This invention relates to a method and a device for the storage of chemical products in a container for chemical substances that are to be transported and further processed in a liquid form but that have a melting point that is above the desired or customary storage temperature.
These substances can be best stored in heated containers because removal from storage and insertion for storage will then not create any difficulties. Of course, this calls for high energy expenditures to maintain sustained heating. Besides, it is disadvantageous that the possibly occurring aging reactions and undesirable reactions with impurities will be accelerated at higher temperature.
When these substances are stored over longer periods of time, it is better in terms of energy to store the product in a solid or rigidified form and then to liquefy a part that is to be taken out.
The problem thus described for example is encountered during the storage of heavy oil that is viscous at environmental temperature and that can become completely solidified in cold regions and in the winter. Various devices have been developed for the storage of heavy oil; they facilitate storage in the at least partially solidified state.
DE 534084 discloses a storage container with a device for suctioning a viscous fluid where a heatable catch hood is arranged in the container so as to heat a part of the viscous fluid in a specifically targeted manner and to make it more liquid for removal. The method featuring the described device is suitable only for viscous fluids but not for completely solidifying substances because the solidified solid substance could not continue to flow under the hood.
DE 2432955 now discloses a method for the underground storage of heavy products, such as heavy oil, that rigidify at ordinary temperatures, where the surface of the rigidified product is placed in contact with at least one circulating warm fluid and where the liquefying product is pumped out. The method is designed for underground galleries and requires relatively much pumping work so as to wash away the stored product with the help of the warm fluid that constantly flows past. This requires all the more work when a crystallizing product with a high melting heat is stored. Heavy oil is to be thus washed out with water but that procedure is not suitable for all products.
Furthermore, DE 83 31 135 U1, discloses an asphalt container where a vertical pipe is arranged in the container; the feeder line empties into the open upper end of that pipe and the lower end of that pipe is arranged at a distance above the bottom of the container. If fresh, hot asphalt is poured from above into the vertical pipe, then, according to the principle of communicating pipes, the fresh, hot asphalt is stored in the container from bottom upward. At the end of the filling phase, there is, accordingly, in the lower end of the container, fresh, hot asphalt as a result of which the asphalt container, after filling, is immediately ready for operation over a certain span of time without any outside heating.
The known devices and methods are not suitable or are only poorly suitable for the storage of very fast rigidifying products, such as, for example, for organic-chemical products that are solidified within a narrow crystallization range. For example, dimethylterephthalate (DMT, C10H10O4) is supplied in a liquid state with a melting range of 140.6° C. for the artificial fiber industry and accordingly is put up for intermediate storage in a liquid state from the very beginning. This has been done so far with a high energy expenditure in heated containers.
The object of the invention is to provide a method and a device for the storage of chemical products in a container which will make it possible, in a liquid fashion, to insert and remove quickly rigidifying products while a part of the product, stored in the container, is in the solid state.
To solve this problem, the invention proposes a method for the storage of chemical products in a container, where the product is inserted for storage in the liquid state with a temperature above its melting temperature and where it remains, at lower environmental temperature, in an at least partly rigidified state until it is removed from storage.
The invention-based process is distinguished by the fact that the evacuation of the product from the container takes place at the end of storage in such a manner that the liquid product, coming out of the production process or being piped in a cycle, will be fed into the container via an essentially vertical feed flow consisting of heat-conducting material and where said product is distributed essentially horizontally over the cross-section of the container below at least one melting member consisting of heat-conducting material, whereby the heat content of the liquid product, in combination with the heat conductivities of the feed line and the melting member or the melting members, is used for melting the product located in the container, and where the product is evacuated via at least one horizontal flow level below the melting member or the melting members and vertically along the feed flow.
The container can in particular be a tank, that is to say, a storage container that is generally supplied with an inlet and an outlet, also having a large volume, with a storage volume of more than 1 m3 (one cubic meter), preferably more than 5 m3.
As part of an advantageous development of the invention, the inlet and possibly additionally the surface below the melting member is blown clear after the passage of liquid product and is filled with a gas until the next use. The introduced gases should be product-friendly (inert) and should be as easily compressible as possible. Air, nitrogen, CO2, or inert gases can be suitable, depending on the product involved.
With the help of an internal partition heating unit, provided on at least one outer wall of the container, one can generate additional liquid product outside a core of rigidified product that is stored below the melting point. The product, that is liquefied on the outer wall, can then be used for the melting of additional product that is to be evacuated or, during insertion for storage, it is used to adjust the pressure during storage insertion so as to guarantee a safe pressure adjustment, that is to say, to protect the container walls and accessories. When, during certain phases of storage insertion or removal or, quite generally, product is kept in a liquid state along the feed line and below at least one melting member, then, reusing the internal partition heating unit, one can generate an approximately ring-shaped core, enveloped by liquid product, said core consisting of rigidified product; this core then facilitates the turbulent allaround mixing of existing product.
