Patent Grant
8088186
The present invention relates to equipment for the atomisation of liquid streams by means of a dispersing gaseous stream and for mixing the atomised product with a further gaseous stream.
The equipment claimed is used for feeding chemical reactors and is capable of mixing the atomised product and the gaseous stream in the space between the outlet of the equipment itself and the solid filling contained in the reactor.
The axial symmetry of the equipment makes it possible to extend this in the case of the feeding/mixing of several liquid streams.
In some chemical processes, for example in catalytic partial oxidation reactions of hydrocarbon charges, it is important to guarantee a fast and efficient dispersion of the liquid charge (for example naphtha, gas oil, deasphalted oil, etc.) and close contact with the reagents contained in a second phase (for ex. air, oxygen). If this requisite is not satisfied, various disadvantages can arise, among which a loss of selectivity to the desired products and the production of carbonaceous residues which, with time, make frequent running stoppages and internal cleaning of the reactor, necessary.
Knowledge acquired from FCC (Fluid Catalytic Cracking) technologies—which, as is well known from literature, have already dealt with and solved similar problems—has led to the above result.
It is not possible, on the other hand, to simply make use of FCC devices, as they do not include the co-feeding of a second reagent phase; they are in fact limited to the simple atomisation of a hydrocarbon charge inside a fluidised bed to give an atomised product having a suitable geometry.
The main mechanisms on which the functioning of FCC nozzles is based are (U.S. Pat. No. 5,289,976):
Devices used in other technologies, such as diesel engine injectors and ultrasound atomizers have also been considered but it is held that they cannot achieve significantly higher performances with respect to FCC devices; in the case of diesel injectors, there is the problem of combining a pulse device with a reactor operating continuously, whereas in the case of ultrasound atomizers, problems arise due to the running of the atomising element. The present invention therefore combines a component deriving from FCC devices (for ex. those cited in U.S. Pat. No. 5,289,976, U.S. Pat. No. 6,257,504) with an additional component: in the particular case of catalytic partial oxidations, said second component is added with the purpose of uniformly mixing the phase containing the oxidizing agent (air/oxygen/nitrogen) with that containing the hydrocarbon.
The equipment, the main object of the present invention, for atomising a liquid stream with a dispersing gaseous stream and mixing the atomised product with a further gaseous stream, is characterized in that it comprises:
An element suitable for increasing the extent of the spurt emerging from the nozzle itself, can be installed close to the nozzles (9) of the distribution zone.
The nozzles (5) of the tubular core can preferably:
The nozzles (9) of the distribution zone are preferably more than 2, symmetrically distributed between each other.
The nozzle(s) (6) of the second atomisation stage and the nozzles (9) of the distribution zone can be positioned at the same height or at different heights: arrangement at the same height is preferred.
A further object of the present invention relates to equipment for the catalytic partial oxidation of liquid fuels, characterized in that it comprises equipment for atomising liquid streams, as described above, according to the invention, and that it also comprises the following zones:
The essentially empty chamber of the mixing zone is preferably of a cylindrical or truncated conical shape wherein the various spurts coming from both the distribution zone (D) and the second stage of the atomisation zone (N1), interpenetrate in the absence of gyrating motions.
Means having geometrical forms which are such as to minimize reflection phenomena of the atomised product can be preferably present, at least at the head of the catalytic bed, (so as to minimize reflection phenomena of the atomised product): in particular, monoliths with parallel channels can be used.
Furthermore, in the equipment according to the invention, mixing between the two reagent phases preferably takes place in the space between the outlet of the device and the inlet into the actual catalytic bed. The formation of gyrating motions in the equipment is deliberately minimized, as they can cause deposits of part of the feed on the reactor/feeder walls; experience has in fact demonstrated that said deposit can produce solid residues or other unbalances in the running of the equipment.
This problem is particularly important in the case of heavy hydrocarbons, having a final boiling point (>200° C.) significantly higher than the feeding temperature.
What is specified above should not be interpreted as a limitation of our invention as, by operating under suitable safety conditions, it is also possible to mix the two flows inside the equipment itself.
The advantages of said equipment are:
Tests carried out on models of said distributor have shown great flexibility of use, scarce ties between liquid/gaseous charge, in addition to an easy start-up and shut-down. The scarce ties between liquid/gaseous charge are important when reactions such as that cited above are effected.
The assembly of the two elements preferably follows an axial symmetry, as shown in
The atomisation stage of the hydrocarbon is based on a combination of atomisation mechanisms which allow the simple construction of equipment suitable for processing a wide range of flow rates: from small residential plants up to reactors such as those for catalytic partial oxidation.
