MXPA98002780A - Steam and catalytic conversion process - Google Patents

Abstract

A process for vapor conversion of a hydrocarbon charge in the presence of a catalyst, which includes the steps of (a) providing a catalytic emulsion consisting of a water-in-oil emulsion containing a first alkali metal and a second selected metal from the group consisting of non-noble metals of group VIII, alkaline earth metals and mixtures thereof, (b) mixing the catalytic emulsion with a hydrocarbon charge to provide a reaction mixture, and (e) subjecting the reaction mixture to steam conversion conditions in order to provide a concentrated hydrocarbon product. It also provides a catalytic emulsion and a process to prepare

Description

~ ^ PROCEDURE FOR CONVERSION OF STEAM AND CATALYST BACKGROUND OF THE INVENTION The invention relates to a vapor conversion process and to a catalyst to provide a high conversion rate from a heavy hydrocarbon material to more valuable and lighter hydrocarbon product, as well as a procedure to prepare the catalyst. Several processes are known for converting heavy hydrocarbons into more desirable liquid and gas products. These procedures include reduction of viscosity and extreme thermal cracking. However, these processes are characterized by low conversion rates and / or a large percentage of undesirable byproducts such as coke which, among other things, may have problems of transportation and transportation. scrap. Therefore, the main object of the present invention is to provide a steam conversion process, where a good conversion is obtained with reduced levels of undesirable byproducts, such as coke.

A further object of the present invention is to provide a steam conversion catalyst useful for carrying out the process of the present invention. A further object of the present invention is to provide a process for preparing the vapor conversion catalyst of the present invention, it is another object of the present invention to provide a method for recovering catalyst metals from by-products of the steam conversion process for use in the preparation of catalyst for subsequent steam conversion processes. Other objects and advantages of the present invention will be apparent below.

BRIEF DESCRIPTION OF THE INVENTION According to the invention, the above objects and advantages are easily obtained. According to the invention, a method for the vapor conversion of a hydrocarbon material in the presence of a catalyst is provided, the method comprises the steps of: (a) providing a catalytic emulsion comprising a water-in-oil emulsion containing a first alkali metal and a second metal selected from the group consisting of Group VIII non-noble metals, earth alkaline earth metals and mixtures thereof; (B) mixing the catalytic emulsion with a hydrocarbon material to provide a reaction mixture; and (c) subjecting the reaction mixture to steam conversion conditions in order to provide a better grade hydrocarbon product. Further, according to the invention, the process for vapor conversion preferably comprises the steps of providing an acid hydrocarbon stream having an acid number of at least about 0.4 mg KOH / g hydrocarbon; providing a first solution of the first alkali metal in water; mixing the acidic hydrocarbon stream and the first emulsion so as to at least partially neutralize the hydrocarbon stream and form a substantially homogeneous mixture, wherein the alkali metal reacts with the hydrocarbon stream to form an alkaline organic salt; providing a second solution of said second metal in water; and mixing the substantially homogeneous mixture and the second solution to provide the catalytic emulsion. A catalytic emulsion is also provided for the vapor conversion of a hydrocarbon material, according to the invention; which comprises a water-in-oil emulsion containing a first alkali metal and a second metal selected from the group consisting of non-noble metals of Group VIII, alkali metals earths and mixtures thereof. A process for preparing the catalytic emulsion of the invention is provided, which comprises the steps of providing an acidic hydrocarbon stream, having an acid number of at least about 0.4 mg KOH / g hydrocarbon; providing a first solution of the first alkali metal in water; mix the acid hydrocarbon stream and the first solution in order to partially neutralize the stream of Hydrocarbon and forming a substantially homogeneous mixture, wherein the alkali metal reacts with the hydrocarbon stream to form an organic alkaline salt; provide a second solution of the second metal in water; and combining the mixture of its partially homogeneous and the second solution to provide the catalytic emulsion.

BRIEF DESCRIPTION OF THE DRAWINGS A detailed description of the preferred embodiments of the invention is presented below, with reference to the accompanying drawings, in which: Figure 1 is a schematic representation of a vapor conversion process according to the present invention; Figure 2 is a schematic representation of a process for the production of a synthetic crude oil according to the present invention; and Figure 3 is a schematic illustration of a process for the preparation of a catalytic emulsion according to the present invention.

DETAILED DESCRIPTION The invention relates to a steam and catalyst conversion process for use in improving a heavy hydrocarbon material such as an extra heavy crude or material including a fraction of residue having a boiling point greater than 500 ° C, and a process for preparing the catalyst. According to the invention, a vapor conversion process and a catalyst are provided, which advantageously improve the conversion of the heavy hydrocarbon material as compared to the conversion obtained using conventional thermal viscosity reduction methods or additives, and in addition which provides a lower production rate of undesirable solid byproducts, such as coke. The material to be treated according to the present invention can be any heavy hydrocarbon material, where the conversion of more valuable, lighter products is desired. The material can be, for example, a material that includes a fraction of residue that has a boiling point greater than 500 ° C, or that has a portion meaning iva having a boiling point greater than 500 ° C and an additional portion that have a boiling point in the 350-500 ° C scale, or can be substantially the same fraction of residue, for example, after the fractionation of a particular initial material, or it can be a vacuum residue or any other suitable food. Table 1, presented below, contains characteristics of a typical example of a material suitable for the treatment according to the invention.

