed tube 90. One skilled in the art can determine the relative positions of light source 120, feed tube 90, and detector 122 and the appropriate instrument and control settings. For example, light source 120 should be positioned sufficiently close to feed tube 90 for detector 122 to accurately monitor light transmitted through feed tube 90 during operation, e.g. as dust collects on the inner surfaces of feed tube 90. Although compacting the silver nitrate crystals helps to minimize the amount of fines present in the product, fines are not reduced to zero. Fines can be further removed from the compacted product prior to storing the product by contacting the compacted product with a motive airstream to sweep fines from the product. In a preferred embodiment further described below, the airstream containing fines is also employed to dry separated silver nitrate crystals in the centrifuge and fines are recovered for compacting. The feeding of crystals to the compactor in the continuous process of the invention should achieve a uniform and continuous crystal feed. Feeding can be either gravity feeding or force feeding, both of which are well known in the art. By using a centrifuge separator/dryer, with the compactor positioned under the centrifuge as shown in FIG. 7, gravity feed of crystals should generally suffice. Compacted bodies of silver nitrate are discharged from compactor 100 to line 126. Means for passing air through the compacted bodies to remove fines comprises line 127 by which air is introduced to line 126 to contact and pass through the compacts. Line 128 is means for recycling air containing fines via line 86 to centrifuge 78. The compacted product can be discharged directly into storage container 130, which can be maintained at a positive pressure to prevent contamination of the stored silver nitrate product by providing a filtered air supply as shown to storage container 130. Figure 8 illustrates a typical compact prepared by the invention. The compact is preferably spherically or elliptically shaped as shown, presenting fewer contact points for crystals to fuse and allowing the compacts to separate easily such as when poured from a storage container. The process for preparing the compacted silver nitrate crystal product is continuous. Accordingly, it is important to substantially match product flow rates in the subsystems that comprise the overall system and apparatus, e.g. the crystallizer, the separator, and the compactor. One skilled in the art can readily select the appropriate such flow rates and can select the specific component sizes to achieve the desired system stability. Means for adjusting subsystem product flows to compensate for such changes or transients in flow rates can be provided. For example, the speed of the compactor is adjusted as described above to maintain a desired level of crystal feed to the compactor. Similarly, slurry withdrawal rate can be adjusted by varying the speed of pump 70 to adjust slurry flow to the separator. It is preferred that the process of the invention is carried out at a system pressure below ambient air pressure in order to minimize leakage of material from the system to the environment to limit exposure to workers and others. The invention is further illustrated by the following Examples. Example 1 Silver nitrate crystals were prepared by evaporative crystallization and by cooling crystallization to compare crystal growth rates and estimate comparative residence times. Tests were run with both types of crystallizers on a feed silver nitrate solution containing impurities, and also with the evaporative crystallizer on a feed silver nitrate solution substantially without impurities. Each test was conducted using a 4 liter crystallizer as follows: Vacuum cooling crystallizer : A feed solution of silver nitrate containing impurities was introduced to a cooling crystallizer. The residence time in the crystallizer was 1.5 hours, and the crystal growth rate was calculated to be 0.2444 mm/hr. Evaporative crystallizer : A feed solution of silver nitrate, which in a first run contained impurities and in a second run was substantially free of impurities, was introduced to an evaporative crystallizer. The residence time in the first run was1.5 hours, and the crystal growth rate was calculated to be 0.3474 mm/hr. The residence time in the second run was 30 minutes, and the crystal growth rate was calculated to be 1.2360 mm/hr. The results demonstrate that the evaporative crystallizer provides improved silver nitrate crystal growth rate, especially for a silver nitrate feed solution containing a low level of impurities. Example 2 A feed solution comprising 79 percent by weight of silver nitrate and about 0.02 percent by weight of impurities was introduced to a 3 liter, jacketed, draft tube, evaporative crystallizer having an A310 impeller agitator that was run at a speed of 800 rpm. The solution was heated to 50°C. The solution was then cooled at a rate of 25°C for 2 hours (which is therefore the 'mean residence time' for the test) to form a slurry comprising silver nitrate crystals. The slurry was then removed and immediately filtered to collect the silver nitrate crystals. Figure 3 is a photomicrograph of the silver nitrate crystals. The crystals exhibited a platelet-type of crystal habit not readily dewaterable by separation techniques such as