Preferably, the product, that is melted along the internal partition heating unit, can be evacuated in vertical ducts which, for instance, can be formed with the help of the heat exchanger that is arranged on the interior wall for interior wall heating.
The method can be so implemented that the stored liquid product can on the whole be left to rigidify in the container. In that case, the feed line is kept clear by gas during the rigidification or crystallization process; this gas is piped in through the feed after the liquid product. Depending on the filling level—that is to say, especially if the filling level is at a maximum or near maximum—the underside of the (upper) melting member can be kept clear by gas or by blowing it clear.
As an alternative, the method however can also be implemented in the following manner: a part of the product, that is stored in the container, can be kept liquid by heating via heating elements, in particular, the interior partition heating unit and/or the feed and/or the melting member during the storage procedure. (Because the feed and the melting member according to the invention consist of heat conducting material, they can be easily heated).
A part of the product for the melting of rigidified product can preferably be conducted in a cycle via an additional, heated accessory container that is connected with the container. In one particular embodiment of the invention, the product can also be conveyed in a cycle within the container. For this purpose, for example, bottom heating can be provided additionally along with the outer wall heating.
The melting takes place especially by means of progressing liquefaction from the top to the bottom and/or from the bottom to the top, preferably while moving the melting members accordingly.
Particularly for the performance of the above-described method, the invention for the purpose of solving the problem furthermore provides a device for the storage of those chemical products that have a melting point below the storage temperature range, within a container that comprises the following elements:
The outlet as well as the inlet can be provided with a valve at the entrance of the feed line.
The melting member is preferably arranged in a movable manner along the feed line, something that facilitates the gradual melting from the top to bottom or from the bottom to the top.
As part of a specially preferred embodiment, the feed line is made as a telescoping pipe. In all of its embodiments, the container is preferably at least partly cylindrical and the feed line is located along the axis of the cylinder. As an alternate model, the container or tank can also have a square or rectangular cross-section; in all of the embodiments, the feed line is preferably in a central position. The melting member can then preferably comprise an upper melting member which has a hat-like shape and which is arranged at the end of the feed line: in an advantageous embodiment of the invention, the upper melting member is provided with floats, preferably in the shape of a floating ring. The floating ring can retain the upper melting member at a certain level below or at the product level. The melting member can be adjusted in such a manner that it will dip higher or lower, in that the floating ring is filled exclusively with gas or partly with gas and partly with fluid or a suitable medium. The floating ring can also be used for heat supplied in that, for instance, a heating element is provided in a chamber of the floating ring.
As a development of the invention, the melting member additionally comprises a lower melting member that preferably extends in a ring-shaped manner around the feed line in the lower third of the container.
The melting member or the melting members can also have downward pointing accessories in the form of flow resistances. These flow resistances are used to distribute the liquid product uniformly underneath the particular melting member. This is also done by partial banking and swirling.
On at least one outer wall one can additionally provide an internal partition heating unit, preferably on a cylindrical outer wall. Ducts for the evacuation of product (generally downward) can be worked into the internal wall heating. Duct melting prevents damage to the container as a result of heat expansion because the escape of the developing forces is always ensured and because the container thus is not stressed mechanically. If, on the device, there are provided ducts along the outer wall, especially with separate, vertical heating possibility, then the process can be carried out in the following manner: first of all, vertical ducts are melted into the rigidified product and then a cross-section surface is melted clear below a melting member. The melting material resulting from horizontal melting can then flow off via the previously formed vertical ducts.
The interior partition heating unit preferably extends higher than the maximum filling level of the product in the container so that the entire internal wall surface can be kept clear of rigidified product. Guide elements can be provided on the upper melting member and they engage on the internal partition wall heating unit in a suitable manner and ensure a continuous and geometrically clearly determined melting zone.
To check the filling level and the storage condition of the product, measurement sensors can be provided, preferably on the melting member or on the melting members and/or on the outer wall.
Using a suitable measurement method, one can also determine whether and how much product is present and whether there is a gas phase below the melting member.
By way of a spatial arrangement with respect to the outlet of the feedline, one can provide an asymmetrical insert whose position can be altered and which for instance has the shape of a guide plate, by means of which one can impart to the product a certain preferential direction in the course of its distribution, during the storage insertion or removal phase. In case of detached containers, that can make it possible to balance temperature differences via the container cross-section. In colder regions, more hot liquid product is introduced with the help of the distribution insert so that the rigidified stored product can be melted uniformly.