Mechanisms such as expansion through a hole (U.S. Pat. No. 3,071,540) can be equally efficient, but, in the case of small flow rates, they require the use of holes with a small diameter, which can easily clog when heavy charges and/or containing suspensions are used.
A combination of one or more of these feeding devices can be used, depending on the type of reactor and its productivity; it is also possible to insert suitable additional elements with the purpose of obtaining a suitable geometry (normally solid cone) to the feeding stream.
It is possible, moreover, to add, at the head of the equipment of our invention, suitable heating elements, in order to appropriately moderate the interface stress and viscosity of the hydrocarbon charge, when the latter is particularly heavy.
Unlike what is normally stated in FCC literature, the nozzle of our invention mainly operates with a flow direction of the top-down type, even if it is not limited to this.
Claims can be found in literature of equipment similar to that present in FCC technologies (for ex. U.S. Pat. No. 4,195,779); the equipment claimed by us is different from those present in literature due to the design of the atomisation and mixing zone, which, in our case, is more suitable for treating heavy charges which can generate deposits along the walls of the mixing duct or obstruct holes with a particularly small diameter (small capacity plants).
We will now provide embodiments of the present inventions with the help of
With reference to
The liquid hydrocarbon charge (1) enters the feeding zone (A), from which, in the atomisation zone (N1), it passes through the main duct (the tubular core) (2), where it is mixed with water (3), whereas the dispersing gaseous stream (for ex. Methane, hydrogen, natural gas, off gas, etc.) enters the feeding zone (A), flows through the intermediate duct (external duct coaxial with the tubular core((4) of the atomisation zone (N1) and, passing through the series of nozzles (5) in an extern intern direction, it meets the liquid charge (1) causing a first atomisation. The atomisation degree proceeds further when the charge passes through the nozzle (6) of the second stage of the atomisation zone (N2), from where the charge enters the mixing zone (M) at the head of the reactor.
The second gaseous stream (7) enters the feeding zone (A) and the distribution zone (D) through the external duct (outer coaxial jacket) (8) to be distributed through the series of holes/nozzles (9). The spurts from the holes/nozzles (6), (9) combine to provide a good degree of overall mix.
In order to reduce the interface stress of the hydrocarbon, it is possible to add, at the head of the distributor, a suitably controlled heating element (10).
As far as the operating temperature is concerned, preferred use envisages maintaining, close to the tip of the distributor (6), (9), a temperature higher than that of the lower-boiling liquid (normally water); under these conditions, a complete vaporization of the low-boiling product is guaranteed, between the atomisation point (5) and the nozzle (6), which causes an improvement in the overall performances.
With respect to the running pressures, these mainly depend on the operating values of the reactor and on the pressure drops particularly associated with the passage through the holes/nozzles (59, (6); even if the atomisation degree of the liquid improves with a reduction in the nozzle diameter, the negative aspects of the greater pressure drops and possibility of the plugging of the nozzles due to impurities present in the liquid charge, are well known to experts in the field.
As far as the geometry of the outlet stream is concerned, this is approximately a solid cone, with an angle which depends on both the geometry of the outlets (6), (9) and on the flow rate values of the oxidizing stream/hydrocarbon stream.
In
It is preferable to apply these elements to the oxidizing gaseous stream rather than to the hydrocarbon stream, to minimize the formation of possible deposits of hydrocarbon in the line.
The outlet nozzles of the oxidizing phase can be suitably inclined to obtain a better interaction with the hydrocarbon phase as shown in
A further object of the present invention relates to the process for the catalytic partial oxidation of liquid hydrocarbon fuels, selected from gasoline, naphtha, medium distillates, deasphalted oils and heavy refinery residues and/or of oxygenated products, selected from methanol, DME and ethers, characterized in that it is effected by means of the equipment described above and in that it comprises the following steps:
The catalytic system preferably consists of oxides, nitrides or oxy-nitrides containing one or more elements selected from Rh, Ru, Ir, Pt, Ni, Fe, Co, Cr and Cu.
The element(s) contained in the oxides, nitrides or oxy-nitrides is preferably in a quantity ranging from 0.05 to 15% by weight.
The above-mentioned materials have generally shown a considerable resistance to thermal shock, particularly relevant under the activation conditions of the reaction. These properties have proved to be better than those of oxide materials used in OPC reactions. Moreover, said catalytic materials have shown an activity higher than, or equal to, that of the known materials.