TABLE 1 Characterization of the vacuum residue Content Carbon (% / p) 84. .3 Hydrogen (% / p) 10. .6 Sulfur (% / p) 2. .8 Nitrogen (% / p) 0.52 Metals (ppm) 636 Gravity API 6 Asphaltene (% / P) 11 Carbon Conradson (% / P) 18. .6 500 ° C + (% / P) 95 Viscosity ((210 ° F) 98.8 ° C, Cst) 2940 Un Vacuum residue as characterized in Table 1 is an example of a suitable material, which can be advantageously treated in accordance with the present invention. Of course, you can also treat other numerous feeds. According to the invention, ee provides a steam conversion process for improving a heavy hydrocarbon material, such as that of Table 1, in order to improve the hydrocarbon material to provide lighter, more valuable products. According to the invention, the material is brought into contact, under steam conversion conditions, with a catalyst according to the invention in the form of a water-in-catalytic oil emulsion containing a first alkali metal and a second metal selected from non-noble metals of group VIII, alkaline earth metals and mixtures thereof, whereby the heavy hydrocarbon material is improved. The steam conversion conditions according to the invention include a temperature between about 360 ° C and about 520 ° C, preferably from about 410 ° C to about 470 ° C.; a pressure less than or equal to about 42.18 kg / cm2 (600 psi), and preferably between about 0.3515 kg / cm2 (5 psi) to about 42.18 kg / cm2 (600 psi), also less than or equal to about 21.09 kg / cm2 (300 psi) and preferably from approximately 0.703 (10 psi) to approximately 21.09 kg / cm (300 psi); a space velocity per hour and day of between approximately 0.001 h "1 to approximately 3.5 h", depending on the desired severity of the treatment; a steam in an amount of between about 1% and about 15% by weight, preferably between about 3% and about 12% by weight, based on the feed. Depending on the material to be treated, the process pressure may be adequate and substantially atmospheric, or it may be a little higher, for example between about 3.515 kg / cm2 (50 psi) to about 42.18 kg / cm2 (600 psi), preferably from about 7.03 kg / cm2 (100 psi) to about 21.09 kg / cm2 (300 psi). The steam conversion conditions are advantageous when compared to conventional conversion, with hydrogen, since lower pressures than would be needed to maintain hydrogen can be used. In this way, the vapor conversion process of the present invention allows the reduction in the cost of equipment and the like, to operate at high pressures. The catalytic catalyst or emulsion according to the present invention is preferably provided in the form of a water-in-oil emulsion, preferably having an average droplet size of less than or equal to about 10 microns, more preferably less than or equal to about 5 microns, and having a water to oil ratio in volume of between approximately 0. 1 to about 0.4, more preferably from about 0.15 to about 0.3. According to the present invention, the catalytic emulsion is provided for the purpose of including a first alkali metal, preferably potassium, sodium or mixtures thereof, and a second metal, which may be preferably a non-noble metal of Group VIII , preferably nickel or cobalt, or an alkaline earth metal, preferably calcium or magnesium, or mixtures thereof. The catalytic emulsion may suitably contain various combinations of the first and second metals, and particularly preferred combinations include potassium and nickel; sodium and nickel; sodium and calcium; and sodium, calcium and nickel. The catalytic emulsion preferably contains the first alkali metal at a concentration of about 10,000 ppm based on the catalytic emulsion, and also preferably contains a first alkali metal and a second metal at a weight ratio of between about 0.5: 1. at about 20: 1, or preferably between 1: 1 # to 10: 1, approximately. According to the invention, the emulsion Catalyst is preferably prepared by providing an acidic hydrocarbon stream, preferably having an acid number of at least about 0.5 mg KOH / g hydrocarbon, wherein the acid number is defined through ASTMD 664-89. The acid number, as set forth in ASTMD 664-89, is the amount of bases, expressed in milligrams, of potassium hydroxide per gram of sample, required to titrate a sample in the solvent from its initial measurement reading to a measurement reading corresponding to a freshly prepared non-aqueous basic buffer solution. In the present invention, this number is used to refer to the amount of base required to neutralize the Acidity of the acidic hydrocarbon stream that is used to prepare the catalytic emulsion of the present invention. To the acidic hydrocarbon stream, water solutions of desired catalyst metals are added as follows to prepare the desired catalytic emulsion. A solution of the first alkali metal in water is provided to mix with the acid hydrocarbon stream. According to the invention, the alkali metal solution in water is preferably a saturated solution containing an alkali metal within about 5% of the saturation point of the solution at room temperature, where the saturation point is beyond from where the additional alkali metal can not dissolve in solution and, rather, could be precipitated from the solution. However, more diluted solutions can be used, the volume of added water ends as part of the catalytic emulsion and finally it must be vaporized during the treatment of the material. Therefore, it is preferred to provide the solution as stated above at approximately 5% of the saturation point in order to avoid the demands of unnecessary heating.

