Hydroconversion process to upgrade the transport properties of heavy and extra-heavy crude oils at low severity conditions using dispersed-phase catalyst

Abstract

The present invention relates to a catalytic hydroconversion process in dispersed phase of extra-heavy and heavy crude oils for upgrading their transport properties, that operates at low severity conditions, in such a way that the obtained product can be transported by conventional pumping to the distribution and refining centers. The main technical contributions of the hydroconversion process in dispersed phase of this invention to upgrade the transport properties of heavy and extra-heavy crudes are: Compact size and can be localized next to the production facilities on ground or offshore Use of operating conditions at low severity Reduction of the viscosity and increase of the API gravity at values that allow the transportation by pipeline of heavy or extra-heavy crude Upgrading of the crude oil properties in a permanent way Hydrocarbon and gases from production centers are used as supplies Operation in dispersed phase avoiding plugging problems Use of low-cost disposable catalysts at low concentrations.

Claims

1. A catalytic hydroconversion process in dispersed-phase at low severity for upgrading properties of extra-heavy and heavy crude oils having API gravity between 3 to 16 and kinematic viscosity at 37.8 C. higher than 6000 cSt for transporting the crude oil, said process comprising mixing an extra heavy or heavy crude oil stream with a hydrogen stream in a hydrogen/hydrocarbon ratio of 400-2500 ft.sup.3/bbl and a catalyst stream at a concentration of 0.5 to 2 wt % based on the weight of the crude oil to produce a reaction stream, feeding the reaction steam to a direct fire heater to heat the reaction stream; feeding the heated reaction stream of said extra heavy and heavy crude oil at temperature in the range of 50 to 200 C. to a feed/product heat exchanger and recovering heat from the reaction stream for heating said extra heavy and heavy crude oil stream; feeding the reaction stream to an adiabatic reactor and subjecting the reaction stream to hydroconversion at a temperature of 320-400 C., pressure of 30-100 Kg/cm.sup.2, and liquid space-velocity between 0.1 and 3.0 h.sup.1; feeding the resulting reactor effluent to a gas/liquid separator and recovering a hydroconverted liquid hydrocarbon fraction for transportation by conventional processing lines and a gaseous fraction containing hydrogen, hydrogen sulfide and light hydrocarbons at low concentrations; and recycling said gaseous fraction to said hydrogen stream for mixing with and preheating the extra heavy or heavy crude oil stream and hydrogen stream for feeding to the direct fire heater.

2. The catalytic hydroconversion process at low severity in accordance with claim 1, wherein said catalyst is a powder or oil soluble and dissolved in a hydrocarbon or water soluble and dissolved in water.

3. The catalytic hydroconversion process at low severity in accordance with claim 1, wherein said adiabatic reactor is at a reactor pressure between 40 to 80 Kg/cm.sup.2, reaction temperature between 350 to 380 C., hydrogen/hydrocarbon ratio between 400 to 1500 ft.sup.3/bbl, and liquid space velocity between 0.1 to 0.5 h.sup.1.

4. The catalytic hydroconversion process at low severity in accordance with claim 1, wherein said catalyst includes at least one selected from the group consisting of Mn, Fe, Co, Ni, Mo, Cu, and Cr, and where said catalyst is fed to the adiabatic reactor together with the extra-heavy or heavy crude oils.

5. The process of claim 4, wherein said catalyst is selected from the group consisting of molybdenum and iron oxides and sulfides.

6. The catalytic hydroconversion process at low severity in accordance with claim 1, wherein said catalyst is in powder form with a particle sizes of 5 to 500 microns.

7. The process, in accordance with claim 1, wherein said catalyst comprises up to 80 wt. % of Mo or Fe.

8. The catalytic hydroconversion process at low severity, in accordance with claim 1, wherein said adiabatic reactor comprises two reactors in parallel.

9. The catalytic hydroconversion process at low severity, in accordance with claim 1, where said process produces a liquid hydrocarbon yields of up to 98 vol. %.

10. The process according to claim 1, wherein said process increases the API gravity of said recovered liquid hydrocarbon fraction by 8.4 units and reduces the viscosity of said recovered hydrocarbon fraction as measured at 37.8 C. by up to 98.5% relative to said extra-heavy and heavy crude oil feed.

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) FIG. 1 shows a typical flow diagram of the hydroconversion process in dispersed-phase of heavy crude oils which illustrates the best way known by the applicants of this invention and that serves as a reference in the application examples.

(2) Although the diagram of FIG. 1 illustrates the specific provisions of equipment whereby this invention can be practically applied, it should not be to understand that this limits the invention to some specific equipment.