centrifugation. Example 3 Tests were conducted using the apparatus as illustrated in Figure 1, which was scaled up from the crystallizer apparatus used in Example 1. A silver nitrate feed solution with a density of 2.7 g AgNO 3 /cc solution and a temperature of 74°C was introduced to a 125 gallon (473 liter), draft tube, agitated, evaporative crystallizer at a flow rate of 4 gallons per minute. The solution was agitated, and vacuum was maintained in the crystallizer of from between 61 mm Hg absolute and 112 mm Hg absolute, corresponding to solution temperatures of between 54°C and 65°C. The residence time varied from about 1.5 to 3.5 hours. FIGS. 4 and 5 are electron micrographs of the crystals formed at a 1.5 hour residence time. Surprisingly, the silver nitrate crystals formed in the scaled-up apparatus exhibit more even growth along the crystal axes, that is, they are regularly shaped cubical crystals and less platelet in shape than the silver nitrate crystals formed in the 3 liter evaporative crystallizer in Example 2 at the same residence time of 1.5 hours. The cubical crystals have a mean particle size in the range of from about 200 to about 600 µm, depending on process parameters such as residence time and crystallizer slurry homogeneity. The cubical crystals of FIGS. 4 and 5 were found to filter out, and therefore are deliquored, more easily than the platelet-like crystals of FIG. 3. Representative distributions of particle size are shown in FIG. 2 in which the mean particle size is indicated for each curve. Example 4 : Silver nitrate crystals prepared in the process of the invention, as illustrated by FIGS. 1 without air supplied to the centrifuge, and with drying air supplied to the centrifuge at various flow rates. The results are shown in Table 1 below and in FIGS. 10-12. "N/A" means that data was not taken or was not available. Run Air Flow Rate in CFH (m 3 /hr) Moisture Content (Wgt %) Slurry Pump Speed % Slurry Density (g/cc) Dried Silver Nitrate Product Rate in lb/hr (kg/hr) Air Flow/Product Rate in CFH of air/lb/hr of crystals (m 3 / hr of air/kg/min of crystals) 1 0 (0) 0.3000 8.9 3.06 N/A N/A 2 300 (8.5) 0.0130 7.0 N/A 281 (128) 1.0 (0.06) 3 500 (14) 0.0800 7.0 N/A 281 (128) 1.7 (0.10) 4 500 (14) 0.0140 8.5 N/A 342 (155) 1.7 (0.09) 5 540 (15.3) 0.0470 10.5 2.960 135 (61) N/A 6 500 (14) 0.0045 9.0 3.000 182 (83) 2.7 (0.16) 7 500 (14) 0.0035 9.2 2.990 212 (96) 2.3 (0.14) 8 500 (14) 0.0016 12.4 3.400 316 (144) 1.5 (0.09) 9 387 (11) 0.0035 10.0 3.070 285 (130) 1.3 (0.08) 10 583 (16.5) 0.3300 8.1 3.030 285 (130) 2.0 (0.12) 11 583 (16.5) 0.0011 8.5 3.040 285 (130) 2.0 (0.12) 12 387 (11) 0.2100 22.7 2.970 667 (303) 2.0 (0.03) 13 420 (11.9) 0.05 23.1 2.870 292 (133) 1.44 (0.08) The product pH in runs 11, 12, and 13 was 5.5, 4.0, and 4.9, respectively, and the results are shown in FIG. 11. As can be seen from Table 1 and the Figures, good percentage decreases in product moisture are exhibited until the drying air flow rate is about 1 CFH/(lb/hr) (see FIG. 10), at which point increases in flow rate do not provide a high percentage of drying of the product. FIG. 11 shows that the product pH increases as air flow rate is increased. Thus, as the moisture content in the product decreases, the pH increases, due to removal of residual acidic liquors in the crystal product during the air-drying process. Variations in the results occurred and can be explained as follows: Run 3- the product exhibited a higher than expected moisture content, which was probably attributable to residual water blown into the product from the air lines upon start-up of the drying air. Run5- moisture content in the product was higher than expected, probably due to the relatively low slurry density. Run 10-the moisture content in the product was higher than expected, probably attributable to residual water blown into the product from the air lines upon start-up of the drying air. Example 5 Compaction tests were carried out to determine the feasibility of compacting silver nitrate to form coherent, flowable compacted bodies. The compactor was a hydraulic press employing a cylindrical ram die with an inside diameter of 1.127 inches (28.6 mm) and a cross-sectional area of 0.9975 square inches (6.43 cm 2 ). Each test was conducted with a die loading of about 10 grams of silver nitrate powder. The uncompacted powder density was about 2.28 g/cc and had a moisture content of between 0.15 and 0.25 weight percent. The ram was inserted and spun gently to level out the surface of the powder. Measurements of the die length prior to compression were used to determine the uncompressed bulk density of the powder. The die was placed in the press and placed under the selected load for about 10 seconds. The resulting wafer was ejected from the bottom of the die and weighed and measured to determine the resulting wafer density. The results are shown in Figure 13 as a graph of wafer density versus compression pressure. Compression pressures as low as 1000 psi (145 kPa) formed coherent wafers that were hard and brittle. At compression pressures of 20,000 psi (2900 kPa) and greater, the wafers did not readily eject from the die. At pressures of 40,000 psi (5800 kPa) and greater, a blow with a mallet was required to eject the wafers. At such pressures, the wafers formed were harder than those formed at pressures under 20,000 psi (2900 kPa). At high