According to the invention, the acid hydrocarbon stream and the alkali metal solution in water are combined and mixed in order to at least partially neutralize the hydrocarbon stream and form an essentially homogeneous mixture, wherein the alkali metal reacts with the hydrocarbon stream to provide an alkaline organic salt, and preferably reacts with naphthenic acid contained in the hydrocarbon stream to provide an alkaline naphthenic salt. This step can be carried out completely, within the mixer, if desired, or the streams can be combined upstream of a mixer and fed to the mixer to mix properly and provide the desired substantially homogeneous mixture, which can at this point, be an emulsion The hydrocarbon stream and the amount of alkali metal are preferably selected so that substantially all of the alkali metal reacts to form an alkaline organic salt, preferably an alkaline naphthenic salt, while at least partially and preferably substantially neutralizing the acidity of the hydrocarbon stream. This helps to ensure the incorporation of its essentially homogeneous alkali metal in the final catalyst emulsion. The conversion of the alkali metal to the alkaline organic salt is desired, since the alkali metal remains in the hydroxide form in the mixture and can react with the second metal salts during the last mixing to provide second undesired metal oxides, such as nickel oxide, which adversely affects the entire procedure. In addition, while remaining high in acidity, in most cases it is undesirable as corrosive to mixing equipment and the like. A second solution of the second metal, the non-noble metal of Group VIII, the alkaline earth metal or a mixture of both, is provided in water. The second solution is preferably also a saturated solution, and more preferably contains the second suitable metal in an amount within about 5%, preferably within about 2% of the saturation point of the second solution. The second metal is preferably provided in the second solution in the form of an acetate, such as nickel acetate, for example. The second solution is then combined and mixed with the substantially homogeneous mixture of the first solution and the acid stream that was described above. The second solution and the substantially homogeneous mixture can be combined in a mixing apparatus to carry out the mixing step, or upstream of the mixing apparatus, as desired according to the parameters of the specific process. This second mixing step, where the second solution is mixed with the mixture Substantially homogeneous, it provides the catalytic emulsion described above, wherein the first alkali metal in the form of an alkaline naphthenic salt is located on the adjoining surface between the water droplets and the phase of continuous oil and acts as a surfactant and where the second metal remains dissolved in L the water droplets of the emulsion. It should be noted that the mixing steps established above are carried out using equipment, which is well known in the art, and which is not part of the present invention. According to the invention, the acidic hydrocarbon stream from which the The catalyst emulsion preferably has an acid number of between about 0.4 mg KOH / g to about 300 mg KOH / g. This current can be obtained from the heavy hydrocarbon material that will be treated, if the material is suitably acidic. Alternately, the acid hydrocarbon stream may be provided from any other suitable source. It is preferred that the acid hydrocarbon stream contains an organic acid, preferably naphthenic acid, which has been found to react advantageously with the alkali metal during the preparation of the catalytic emulsion, in order to provide the desired alkali naphthenic salt, which advantageously acts as a surfactant to provide additional stability and the desired droplet size for the catalytic emulsion of the present invention. During the mixing steps, the alkaline naphthenic salt migrates towards the adjoining surface between the water droplets and the continuous oil phase of the catalytic emulsion and acts as a surfactant to help maintain the stability of the emulsion, and helps to ensure a sufficiently small droplet size, which provides a good dispersion of the second metal in the material. The use of the catalytic emulsion containing the first and second catalytic metals advantageously serves to improve a rapid distribution of the catalytic metals through the material being improved according to the method of the present invention, to greatly improve the conversion of the catalyst. the fraction of heavy residue or other material. When the catalytic emulsion and the material are mixed, the catalytic metals are substantially dispersed throughout the material and it is believed that the vapor conversion conditions then serve to vaporize the water in the emulsion to provide at least some steam requirements for the This process also results in very fine, partially solid and partially melted particles of the first and second catalytic metals in close contact with the material, thus improving the conversion to more light products. In addition, the vapor conversion process of the present invention results, under conditions of increased severity, in the provision of an improved hydrocarbon product, and also a residue or by-product of coke which, while in a greatly reduced amount when it is compared to conventional procedures, it has also been found to contain the first and second spent catalytic metals. The byproduct is either a waste or coke or both, depending on the severity of the procedure. According to the process of the present invention, the coke or waste by-product is preferably further treated, for example, through desalination for the residue or gasification for coke, to recover the catalytic metals for subsequent use in the preparation of an emulsion. catalytic to continue the steam conversion procedures. It has been found that such processes recover a large amount of the alkali metal, when the waste is desalted and, in some cases provides a recovery greater than 100% of the second metal, especially the non-noble metal of Group VIII, when the gasification of the solid by-product carbonaceous (coke) is carried out together with a high recovery performance of alkali metal. When the by-product is mainly a waste, it can be desalted for metal recovery through dilution, for example, up to 14 ° API and then transported for conventional desalination. In a typical process according to the invention, a heavy hydrocarbon feed is passed through a furnace to provide a desired temperature, and then to a fractionator to separate the various fractions to provide the heavy hydrocarbon waste material, the which will be treated according to the present invention. If the byproduct of the process is rich in solid (ie, coke greater than or equal to about 5%), the waste can be gasified or controlled combustion, and the resulting ash can be washed to recover the alkali metal through dissolution of water, while any remaining solid can be treated in the presence of C02 and ammonia to produce NiC03, which can be converted to nickel acetate using acetic acid at room temperature. Of course, this is for the case where the second metal is nickel. In addition, recovery of more than 100% of the spent nickel can be obtained using this method, since some of the nickel innate to the feed is recovered above and beyond the nickel of the process used to form the catalytic emulsion. Referring now to the drawings, Figure 1 