DETAILED DESCRIPTION OF THE INVENTION

(3) This invention relates to the application of a catalytic hydroconversion process in dispersed phase to upgrade the transport properties of heavy and extra-heavy crudes at operating conditions of low severity. It is designed to operate with feeds of heavy and extra-heavy crude oils with API gravity of 3 to 16 units. Due to the nature of the feed, the process includes its preheating and of the pipelines aiming at introducing the feed to the catalytic hydroconversion reactor in disperse phase, that is the object of this invention. Preheating of the feed can be carried out by heat exchange with the hot streams of the same unit, while the heating of pipelines can be carried out using steam jackets. Under these conditions, the configuration of the process and the equipment is aimed at optimizing the energy balance when streams of high molecular weight and high viscosities are handled.

(4) For the purposes of this invention, the term low severity conditions describes a hydroconversion process of heavy or extra-heavy crudes in which the conversion of compounds of high molecular weight is such that allows reducing the viscosity to values that ensure the transportation of such crude oils.

(5) FIG. 1 shows a flow diagram of typical process, in which the hot heavy oil (A), that is an effluent of production center, is fed to the feed/product heat exchanger in order to recover heat from the reactor effluent (B). Before entering the direct fire heater, it is mixed with a hydrogen stream (C) and a catalyst (D). The hydrogen 190 stream may be a mixture of hydrogen of make-up plus the gaseous effluent obtained in the liquid/gas products separator. The catalyst can be added to the hydrocarbon feed dissolved in hydrocarbon or in water. This reaction mixture is added to an adiabatic reactor (E) in which the hydroconversion reaction is carried out. The hot reactor product effluent (B) transfers part of its heat to preheat the fresh feed.

(6) The reactor effluent is recovered in a gas/liquid separator (F). In this equipment, the liquid fraction of hydroconverted hydrocarbon is separated with suitable properties for its transportation by conventional pipelines (G).

(7) A portion of the gaseous fraction (H) is recycled to the direct fire heater for its feedback to the process. The typical composition of this gas includes: hydrogen, hydrogen sulfide and light hydrocarbons in low concentrations. Because the operating conditions of the process are at low severity, the gaseous stream produced in the plant has high hydrogen concentration and low amounts of compounds formed by heteroatoms such as sulfur and nitrogen. Thus, this effluent gas stream (I) may be optionally processed or not in downstream units.

(8) The process can operate with one reactor or two reactors in parallel in order to increase the plant capacity and to reduce production times due to a possible interruption of operation of any of the reactors.

(9) As a result of the catalytic hydroconversion in dispersed phase of the heavy oil, the content of impurities such as organometallic, sulfur and nitrogen compounds is reduced, as well as viscosity is diminished and API gravity of the feed is increased.

(10) The catalyst can be prepared with heavy elements as: Mn, Fe, Co, Ni, Mo, Cu, Cr with different oxidation states and their different types of salts. Preferably compounds of Mo, Fe and Ni are selected due to their low cost. The simplest form of preparation consists of the formation of metal oxides from their different salts. Metal oxides within the reactor atmosphere rich in hydrogen and gaseous sulfur compounds are transformed into sulphides which is the most active form of the metals contained in the catalyst.

(11) The catalytic reaction may develop in a variety of operating conditions, however, it is possible to obtain the transport properties of the upgraded crude oil at low severity conditions in the reactor with operating pressures in the interval of 30 to 100 kg/cm.sup.2, temperatures from 320 to 400 C., hydrogen/hydrocarbon ratio of 400 to 2500 ft.sup.3/bbl, and space velocity (LHSV=Liquid hourly space velocity) from 0.1 to 3 h.sup.1. Depending on the quality of the feed it is possible to combine the different 225 values of these operating conditions and thereby to obtain upgraded crude oils with suitable transport properties.

(12) Since the operating conditions are not of high severity, there is no excessive sediment formation in the process that could plug the reactor or any other equipment of the process.

(13) The amount of catalyst fed to the reactor is between 0.3 to 5 wt. % with respect to the weight of the feed, which is added directly to the feed flow dissolved in the hydrocarbon (when using an oil-soluble catalyst) or in water (when using a water-soluble catalyst).

(14) Within the properties of catalyst, they can have functions of hydrocracking and hydrogenation of the cracked molecules. This is achieved with metal-containing catalysts which have the property to exchange hydrogen atoms such as: Ni, Mo, Fe and Co, among others, and that are also resistant to sulfur poisoning in concentrations in the fresh catalyst up to 70 weight % of the composition depending on the type of compound used.

(15) An additional function of the slurry catalyst used in the process of this invention is to transform the sulfur and nitrogen compounds of the feed into hydrogen sulphide and ammonia, respectively. This is achieved, to some extent, by taking advantage of the property of the catalyst surface to capture by a chemical bond the hydrogen, sulfur and nitrogen atoms, whose function is adequately performed by the active metals of Fe. Ni and Mo in the form of sulfides. They have the ability to break the CC and CNC bonds and they can saturate the sulfur and nitrogen to form hydrogen sulfide and ammonia, respectively.

