HYDROPROCESSING OF HEAVY CRUDES BY CATALYSTS IN HOMOGENEOUS PHASE

Abstract

This disclosure relates to a procedure, which through the application of a catalyst in homogeneous phase, allows the transformation of heavy hydrocarbons (vacuum residue, atmospheric residue, heavy and extra-heavy crudes) into hydrocarbons of lower molecular weight, characterized because after its application, the hydrocarbons obtain greater API gravity, lower kinematic viscosity and different composition by hydrocarbon families (SARA) that increases the proportion of saturated and aromatic resins and asphalts. The sulphur and nitrogen content is also reduced, resulting in higher yields to high commercial value distillates and a lighter product as compared to the original crude.

Claims

1. A procedure for the preparation of a catalyst, comprising: 1. mixing a mineral acid and ammonium salts, and shaking the mixture at a temperature of 25° C. until a clear solution is obtained, with a pH variation between 1 and 2; 2. incorporating Nickel salts into the clear solution and solubilize at 40-100° C., then dissolving in water, and maintaining agitation of the solution for a time of 3 h at a temperature of 25° C., resulting in a green and translucent solution; 3. storing the green and translucent solution in a closed container under ambient conditions; and 4. dehydrating the catalyst at 90° C., wherein the catalyst has a final molar ratio of 1.0 Ni, 0.084 Mo, 0.295 H+, 14.42 H.sub.2O, at pH 1 to 3; and wherein the catalyst transforms heavy and extra-heavy crude oils into lighter oils.

2. The procedure for the preparation of a catalyst, in accordance with claim 1, wherein during preparation the water can be one of running water, congenital water, or brine.

3. The procedure for preparation of a catalyst in accordance with claim 1, wherein the catalyst is used in a reaction with heavy crude, feeding hydrogen to raise API gravity and results in lowering the viscosity of the oil, increasing the proportion of saturated and aromatic, and decreasing the amount of long-chain paraffinic resins, asphaltenes, sulfur and nitrogen.

4. The procedure for preparation of a catalyst in accordance with claim 3, further comprising using the catalyst in loads with API gravity of 1 to 14 and viscosities in the range between 60,000 to 1, 000,000 cSt at 65° C.

5. The procedure for preparation of a catalyst in accordance with claim 3, further comprising using the catalyst in a liquid phase, gel or dehydrated phase.

6. The procedure for preparation of a catalyst in accordance with claim 3, further comprising using the catalyst in a supported form.

7. The procedure for preparation of a catalyst in accordance with claim 6, wherein the supported catalyst presents a specific BET specific area between about 30 and about 1250 m.sup.2/g.

8. The procedure for preparation of a catalyst in accordance with claim 7, wherein a support for the supported catalyst is selected from a group consisting of SiO.sub.2, TiO.sub.2, ZrO.sub.2, Al.sub.2O.sub.3, SBA's and MCM's.

9. The procedure for preparation of a catalyst in accordance with claim 8, where the reaction temperature is between about 350 and about 410° C., at a pressure up to about 50 to about 140 Kg/cm.sup.2 and a time of about 0.5 to about 4 h.

10. The procedure for preparation of a catalyst in accordance with claim 9, wherein the catalyst is anchored to a rock formation.

11. The procedure for preparation of a catalyst in accordance with claim 10, wherein the rock formation comprises rocks selected from a group consisting of dolomites, limestones, magnesites, diatomites and mixtures thereto, rocks of carbonated deposit, and synthetic rocks of Berea or Bedford limestone.

12. The procedure for preparation of a catalyst in accordance with claim 11, wherein the catalyst is injected directly into the injector well of a reservoir of the rock formation.

13. The procedure for preparation of a catalyst in accordance with claim 12, wherein the rock formation further comprises a carbonated deposit at a variable ratio of 1 to 10% weight with respect to hydrocarbon.

14. The procedure for preparation of a catalyst in accordance with claim 13, further comprising activation of active metals carried out on-site at the rock formation.

15. The procedure for preparation of a catalyst in accordance with claim 14, further comprising a coke generation of only 0.001-0.6% weight.

16. The procedure for preparation of a catalyst in accordance with claim 15, wherein use of the catalyst promotes the disintegration of resins and asphaltenes to hydrocarbons of lower molecular weight, said hydrocarbons including heavy gas oil, diesel and gasoline.

Description

BRIEF DESCRIPTION OF THE FIGURES OF INVENTION

[0025] FIG. 1 illustrates, through a block diagram, the experimental system with rock core.

DESCRIPTION DETAILED OF THE INVENTION

[0026] The present disclosure relates to the synthesis and application of a homogeneous phase catalyst, which allows the transformation of heavy and extra-heavy crude oils into lighter oils, by hydro-disintegration and hydrogenation reactions, in a cyclic process either in a reactor belonging to a surface installation or at the bottom of the well, simulating reservoir conditions.