schematically illustrates an example of a system for carrying out the vapor conversion process of the present invention. Referring to Figure 1, the heavy hydrocarbon material to be treated is fed to a furnace 10 to be heated to a suitable temperature, and then to an atmospheric or vacuum fractionator 12 to separate the light components. The heavier components of the fractionator 12 are fed to another oven 14 for further heating, and subsequently to a reactor / maturator 16 to carry out the conversion process. As shown in Figure 1, a catalyst preparation unit or station 18 is provided, wherein the catalytic emulsion of the present invention is prepared. This catalytic emulsion can be mixed with the material that will be converted into a number of different locations. Figure 1 shows the catalytic emulsion that is injected into the material after the fractionator 12 and before the kiln 14. Alternatively, the catalytic emulsion can be mixed with the hydrocarbon material after the kiln 10 and before the actuator 12, as indicated by the point 20, or can be introduced after the oven 14 and before the ripening / reamer 16, as shown in point 22. Still referring to Figure 1, the product of the ripening / reactor 16 is reconnected with products of the fractionator 12, and fed to a cyclone separator 24, wherein the improved hydrocarbon products are separated from the by-products. The improved product is fed to the fractionator 26, wherein the improved product is separated into several fractions including an upper part of gas, naphtha, gas oil and distillation residues, while the by-product is fed through a heat exchanger 28 to a unit of desalting 30 for further processing, as desired. The diluent can be added to this fraction, as shown in the drawing, as desired. In the desalting unit 30, the catalytic metals are recovered from the by-products, and preferably are returned to the catalyst preparation unit 18 for use in the preparation of an additional catalytic emulsion for use in the process of the present invention, with additional or development metals that are added as desired. further, and as also shown in Figure 1, a portion of the material from the furnace 10 can be amusing to the catalyst preparation unit 18, if desired to be used as the acid hydrocarbon stream, wherein the catalytic emulsion is prepare. This is particularly preferable, if the hydrocarbon material to be treated has sufficient acidity or other surfactant content. Of course, it should be noted that although a schematic representation of a system for carrying out the conversion process of the present invention is shown in Figure 1, the procedure can, of course, be performed using different steps and a different equipment, and without intending any limitation on the scope of the present invention. Referring now to Figure 2, there is illustrated an alternative schematic representation of a process according to the present invention, with respect to a process for producing synthetic crude oil from extra heavy crude oil. Referring to Figure 2, an extra heavy crude material typically having a low API gravity, for example, less than or equal to about 10 °, can be suitably »Mixed with a diluent to increase the gravity API, for example, at about 14 °, to allow the treatment of the material in a conventional desalination unit 32. From this desalination unit 32, the desalted feed can be suitably fed to a atmospheric distillation unit 34, where the diluent is separated for dilution of the subsequent material, as are other lighter products and an atmospheric residue. The atmospheric residue is preferably mixed with the catalytic emulsion according to the invention from a catalyst preparation station 36, and is fed to a maturator / reactor 38 to carry out the conversion of the present invention. As shown, mixing the material and The catalytic emulsion is exposed in the maturator / reactant 38 to steam conversion conditions, for example, at a pressure of 10 barg and at a temperature of 440 ° C. From the maturator / reactant 38 an improved hydrocarbon product and a byproduct containing a residue and / or coke as well as a catalytic metal from the catalytic emulsion are provided. This by-product mixture is fed to a heat exchanger 40 and then to a desalination unit fF 42, where the catalytic metal salts through gasification and / or desalination and returned to the catalyst preparation station 36, while a synthetic, transportable crude oil product of the present invention is typically provided. having an improved API gravity, for example greater than or equal to 13. Of course, it should be appreciated that although Figure 2 constitutes a schematic representation of a preferred embodiment of the method of In accordance with the present invention, no limitation is intended in the scope of the present invention. With reference to Figure 3, a further schematic representation of a method for preparing a catalytic emulsion according to the present invention. Figure 3 shows an entry of an acid hydrocarbon stream such as a hydrocarbon stream enriched with naphthenic acid, which is fed to the heat exchanger 44, and then mixed with a saturated solution of alkali hydroxide in water. The stream enriched with naphthenic acid and the saturated alkaline solution are preferably mixed in a suitable ratio that the acidity of the hydrocarbon stream is at least partially neutralized, and its all of the alkali hydroxide in the saturated solution is reacted to form the alkaline naphthenic salt. This reaction is improved, and an emulsion can be formed in the mixture 46, which is fed to the hydrocarbon stream / the saturated alkaline solution mixture. After this step, the mixture is passed from the mixer 46 to a finishing station 48, for the neutralization of any remaining acidity of the hydrocarbon stream, if needed. After the finishing station 48, a second saturated solution of the second catalytic metal, in this example, a solution of nickel acetate in water, is combined with the mixture of the finishing station 48 and passed to an additional mixer 50, in where sufficient mixing energy is imparted to provide the desired water-in-oil emulsion, having the first alkali metal in the form of an alkaline naphthenic salt, located on the adjoining surface between the water droplets and the phase continuous oil and also acting as a surfactant, and having the second metal, in this case nickel acetate, dissolved in the water droplets of the emulsion. The alkaline naphthenic salt surfactant serves to provide the desired small droplet size, which advantageously results in a good dispersion of the catalytic metal, especially the second catalytic metal., through the material that will be improved according to the invention. Then, the emulsion can be passed to a regulating tank 52, if needed, and subsequently a treatment system for vapor conversion of a heavy hydrocarbon feed according to the present invention. The catalytic emulsion thus formed preferably has a droplet size less than or equal to about 10 microns, more preferably less than or equal to about 5 microns, and ideally about 1 micron. Of course, it should be noted that although Figure 3 shows a schematic representation of a system for preparing a catalytic emulsion according to the present invention, this schematic representation is not intended to be a limitation on the scope of the present invention. The following examples demonstrate the advantages of the process and the catalytic emulsion of the present invention.