(16) Among the main technical contributions of the process of this invention, compared to conventional processes to upgrade the transport properties, are the following: It can be located next to the production facilities It uses operating conditions of low severity It is compact and it can be installed in production facilities on ground or offshore It upgrades the crude oil properties in a permanent way It uses as feed hydrocarbons and gases existing in the production centers It operates using dispersed phase reactor to avoiding problems of plugging It uses disposable catalysts at low concentrations

EXAMPLES

(17) Some practical examples are described in the following sections in order to have a better understanding of the present invention, without limiting its scope.

Example 1

(18) A heavy oil with 12.93API and other properties presented in Table 1 was upgraded with the hydroconvers on process of this invention.

(19) TABLE-US-00001 TABLE 1 Properties of the heavy crude oil to the process of this invention of Example 1 Properties Heavy Crude Oil Specific gravity @ 60/60 F. 0.9812 API gravity 12.71 Viscosity, cSt @: 25.0 C. 22791 37.8 C. 6110 54.4 C. 1518 Ramsbottom carbon, wt. % 16.07 Conradson carbon, wt. % 16.40 Total sulfur, wt. % 5.27 Total Nitrogen, ppm 4870 Basic Nitrogen, ppm 1740 Insoluble in nC.sub.5, wt. % 24.7 Insoluble in nC.sub.7, wt. % 18.78 Ash, wt. % 0.086 Nickel, ppm 78 Vanadium, ppm 456 Ni + V 534

(20) Operating conditions used are shown in Table 2. The added amount of catalyst was 1 wt % of molybdenu trioxide (MoO.sub.3) of high purity whose properties are shown in Table 3.

(21) Table 4 shows the properties of the upgraded crude rail by the process object of this invention.

(22) TABLE-US-00002 TABLE 2 Operating conditions of the hydroconversion process of heavy crude oil at low severity of this invention for the Example 1 H.sub.2/hydrocarbon ratio, Pressure, ft.sup.3/bbl Kg/cm.sup.2 Temperature, C. LHSV, h.sup.1 360 C. 380 C. 40 360 380 0.25 507 490 60 360 380 0.25 760 736 100 360 380 0.25 1270 1230

(23) TABLE-US-00003 TABLE 3 Properties of molybdenum trioxide catalyst used in the hydroconversion process of heavy oil of this invention for the Example 1 Size particle <5 m Appearance (color) White Appearance (form) Powder Purity 99.5% Insoluble material (NH.sub.4OH) 0.01%

(24) TABLE-US-00004 TABLE 4 Properties of the upgraded crude oil obtained by hydroconversion process of heavy crude oil of this invention for the Example 1 Viscosity Metals API Sulfur @ 37.8 C. (Ni + V) Gravity wt. % cSt ppm Temperature C. 360 380 360 380 380 360 380 Pressure, Kg/cm.sup.2 40 14 19.5 4.83 3.5 150 533 533 60 14.1 17.9 4.82 3.6 120 531 530 100 14.2 17.8 4.86 3.7 100 530 528

(25) Table 4 shows that at 380 C. in ail cases, the upgraded crude oil has the viscosity specification (<250 eSt at 37.8 C.) with API gravity between 17.8 and 19.5 units, Because it is a dispersed unsupported catalyst, they is not space for the metals to be deposited as in a supported catalyst, for this reason the metal content in the feed (Ni+V=534 ppm) is practically the same than in the products (528-533 ppm). In the case of sulfur removal, the content in the feed (5.27 wt. %) is reduced to between 3.50 and 4.86 weight %, which is equivalent to a reduction between 33.6 and 7.8% respectively.

Example 2

(26) The heavy oil of Example 1, whose properties are presented in Table 1 was upgraded by hydroconversion process using the dispersed phase of this invention, with the same catalyst of Example 1 but varying the amount of catalyst in the reactor from 0.5 to 2 wt. % with respect to the feed at the operating conditions shown in the Table 5.

(27) TABLE-US-00005 TABLE 5 Operating conditions for the hydroconversion process of heavy oil at low severity of this invention for the Example 2 Pressure, Kg/cm.sup.2 40 Temperature, C. 380 H.sub.2/hydrocarbon ratio, ft.sup.3/bbl 490 LHSV, h.sup.1 0.25

(28) The results shown in Table 6 indicate an upgrading in the transport properties of the crude oil. API gravity is increased to values between 18 to 21 units and the viscosity at 37.8 C. is reduced to between 100-180 cSt. Again, metal removal is not observed because an unsupported catalysts is used, and sulfur removal is between 12.7 to 16.5 wt. %.