compression forces, the density of the wafers approached the theoretical silver nitrate density of about 4.35 g/cc. Two samples of wet silver nitrate crystals prepared in a pusher centrifuge were also compaction-tested. Compression pressures of 5,000 psi (725 kPa) and 20,000 psi (3190 kPa) were employed. It was observed that at about 5,000 psi (725 kPa) several drops of liquid were forced out of the die, so that the crystals were being further dewatered in the press. In the test at 20,000 psi (3190 kPa), both fluid and a paste were extruded from the die. In both tests, coherent, hard wafers were produced. The results show that silver nitrate powder, in either wet or dry form, can be pressed into coherent compacts without necessitating the addition of a binder. Operation of the present invention is believed to be apparent from the foregoing description and drawings, but a few words will be added for emphasis. Industrial Applicability The process of the invention provide an economical, expedient way to prepare silver nitrate. The compacted silver nitrate product of the invention has superior flowability characteristics and is less prone to fuse than non-compacted silver nitrate. The process of the invention is particularly suited for processing a substantially cubic crystal form of silver nitrate, which is easier to deliquor or separate from a slurry but has an increased tendency to fuse compared to silver nitrate having a platelet crystal morphology. While the invention has been described with particular reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements of the preferred embodiment without departing from invention. In addition, many modifications may be made to adapt a particular situation and material to a teaching of the invention without departing from the essential teachings of the present invention. For example, the invention is also considered to encompass a precompacting step for initially compacting the silver nitrate crystal output of the separator and dryer prior to feeding the material to the compactor. As is evident from the foregoing description, certain aspects of the invention are not limited to the particular details of the examples illustrated, and it is therefore contemplated that other modifications and applications will occur to those skilled in the art.

Claims: A process for continuously producing silver nitrate crystals from an aqueous silver nitrate solution, comprising the steps of : introducing a feed solution of the aqueous silver nitrate solution to an evaporative crystallizer, heating and concentrating by evaporation the aqueous silver nitrate solution in a crystallization zone of the crystallizer while maintaining a partial vacuum in the crystallizer to form a supersaturated slurry comprising silver nitrate crystals ; agitating the slurry to maintain the crystals in a well-mixed suspension ; establishing a mean residence time of the slurry in the crystallization zone of at least about 60 minutes ; controlling the slurry density by measuring on-line the slurry density, generating a control signal in response to the slurry density measurement, and controlling the heating in the crystallizer ; controlling the agitation, residence time, and slurry density to obtain silver nitrate crystals having a size in the range of from about 20 µm to about 600 µm and having an aspect ratio in the range of from about 1:2:3 to about 1:1:1 ; said introducing being at a rate sufficient at steady state operating conditions to compensate for the withdrawal of slurry from the crystallizer ; withdrawing slurry from the crystallizer ; separating from the withdrawn slurry silver nitrate crystals ; and drying the separated silver nitrate crystals. The process of Claim 1, wherein the residence time of the slurry in the crystallization zone is in the range of from about 60 minutes to about 3 hours. The process of Claim 1, wherein the mean particle size of the silver crystals in the withdrawn slurry is in the range of from about 200 mm to about 600 mm. The process of Claim 1, wherein the separated silver nitrate crystals have an aspect ratio in the range of from about 1:2:3 to about 1:1:1. The process of Claim 1, wherein the vacuum is maintained at about 112 mm Hg absolute. The process of Claim 1, wherein the slurry density is in the range of from about 2.7 g/cc to about 3.2 g/cc. Silver nitrate crystals having an aspect ratio in the range of from about 1:2:3 to about 1:1:1, a mean particle size in the range of about 200 µm to about 600 µm and a size distribution of from about 70 µm to about 1000 µm. The silver nitrate crystals of Claim 7, wherein the crystals are produced by evaporative crystallization.

Inventors: DRAKE PAUL CARLTON, HENNENKAMP JEFFERY R, LOGSDON KEVIN MICHAEL, PELTO RALPH HERMAN, SIMPSON BRIAN LEIGH, WALKER THEODORE EUGENE, DRAKE, PAUL CARLTON, HENNENKAMP, JEFFERY R., LOGSDON, KEVIN MICHAEL, PELTO, RALPH HERMAN, SIMPSON, BRIAN LEIGH, WALKER, THEODORE EUGENE, Drake, Paul Carlton, c/o EASTMAN KODAK COMPANY, Hennenkamp, Jeffery R., c/o EASTMAN KODAK COMPANY, Logsdon, Kevin Michael, c/o EASTMAN KODAK COMPANY, Pelto, Ralph Herman, c/o EASTMAN KODAK COMPANY, Simpson, Brian Leigh, c/o EASTMAN KODAK COMPANY, Walker, Theodore Eugene, c/o EASTMAN KODAK COMPANY
Applicants: EASTMAN KODAK CO, EASTMAN KODAK COMPANY
Application year: 1993
Main classification: C01G5
IPC codes: C01G5