EXAMPLE 1 This example illustrates the advantages of the process of the present invention when compared with a conventional viscosity reduction process (viscosity reduction) the material of Table 1 (acid number, 25 mg KOH / g) was used to prepare a catalytic emulsion according to the invention using potassium and nickel. The catalyst emulsion was prepared by first mixing a stream of material and a 40% by weight solution of KOH, and then mixing a nickel acetate solution at a K: Ni (P) ratio of 4: 1. The catalytic emulsion was mixed with the material in order to provide 1,000 ppm of potassium and 250 ppm of nickel acetate with respect to the material, and the reaction mixture was subjected to steam conversion conditions including a temperature of 430 ° C and LHSV = 2h "1, 8% by weight of steam based on the feed (Procedure 1) .The emulsion and the material were treated in a ripener having a volume of 1.2 liters.The feeding flow was 2,400 g / h, while the flow of the catalytic emulsion was 113 g / h The same material was subjected to viscosity reduction under the same conditions, without using a catalyst and * using a small amount of steam (Procedure 2). other procedure completion parameters are set forth in Table 2.

Table 2 T: 430 ° C, LHSV = 2h ": Procedure 1 Procedure 2 CONV., 500 ° C + (% / p) 40 25 ASPH CONV. (% / P) 12 -32 Vise., 350 ° C (Cst) 1269 9973 V50 350 ° C 34 46.5 API Grav (350 ° C) 7.4 2.8 AV50 (350 ° C) 5.5 4.8 Fuel Gain (% / p) 80 28.9 As shown, the results obtained using the method of the present invention (Procedure 1) provide improved conversion results (40%) when compared to conventional viscosity reduction (25%) (Procedure 2). In addition, the final product of process 1 according to the invention includes an improved hydrocarbon, as well as a long and short chain residue, which has been found according to the invention, which contains more, if not all, of the catalytic metal of the catalyst emulsion. This catalytic metal can be recovered according to the invention through desalination or gasification for use in the preparation of the additional catalytic emulsion for subsequent processing according to the invention. In this case, the residue fraction product of procedure 1 was desalted and potassium was recovered up to 94% (P) of original starting potassium.

EXAMPLE 2 In this example, the steam conversion process of the present invention was used, under more severe vapor conversion conditions, using a waste material having the composition set forth in Table 3, below: Table 3 Material Product or Conv. 500 'DC (% / p) 65.00 API 5.50 13.00 Azuf re (% / p) 3.50 2.86 Carbon (% / p) 84.44 84.54 Hydrogen (% / p) 10.19 10.80 Nickel (ppm) 106.00 60.00 Nitrogen (% / p) 0.50 0.40 Vanadium (ppm) 467.00 100.00 As f to the dye (% / p) 12.37 8.00 C. Conradíson (% / p) 17.69 10.00 Solids (% / p) 0.17 8.50 (210 ° F) (Cst) 3805.67 344. "90 Des ti lation% / p API% / p API IBP-200 ° C 0.00 0.00 6.00 50.00 200 -350 ° C 0.00 0.00 19.00 27.00 350-500 ° C 17.00 18.50 36.00 12.00 > 500 ° C 83.00 3.00 29.00 2.50 The material was treated with a catalytic emulsion as prepared in Example 1, in the The same proportions established above. As shown, the process according to the present invention provides an excellent conversion of the residue fraction of 500 ° C +, and r provided a high fraction fraction production. lighter hydrocarbon, too. In addition, coke production was substantially less than 9% when compared to more than 30% coke, which is typically obtained using delayed coke formation procedures conventional. This reduction in coke is particularly useful for reducing solids, which can be transported or disposed of. In addition, the process of the present invention provides a by-product of solids carbonaceous that contains almost all the metals of the catalyst. Through the gasification of the coke, 95% (p) of the starting alkali metal (potaaio) was recovered for use in the preparation of the additional catalytic emulsion, and through a simple solution with acetic acid, 110% of the metal was recovered transition (nickel).

EXAMPLE 3 This example demonstrates the process of the present invention when compared with the reduction of the conventional viscosity in a process for the production of synthetic crude. A material was provided having a composition as set out below in Table 4.

Table 4 API 9.4 Sulfur (% / p) 3.6 Carbon (% / p) 82.12 Hydrogen (% / p) 10.75 Nickel (ppm) 86.00 Nitrogen (% / p) 0.53 Vanadium (ppm) 403.00 Asphaltenes (% / p) 8.93 C. Conradson (% / p) 12.66 (% / p) Ash _ 0.09 Viscosity 40 ° C (104 ° F) (c S t) 14, 172.00 100 ° C (212 ° F) (c S t) 149.90 Distillation% / p API IBP - 200 ° C 1. 0 9 38.60 > 500 ° C 56.60 3.00 This feed was treated using a catalytic emulsion and a vapor conversion process according to the present invention, in Where the catalytic emulsion was prepared online using a material having an acid number of 3.5 mg KOH / g. Catalytic emulsion sufficient to neutralize 1 mg KOH / g was mixed "with the feed The emulsion was prepared from 40% in_ weight of a solution of KOH at 6 g / h and 14% in weight of a solution of nickel acetate at 13.6 g / h. The flow of the feed was 2,400 g / h. The material was also treated following a procedure of viscosity reduction conventional to the same conditions. The results are set forth below in Table 5. Table 5 Present Reduction of invention Vi seosity Conv. 500 ° C + (% / p) 35.00 15.00 API 14.80 11.90 * • Sulfur (% / p) 2.96 3.12 Carbon (% / p) 85.54 85.80 Hydrogen (% / p) 10.90 10.54 Nickel (ppm) 340.00 87.00 Nitrogen (% / p) 0.40 0.49 Vanadium (ppm) 409.00 411.00 As fáltenos (% / p) 7.71 11.80 C. Conradson (% / p) 10.30 15.10 Viscosity 105.5 ° C (122 c 'F) (CSt) 53.20 62.30 Disinfection 20% / p API% / p API IBP - 200 ° C 4.62 47.30 4.00 50.60 200 - . 200 - 350 ° C 26.63 25.40 20.00 24.50 350 -. 350 -. 350 - 500 ° C 30.40 13.70 25.90 12.70 > 500 ° C 36.79 3.00 48.11 2.60 Food-Based Production. As shown in Table 5 above, the process of the present invention provided better performance and properties of the crude Synthetic produced when compared to the reduction of viscosity.