[0027] The preparation of the catalyst is carried out in aqueous phase (based on running water, congenital water, and/or brine), using inorganic salts of a metal of groups VIIIB, VIB, IB, such as Fe, Co, Ni, Cu, Mo, W. The preparation of the catalyst of the present disclosure includes the following steps: [0028] 1. Using conventional vessel, phosphoric acid (H3PO4, technical grade) and ammonium molybding ((NH4) 6Mo7O24.4H2O, technical grade) are mixed, stirring moderately at 25° C., until a dear solution is obtained, The pH of the solution varies between 1 and 2. [0029] 2. In the second step, the nickel sulfate hexahydrate (NiSO4.6H2O technical grade) is incorporated and solubilized at 40-100° C., preferably 60-90° C., dissolving in running water, keeping the agitation constant for three hours at 25° C. [0030] 3. The solution formed above is stored in a closed container under environmental conditions, where the catalytic solution must be green and translucent. [0031] 4. Finally, the catalyst is dehydrated at 90° C., depending on the type of application to which it will be directed (liquid phase, gel or particles of the corresponding salts). The final molar ratio is 1.0 nickel: 0.084 molybdenum: 0.295 H+: 14.42 H2O at pH 1-3.

[0032] The catalyst of the present disclosure, presents high catalytic activity for hydrocracking reactions and hydrogenation of heavy hydrocarbons. The procedures used during its application allow the physical and chemical properties of the hydrocarbon to be improved, decreasing its kinematic viscosity, which allows its fluidization in pipes. It increases the gravity API, changing the composition by hydrocarbon families, (SARA), increasing the proportion of saturated and aromatic, while decreasing fractions of resins and asphalts. Likewise, the sulphur and nitrogen content is reduced, resulting in higher yields to distillates of high commercial value, e.g. gasoline, diesel and diesel, mainly reaction products are not carbon-formed and therefore the liquid yield is very high, greater than 95%.

[0033] The evaluations were carried out according to the scheme in FIG. 1 under operating conditions that prevent the generation of coal, optimizing the performance of liquid products. To do this the operation interval is as follows, shown in Table 1:

TABLE-US-00001 TABLE 1 Operating Conditions Presssure Kg/cm.sup.2  70-120 Temperature: 340-420° C. Reaction time:  0.5-4 h Catalyst Concentration:  0.5 10% w

[0034] Results are observed indicating a possible breakdown of asphalt molecules and resins, as well as the removal of sulfur and nitrogen compounds, with an increase in API gravity and a significant decrease in their viscosity.

[0035] In order to show unsamped catalyst reference parameters, the conversion of heavy crude oil with a prototype liquid catalyst formulated based on nickel was evaluated. The results are shown in Examples 1 to 4.

[0036] The load used for the realization of the different experiments, was a heavy crude of the Golden Strip (North of Veracruz, Mexico), its properties are detailed in Table 2. It was also experimented with rocks representative of a carbonated deposit consisting of dolomites (CaCO3—MgCO3), limestone (CaCO3), magnesites (MgCO3), diatom ites (SiO2—H2O) and mixtures thereto; rocks of the site itself and rock of outcrop analogous to the deposit, as well as synthetic rocks of the type Berea (SiO3—Al2O3—MgO—CaO) and limestone Bedford (SiO—MgO—CaO), which are used both in crushed form to different meshes and/or nuclei with different dimensions.

EXAMPLE 1

[0037] The homogeneous Ni-based catalyst was prepared by the aqueous impregnation method. In this method, the required amount of ammonium heptamolibdate [(NH4) 6Mo7O24.4H2O], nickel nitrate [Ni (NO3)2.6H2O], and phosphoric acid [H3PO4], in stochiometric proportions at room temperature and at pH between 2 and 3, with constant agitation, is dissolved.

[0038] In a batch reactor with a capacity of 500 mL, 200 g of heavy crude oil and 2.5 g of liquid catalyst made from nickel, with mechanical agitation at 800 rpm, were placed. The ambient temperature is increased to 350° C. at a speed of 5° C./min. Hydrogen is then fed, reaching the pressure of 100 Kg/cm2 in the system. Once the above conditions are stabilized, the reaction time was one hour, starting the cooling of the reactor, and recovering the hydrotreated crude.

EXAMPLE 2

[0039] In a batch reactor with a capacity of 500 mL, 200 g of heavy crude oil and 2.0 g of liquid catalyst made from nickel, with mechanical agitation at 800 rpm, were placed. The ambient temperature is increased to 380° C. at a speed of 5° C./min. Hydrogen is fed, reaching the pressure of 100 Kg/cm2 in the system, and once the above conditions stabilized, the reaction time was one hour, starting the cooling of the reactor, and recovering the hydrotreated crude.