The ratio between vapour moles/hydrocarbon carbon atom moles (steam/C) preferably ranges from 0 to 3.5, more preferably from 0.1 to 1.5, and the ratio between the molecular oxygen moles/hydrocarbon carbon atom moles (O2/C) preferably ranges from 0.15 to 0.7, more preferably from 0.25 to 0.65.
The OPC processes according to the invention can, as mentioned above, be used as pre-reforming: in this case, the products obtained from the catalytic partial oxidation, effected between the reagents with an O2/C volume ratio lower than 0.5, are sent to an autothermal reforming step.
Some examples are now provided, which should not be considered as representing a limitation of the present invention.
Equipment made of AISI 316 with the dimensions shown in table 1, was tested by co-feeding water and nitrogen, according to the flow rates listed in table 2.
The liquid at the outlet of the device had fine dimensions, particles of relevant dimensions (0.3 mm) were absent.
The cone emerged with an angle (2θ) ranging from about 13 to 20°, depending on the atomisation gas flow rates.
Equipment differing from that of example 1 in a gas holes-nozzle distance equal to 15 mm, was tested under the same experimental conditions as example 1. The spray emitted was of a lower quality, showing a sporadic formation of drops having relevant dimensions.
Equipment differing from that of example 1 in a diameter of the nitrogen holes equal to 0.4 mm instead of 0.5 mm, was tested under the same experimental conditions as example 1. A good quality spray was emitted.
The same equipment as example 1 was tested inside a closed transparent container, capable of tolerating pressures of 8 bar.
A visual inspection showed a good atomisation degree in a pressure range varying from 1 to 7 bar, the gas flow rates (N1/h) being maintained constant. The atomisation degree at 7 bar surprisingly appeared higher than that at 1 bar.
The same equipment as example 4 was tested by co-feeding nitrogen from the external duct. The spray remained of a good quality and no canalisations were observed in the stream. The spurt remained homogeneous along the whole duct.
The same equipment as example 1 was inserted in a bench scale plant to produce syn-gas from LCO. The flow rates used are listed in table 3, the equipment operated at a pressure of 6 bar ate and at temperatures of the nozzle ranging from 160 to 205° C.
The atomizer was equipped with a heating band at 250° C., in order to maintain a suitable surface tension and facilitate reaching the above-mentioned temperatures at the nozzle.
The equipment ran continuously for 200 hours without relevant problems. At the end of the test a visual inspection did not reveal any mechanical damage to the distributor; the amount of heavy residues at the head of the bed was irrelevant.
| Number | Date | Country | Kind |
|---|---|---|---|
| MI2004A1860 | Sep 2004 | IT | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2005/010574 | 9/26/2005 | WO | 00 | 3/6/2007 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2006/034868 | 4/6/2006 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 3071540 | McMahon et al. | Jan 1963 | A |
| 3705106 | Muzyczko et al. | Dec 1972 | A |
| 3705108 | Marion et al. | Dec 1972 | A |
| 3847564 | Marion et al. | Nov 1974 | A |
| 3884648 | Crouch | May 1975 | A |
| 4006099 | Marion et al. | Feb 1977 | A |
| 4006100 | Crouch | Feb 1977 | A |
| 4097366 | Tanaka et al. | Jun 1978 | A |
| 4400180 | Marion et al. | Aug 1983 | A |
| 4443230 | Stellaccio | Apr 1984 | A |
| 4789384 | Martens et al. | Dec 1988 | A |
| 4888031 | Martens | Dec 1989 | A |
| 4946475 | Lipp et al. | Aug 1990 | A |
| 5785721 | Brooker | Jul 1998 | A |
| 5935489 | Hershkowitz et al. | Aug 1999 | A |
| 5962606 | Williams et al. | Oct 1999 | A |
| 6001938 | Chinh et al. | Dec 1999 | A |
| 6193936 | Gardner et al. | Feb 2001 | B1 |
| 6713036 | Vanden Bussche et al. | Mar 2004 | B1 |
| 6736960 | Chen et al. | May 2004 | B1 |
| 6773630 | Stellaccio et al. | Aug 2004 | B2 |
| 6872379 | Zahringer et al. | Mar 2005 | B2 |
| 7399329 | Arcuri | Jul 2008 | B2 |
| 7785491 | Bedetti | Aug 2010 | B2 |
| Number | Date | Country |
|---|---|---|
| 20 05 972 | Sep 1971 | DE |
| 0 593 171 | Apr 1994 | EP |
| 1 095 904 | May 2001 | EP |
| 1 460 594 | Mar 1966 | FR |
| 9319837 | Oct 1993 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20070278328 A1 | Dec 2007 | US |