EXAMPLE 4 ^ This example illustrates the process of This invention is carried out at more severe conditions (T = 440 ° C, P = 10,545 kg / cm2 (150 psig), space velocity (volume of ripener / volume of waste / hour) = 0.5 h "1, pressure partial steam of 9.139 kg / cm (130 psig)) and compared to a conventional delayed coke formation process m. The material for this example was the same as that established in Table 4 of Example 3 above. The same catalytic emulsion separation of Example 3 was used. The material flow was reduced to 600 g / h to provide a space velocity of 0.5 h. "The flows of the KOH solution over the nickel acetate solution were 1.5 g / h and 3.4 g / h respectively, the results of both procedures were they fix in the next Table 6.

Table 6 Present Coque Delayed Invention Training Conv. 500 ° C + (% / p) 65.00 68.00 API 20 .20 28.40 Sulfur (% / p) 2 .57 1.80 Carbon (% / p) 85 .00 86.50 Hydrogen (% / p) 11 .11 13.50 Nickel (ppm) 10.00 0.00 Ni t rógeno (% / p) 0 .31 0.13 Vanadium (ppm) 80. .00 0.00 As fáltenos (% / p) 6. 20 0.00 C. Conradson (% / p) 8. .79 0.00 Viscosity 105.5 ° C (122 ° F) (cSt) 46.40 Desi lation% / p API% / p API IBP - 200 ° C 11.80 49.90 16.61 49.30 200 - 350 ° C 36.57 25.00 31.81 26.3 350 - 500 ° C 25.50 15.10 22.95 16.2 > 500 ° C 19.81 3.00 0.00 0.00 Solids 4.92 20.40 Food-Based Production. From Table 6, several observations can be made. It is evident that the synthetic crude obtained from delayed coke formation has a major improved quality when compared to that provided in accordance with the process of the present invention. However, the proportion of conventionally produced solids is much higher than that produced in accordance with the present invention. In addition, the process of the present invention produced an increased proportion of middle distillates, and the residue of this process can, of course, be further refined, still using delayed coke formation, if desired, to produce higher total fractions yields. of boiling point, lower. The reduced coke production of the process according to the present invention is advantageous, for example, when synthetic crude is produced in remote areas, where the largest investments are required in facilities for the transport of the solid to transport the coke and of this way to avoid environmental damage in the far area. In addition, the coke produced in accordance with the present invention can be completely burned using heat released from other necessary internal processes, while simultaneously recovering from the resulting ash in the catalytic metals as discussed above for reuse in catalytic emulsion preparation. additional.

EXAMPLE 5 This example illustrates the effective conversion of the hydrocarbon feed, following the procedure of. the present invention using catalytic emulsion having different combinations of catalytic metals. Conversions were performed using the 500 ° C + fraction obtained from the vacuum distillation of the crude in Table 4. The examples were carried out at a temperature of 440 ° C, pressure of 1 barg, and a feed / steam ratio of 7. A continuous operation was implemented with a constant flow of material (60 ml / h) and steam, for 4 hours, for example. A stirred tank reactor having a volume of 100 ml was used. The results are set forth below in Table 7.

Table 7 Distillate Distribution I Catalyst formulation% conv. gases IBP-220 ° C 220-3S0 ° c 35? -soo ° c 5 ?? ° c + coke * sooßc +% by weight% by weight% by weight% by weight% by weight% by weight without cat 50 - 5 11 21 51 17 40 Na-Ni 1: 1, 69 5 14 30 51 5 28 180oppm Na-Ca 1: 2, 10 '2 13 23 53 11 21.5 VD 300Oppm K-Ni 1: 1, 65 11 22 50 17 22.2 1400ppm Na-Ca- 1: 1: 1, 4 5 10 21 46 23 5.2 Ni 2500ppm * The atomic ratio of the metals used, are presented in this column together with the concentration of the catalyst in ppm based on the food The atomic ratio of the metals used is presented in this column along with the concentration of ppm catalysts based on the ation.

As shown, each of the catalytic metal combinations in the catalytic emulsion of the present invention provides excellent material conversion and advantageously reduced amounts of coke. In this way, it provides a process for the conversion of steam, a heavy hydrocarbon material, a catalytic emulsion to be used in the steam conversion of a heavy hydrocarbon material, a catalytic emulsion to be used in the steam conversion and a process for preparing the catalytic emulsion to obtain the objects and advantages of the present invention. This invention can be modalized in other forms or carried out in other ways without departing from the spirit or its essential characteristics. Therefore, the present modality should be considered in all aspects as illustrative and not as restriction, the scope of the invention being indicated with the appended claims, and all changes that are within the meaning and scale of equivalence are intended be covered in them.

Claims (59)

v ^ CLAIMS

1. A process for the conversion of a hydrocarbon material in the presence of a catalyst, comprising the steps of: (a) providing a catalytic emulsion comprising a water-in-oil emulsion containing a first alkali metal and a second metal ^ "selected from the group consisting of non-metals 10 noble of Group VIII, ferrous alkali metals and mixtures thereof; (b) mixing the catalytic emulsion with a hydrocarbon material to provide a reaction mixture; and (c) subjecting the reaction mixture to steam conversion conditions to provide an improved hydrocarbon product.