The container can be made up of several parts. In particular, melting members, feed line and outlet line can be arranged on a bottomless container cap that, for instance, is set upon a lidless barrel so that, on the whole, one gets a bipartite container according to the invention. The outlet is placed either in the lower area (for example, the lower fifth) of the barrel or it is placed preferably additionally on the container cap, whence the stored, molten product can be suctioned off.
The invention will be explained below with reference to the exemplary embodiments illustrated in the drawing.
The figures are:
FIGS. 1,4 diagram illustrating a longitudinal profile through the storage container in an exemplary embodiment.
a, diagram illustrating exemplary embodiments of 1b, 1c, 1d melting members, looking from top or from bottom.
a, diagram illustrating an internal partition 2b heating unit for block-shaped containers (lateral profiles).
Container 1 is a container suitable for the product, especially with a cylindrical or block-shaped design and has the following main components:
The interior partition heating unit 2a on the outer wall 2 of the container must be aligned along the expected forces, the necessary heat output, as well as in terms of the mechanical and hydraulic effect.
The upper melting member 3 can be a platform with a cylinder (hat 3a) that is aligned centrally upward, as well as with guide plates 10 arranged on the underside (accessories, flow resistances) and a closing edge 6 (guide rails).
The floats 4 can be made in the form of a floating ring and constitute a part on the upper melting member 3. Other floats or a divided design are possible. Preferably, floating ring 4 is suspended between hat 3a and edge 6 of the upper melting member on adjustable connections (cables).
Feed line 5 can be a telescoping pipe that is extended automatically or, alternatively, that is controlled by a motor, by the buoyancy of the floating rings 4 on the upper melting member 3. The telescoping pipe or the feeder line is possibly connected with the distribution accessory 9 so that the product can be guided in a particular fashion. Otherwise, the product is introduced preferably centrally via the telescoping pipe. Guide rails 6 are attached to the upper melting member 3 and ensure the interval between the upper melting member 3 and the interior wall heating unit 2a. Interior wall heating unit 2a can protrude beyond the guide rails 6 by a certain number of heating elements.
The filling and evacuation pipe 7 can be a quarter pipe that is welded upon the bottom around the feeder line 5, with openings for uniform heat distribution in the direction toward the container bottom. Filling and evacuation pipe 7 can be heated via a separate heating coil or via the heat of the feeder line 5.
The lower melting member 8 can be provided with outlet valves that release the flow if the product is evacuated under them or if the pressure above them is greater.
Distribution accessory 9 is moved with a drive in the particular position determined by the personnel or by the process control system.
Accessories 10, in the shape of guide plates 10 on the underside of melting members 3, 8, are used as flow resistances for the distribution and swirling of liquid product.
Measurement sensors 11 and contact makers are used to monitor the filling level and the storage condition of the product.
Floats 12 are used to determine what the distance is between melting members 3, 8 and the product, that is to say, whether or not gas has to be supplied.
a shows a possible embodiment of the internal partition heating unit 2a. Vertical ducts 2b are made in the heat exchanger that is provided for the wall heating and these ducts are used for the perpendicular evacuation of the liquefied product in the direction toward the bottom.
b shows a corresponding wall heating unit, similar to the one in
If, for instance, during the washing phase, the product is colder on one side of the container, then the distribution accessory is lowered and placed in position so that the warmer side will be screened. The rising hot product now presses into the colder regions of the container. The distribution accessory is built into the, this time cylindrical hat 3a of melting member 3 and is connected downward with the telescoping pipe 5 via a cylinder. The cylinder ensures uniform supply of the product and protects the superposed parts. The distribution accessory can be guided via perpendicular guide rails and a spindle 9a, provided with a drive, located between melting member hat 3a and distribution accessory 9. At least two spacing rings and terminal stops 3 provide guidance at all times. A part of the distribution accessory 9 remains in the upper hat-shaped part of the upper melting member 3 to prevent jamming. If the distribution accessory 9 is needed, then it is lowered with spindle 9a until the perpendicular guide rails no longer engage each other. Spindle 9a, whose height can be adjusted, at its lower end no longer has a thread, only a stop, that continues to turn the distribution accessory 9. Distribution accessory 9 now lies on the terminal stop and is moved into the desired position by the drive in the same direction of rotation. If the distribution accessory 9 is no longer needed, the direction of rotation of the drive is changed. Now, spindle 9a sags and the thread engages in order again to pull the distribution accessory 9 upward. The guide rails again engage each other until the drive is shut off.
The container can generally consist of all suitable materials, in particular metal or synthetics. It can be foldable in the empty state for instance by using flexible synthetics.