(29) TABLE-US-00006 TABLE 6 Properties of the products obtained in the hydroconversion process of the heavy crude oil of this invention for the Example 2 Catalyst Sulfur, Viscosity @ 37.8 Metals, Ni + V, wt. % API Gravity wt. % C., cSt ppm 0.5 18 4.5 100 532 1.0 19.2 4.6 158 532 2.0 21 4.4 180 532

Example 3

(30) The heavy crude oil of Examples 1 and 2 was treated with the hydroconversion process in dispersed phase of this invention, but using oxide iron (III) of high purity as finely divided catalyst (Table 7) at the operating conditions shown in Table 5.

(31) TABLE-US-00007 TABLE 7 Properties of iron oxide catalyst (III) (Fe.sub.2O.sub.3) (purity > 99.5%) used in the hydroconversion process of heavy crude oil of this invention for Example 3 Size particle <5 m Appearance (color) Dark Red Appearance (form) Powder Iron content, wt. % 62.9-71.3

(32) The obtained results are shown in Table 8. With the hydroconversion process of this invention an important upgrading in the transport properties of treated crude oil is achieved with a low sulfur removal and a null metal removal.

(33) The liquid yield of the process using either molybdenum trioxide or iron oxide ail) is high as shown in Table 9.

(34) TABLE-US-00008 TABLE 8 Properties of the products obtained in the hydroconversion process of heavy crude oil of this invention for the Example 3 Viscosity @ Metals, Sulfur, 37.8 C., Ni + V API Gravity wt. % cSt ppm Temper- 360 380 360 380 380 360 380 ature C. Pressure Kg/cm.sup.2 60 17.64 18.58 5.19 4.54 188 530 529 85 17.20 18.27 4.76 4.57 136 532 530

(35) TABLE-US-00009 TABLE 9 Yield of liquid obtained by hydroconversion process of the heavy crude oil of this invention for Example 3 Catalyst Molybdenum wt. % trioxide Iron oxide (III) 0.5 88.9 85.1 1.0 98.0 98.0 2.0 98.0 98.0

(36) The formation of byproducts such as hydrogen sulfide is low since a high value of hydrodesulfurization is not obtained as shown in Table 10.

(37) TABLE-US-00010 TABLE 10 Hydrodesulfurization obtained in hydroconversion process of heavy crude oil of this invention for the Example 3 Catalyst Molybdenum wt. % trioxide Iron oxide (III) 0.5 14.2 14.2 1.0 13.7 13.0 2.0 13.7 13.1

Example 4

(38) The same heavy oil of Example 1 was upgraded with the hydroconversion process described in this invention using commercial grade iron oxide with a high iron content and whose chemical composition is shown in Table 11.

(39) The operating conditions for the hydroconversion process of this invention using commercial grade iron oxide are presented in Table 5. Due to its chemical composition, the amount of this catalyst was adjusted such that an equal molar amount of iron was fed to the process than when analytical grade catalysts was used.

(40) The obtained results are summarized in Table 12. With this catalyst a significantly upgrading of transport properties is obtained which is similar to that achieved using analytical grade iron oxides.

(41) TABLE-US-00011 TABLE 11 Chemical composition of commercial iron oxide used in the process described in this invention for the Example 4 Composition Commercial wt. % iron oxide Fe 72.060 O 16.710 Si 0.185 Ca 5.190 C 3.070 Others 2.785

(42) TABLE-US-00012 TABLE 12 Properties of the products obtained by hydroconversion process in the heavy oil of this invention using commercial iron oxide of the Example 4. Viscosity @ Sulfur Metal (Ni + V) Catalyst API Gravity 37.8 C. cSt wt. % ppm Commercial 17.1 203 4.55 532 grade iron oxide

Example 5

(43) The same crude from Example 1 was treated using hydroconversion process of this invention using as catalysts both oxide iron (III) as molybdenum trioxide of high grade of purity at the conditions shown in Table 5 and varying the contact time. The products obtained with the process of this invention have suitable properties for their handling and transportation by pipeline when the contact time is longer than 4 hours, which shown in Tables 13 and 14.

(44) TABLE-US-00013 TABLE 13 Properties of the products obtained by hydroconversion process in the heavy oil of this invention using iron oxide of high grade of purity of the Example 5 Contact time Viscosity@ 37.8 C. Sulfur (h) API Gravity cSt wt. % 4 18.4 190 4.59 5 18.7 189 4.52

(45) TABLE-US-00014 TABLE 14 Properties of the products obtained by hydroconversion process in the heavy oil of this invention using molybdenum trioxide of high grade of purity of the Example 5 Contact time Viscosity@ 37.8 C. Sulfur (h) API Gravity cSt wt. % 4 18.2 185 4.52