2. The procedure according to the 20 claim 1, wherein the steam conversion conditions include a temperature of between about 360 ° C to about 520 ° C, and a pressure of between about 0.3515 kg / cm2 (5 psi) at approximately 42.18 kg / cm2 (600 psi), and 25 a space velocity per liquid hour of between about 0.001 h "1 to about 3.5 h" 1 and steam in an amount between about 1% and about 15% by weight based on the material.

3. The process according to claim 2, wherein the steam conversion conditions include a temperature of between about 410 ° C to about 470 ° C, a pressure of between about 0.703 kg / cm 10 (10 psi) to about 21.09 kg / cm2 (300 psi), and a vapor in an amount of between about 3% to about 12% by weight based on the material.

4. The process according to claim 1, wherein the steam conversion conditions include a pressure less than or r *. equal to 42.18 kg / cm2 (600 psi)

5. The procedure according to the Claim 1, wherein the vapor conversion conditions include a pressure of between about 3.515 kg / cm '(50 psi) approximately 42.18 kg / cm (600 psi)

6. The process according to claim 1, wherein the vapor conversion conditions include a pressure less than or equal to about 21.09 kg / cm (300 psi). 1 .

The process according to claim 1, wherein the steam conversion conditions include a pressure of between about 7.03 kg / cm2 (100 psi) to about 21.09 kg / cm (300 psi).

8. The process according to claim 1, wherein step (c) results in a homogeneously homogeneous dispersion of the first alkali metal and the second metal in the material, whereby vapor conversion is facilitated.

9. The process according to claim 1, wherein step (c) results in the vaporization of substantially all of the water in the emulsion to provide at least a portion of the vapor requirement for such steam conversion.

10. The process according to claim 1, wherein the material is an extra heavy crude having a first API gravity and a first viscosity, and wherein the improved hydrocarbon product is a synthetic crude having a second API gravity greater than the first API gravity and a second viscosity lower than the first viscosity.

11. The process according to claim 1, wherein the material is an extra heavy crude having an API gravity less than or equal to about 10 °, and wherein the improved hydrocarbon product is a synthetic crude having a higher API gravity that or equal to approximately 13 °.

12. The process according to claim 11, further comprising the steps of mixing the extra heavy crude with a diluent, to provide a mixture having an API gravity greater than the extra heavy crude, passing the mixture to a distiller to separate the diluent and a residue, and mix the residue with the catalytic emulsion to provide the reaction mixture. F

13. The procedure according to - claim 1, wherein step (c) provides the improved hydrocarbon product and a byproduct containing the first alkali metal and 5 the second metal of the catalytic emulsion, and further comprises the step of recovering the first alkali metal and the second metal from the by-product to provide recovered metals and using the recovered metal to provide an emulsion 10 additional catalytic step (a).

14. The process according to claim 1, wherein the catalytic emulsion has an average droplet size less than or equal to about 10 microns.

15. The process according to claim 1, wherein the catalytic emulsion has an average droplet size less than or equal to about 5 microns.

16. The process according to claim 1, wherein the first alkali metal is present in such a catalytic emulsion as a Organic alkaline salt in an adjoining surface between the water phase and the oil phase, and wherein the second metal is present in the catalytic emulsion in solution in the water phase.

17. The process according to claim 16, wherein the alkaline organic salt is an alkaline naphthenic salt.

18. The process according to claim 1, wherein the first alkali metal is selected from the group consisting of potassium, sodium and mixtures thereof.

19. The process according to claim 1, wherein the second metal is a non-noble metal of group VIII selected from the group consisting of nickel, cobalt and mixtures of the same.

20. The process according to claim 1, wherein the second metal is an alkaline earth metal selected from the group consisting of calcium, magnesium and mixtures thereof.

21. The process according to claim 1, wherein the second metal comprises a non-noble metal of group VIII selected from the group consisting of nickel, cobalt and mixtures thereof and an alkaline earth metal selected from the group consisting of calcium , magnesium and mixtures thereof.

22. The process according to claim 1, wherein the first alkali metal comprises sodium and the second metal comprises calcium and nickel. . '

23. The procedure according to the 15 claim 1, wherein the catalytic emulsion contains the first alkali metal and the second metal in a weight ratio of about 0.5: 1 to about 20: 1.

24. The process according to claim 1, wherein the catalytic emulsion contains the first alkali metal and the second metal in a weight ratio of about 1: 1 to about 10: 1. 25

25. The procedure according to the - claim 1, wherein the catalytic emulsion contains the first alkali metal at a concentration of at least about 10,000 ppm based on the weight of the catalytic emulsion.

26. The process according to claim 1, wherein the catalytic emulsion contains the first alkali metal sufficient to provide the reaction mixture with a concentration of the first alkali metal of at least 400 ppm based on the weight of the reaction mixture.

27. The process according to claim 1, wherein the catalytic emulsion contains the first alkali metal sufficient to provide a reaction mixture with a concentration of the first alkali metal of about 800 ppm based on the weight of the reaction mixture.

28. The process according to claim 1, wherein the catalytic emulsion has a water to oil ratio by volume of between about 0.1 to about 0.4.

29. The process according to claim 1, wherein the catalytic emulsion has a water to oil ratio by volume of between about 0.15 to about 0.3.

30. The method according to claim 1, wherein step (a) comprises the steps of: providing a current of. "Acidic hydrocarbon having an acid number of at least 0.4 mg KOH / g hydrocarbon; providing a first solution of the first alkali metal in water; mixing the hydrocarbon acid stream and the first solution in order to at least partially neutralize the hydrocarbon stream and form a substantially homogeneous mixture, wherein the alkali metal reacts with the hydrocarbon stream to form an alkaline organic salt; provide a second solution of the second metal in water; and mixing the mixture of its partially homogeneous and the second solution to provide the catalytic emulsion.

The process according to claim 30, wherein the acid hydrocarbon stream has a number between about 0.4 mg KOH / g to about 300 mg KOH / g.

32. The process according to claim 30, wherein the acid hydrocarbon stream comprises naphthenic acid.

33. The process according to claim 30, wherein the step of providing the first solution comprises supplying a saturated solution of the first alkali metal in water, wherein the saturated solution is within about 5% of a saturation point of the solution to room temperature.

34. The process according to claim 30, wherein the step of providing the second solution comprises providing a saturated solution of the second metal in water, in -where the saturated solution is within about 5% of a saturation point of the saturated solution at room temperature.

35. The process according to claim 30, wherein the acid hydrocarbon stream is obtained from the hydrocarbon material. 10

36. The catalytic emulsion for the conversion of a hydrocarbon material, comprising: - a water-in-oil emulsion containing A first alkali metal and a second metal ak selected from the group consisting of non-noble metals of Group VIII, ferrous alkali metals and mixtures thereof.

37. The catalytic emulsion according to claim 36, wherein the catalytic emulsion has an average droplet size less than or equal to about 10 microns.

38. The catalytic emulsion according to claim 36, wherein the catalytic emulsion has an average droplet size less than or equal to about 5 microns.

39. The catalytic emulsion according to claim 36, wherein the alkaline organic salt is an alkaline naphthenic salt

40. The catalytic emulsion according to claim 36, wherein the first alkali metal is present in the catalytic emulsion as an organic alkaline salt in an adjoining surface between the water phase and the oil phase, and wherein the second metal is present. in the catalytic emulsion in solution in the water phase.

41. The catalytic emulsion according to claim 36, wherein the first alkali metal is selected from the group consisting of potassium, sodium and mixtures thereof.

42. The catalytic emulsion according to claim 36, wherein the second metal is a non-noble Group VIII metal selected from the group consisting of nickel, cobalt and mixtures thereof.

43. The catalytic emulsion according to claim 36, wherein the second metal is an alkaline earth metal selected from the group consisting of calcium, magnesium and mixtures thereof.

44. The catalytic emulsion according to claim 36, wherein the second metal comprises a non-noble metal of Group VIII selected from the group consisting of nickel, cobalt and mixtures thereof and an alkaline earth metal selected from the group It consists of calcium, magnesium and mixtures thereof.

45. The catalytic emulsion according to claim 36, wherein the first alkali metal comprises sodium and the second metal comprises calcium and ñique 1.

46. The catalytic emulsion according to claim 36, wherein the catalytic emulsion contains the first alkali metal and the second metal - in a weight ratio of between about 0.5: 1 to about 20: 1.

47. The catalytic emulsion according to claim 36, wherein the catalytic emulsion contains the first alkali metal and the second metal in a weight ratio of between about 1: 1 to about 10: 1.

48. The catalytic emulsion according to claim 36, wherein said catalytic emulsion contains the first alkali metal at a "concentration of at least about 15 10,000 ppm based on the weight of the catalytic jf emulsion.

49. The catalytic emulsion according to claim 36, wherein the catalytic emulsion has a water to oil ratio by volume of between about 0.1 to about 0.4.

50. The catalytic emulsion according to claim 36, wherein the catalytic emulsion has a water to oil ratio by volume of between about 0.15 to about 0.3.

51. A process for the preparation of a catalytic emulsion, comprising the steps of: providing an acid hydrocarbon stream having an acid number of at least about 0.4 mg KOH / g hydrocarbon; providing a first solution of a first alkali metal in water; mixing the acidic hydrocarbon stream and the first solution in order to at least partially neutralize the hydrocarbon stream and form a substantially homogeneous mixture, wherein the alkali metal reacts with the hydrocarbon stream to form an organic alkaline salt; providing a second solution of a second metal selected from the group consisting of Group VIII non-noble metals, ferrous alkali metals and mixtures thereof in water; and mixing the substantially homogeneous mixture and the second solution to provide the emulsion £ y $. talitic

52. The process according to claim 51, wherein the acid hydrocarbon stream has an acid number of between about 0.4 mg KOH / g to about 5 300 mg KOH / g.

53. The procedure according to the - claim 51, wherein the acid hydrocarbon stream comprises naphthenic acid.

The process according to claim 51, wherein the step 'of providing the first solution comprises providing a * saturated solution of the first alkali metal in water, 15 wherein the saturated solution is within about 5% of a saturation point of the solution at room temperature.

55. The process according to claim 51, wherein the step of providing the second solution comprises providing a saturated solution of the second metal in water, wherein the saturated solution is within about 5% of the saturation point of a saturated solution. at room temperature.

56. The process according to claim 51, wherein the acid hydrocarbon stream has an acidity and the first solution has an alkaline hydroxide content, and further comprises mixing sufficient quantities of the first solution and the hydrocarbon stream, so that substantially all the alkali hydroxide reacts with the hydrocarbon stream to provide an alkaline organic salt and at least partially neutralize the acidity.

57. The process according to claim 51, wherein the hydrocarbon stream contains naphthenic acid, whereby the alkali metal reacts with the hydrocarbon stream to form an alkaline naphthenic salt.

58. The process according to claim 51, wherein the substantially homogeneous mixture contains substantially all of the first alkali metal of the organic salt to the haze.

59. The process according to claim 51, wherein the second solution contains the second metal in the form of a second metal acetate.