EXAMPLE 3

[0040] Taking advantage of the porous volume of the rock and its ability to store fluids such as crude oil, gas and brine, the raw oil is saturated with hydrogen in the presence of a catalyst that is anchored to the rock, at a concentration of 2.0% weight. A stainless steel cell, a continuous injection pump for high pressure, with automatic control, and a reverse pressure regulator are required. The cylinders containing the oil are used to perform the injection process, at a controlled speed and pressure, until the oil saturation defined for the test conditions is reached. A core (1.5×2.5″) is placed inside a cell, confinement pressure is applied, vacuumed for a period of one hour and the oil containing catalyst is injected, (same as anchoring to the rock formation is slowly added the necessary amount of crude-catalyst until the desired oil saturation is reached. The ambient temperature is increased to 350° C. at a speed of 30° C./min. Hydrogen is fed, reaching the pressure of 100 Kg/cm2 in the system. Once the previous conditions have been stabilized the reaction time was one hour, the cooling of the reactor starts and the hydrotreated crude is recovered.

EXAMPLE 4

[0041] Taking advantage of the porous volume of the rock and the storage capacity of fluids such as crude, gas and brine, the saturation of the crude oil containing catalyst is performed first. At this stage a stainless steel cell, a continuous injection pump for high pressure, with automatic control, and a reverse pressure regulator are used. The cylinders containing the oil are used for the injection process, at a controlled and pressure speed, until the oil saturation defined for the test conditions is reached. A core of (1.5×2.5″) of carbonate formed by dolomites (CaCO3—MgCO3), placed inside a cell, then a confinement pressure is applied and vacuumed for a period of one hour and the oil containing the catalyst that is anchored to the rock is injected, slowly adding the necessary amount of that fluid (crude-catalyst), until the desired oil saturation is reached. The ambient temperature is increased to 370° C. at a speed of 30° C./min. Hydrogen is fed, reaching the pressure of 100 Kg/cm2 in the system. Once stabilized the above conditions is left a reaction time of one hour, starting the cooling of the reactor and recovering the hydrotreated crude. Examples 3 and 4 are illustrated in Table 3.

TABLE-US-00002 TABLE 2 Load properties and batch reactor products, examples 1 and 2 Properties Heavy Crudes Example 1 Example 2 Temperature, ° C. 350 380 Pressure kg/cm.sup.2 100 100 Gravity ° API 10.7 17 18 Viscosity, cSt 15.75° C. 13,490 135.8 125.7  25.0° C. 4,883 90 69  37.5° C. 3979 55.6 40 Sulfur total, ppm 5.3 3.71 3.58 Nitrogen total, ppm 4994 425 411 Carbon, ppm — 0.5 1.0 SARA, % wt Saturated 16 28.9 31.9 Resins 36 12.6 10.9 Aromatics 25 44.7 46.9 Asphaltenes 22 13.7 10.3 SimDis TIE 73 66 62 5.0/10.0 154/219 156/196 172/241  15/20 269/310 223/248 2511277  25/30 347/382 270/290 306/347  35/40 415/445 309/326 387/401  45/50 477/506 345/364 426/452  55/60 530/550 383/403 481/511  65/70 569/591 425/451 536/557  75/80 614/680 487/529 579/604  90/95 691/518 614/655 652/669 TFE 744 731 735 Gasoline: TIE-221; Diesel: 221-343; Heavy diesel: 343-540; Resids: 540+ (TIE: Initial boiling temperature; TFE: Final boiling temperature).

TABLE-US-00003 TABLE 3 Loading properties and products in a rock core, examples 3 and 4 Properties Heavy Crude Example 3 Example 4 Temperature, ° C. 350 380 Pressure kg/cm.sup.2 100 100 Gravity ° API 12.5 17 18 Viscosity, cSt 15.75 C. 13,490 135.8 125.7  25.0 C. 4,883 90 39  37.5 C. 1,550 55.6 24 Sulfur total, ppm 5.56 3.71 3.2 Nitrogen total, ppm 4494 425 1699 Carbon, ppm 1.0 1.2 SARA, % wt Saturated 16 28.9 30.4 Resins 36 12.6 10.9 Aromatics 25 45.7 37.4 Asphaltenes 26 12.7 9.4 SimDis TIE 73 32.8 78 5.0/10.0 154/219 106.5/115.4 124/151  15/20 269/310 138.2/157.1 165/179  25/30 347/382 171/190 192/205  35/40 415/445 201/216 219/232  45/50 477/506 229/244 245/259  55/60 530/550 259/274 272/286  65/70 569/591 291/309 300/314  75/80 614/680 332/351 330/350  90/95 691/518 415/483 405/457 TFE 744 503 608 Gasoline: TIE-221; Diesel: 221-343; Heavy diesel: 343-540; Waste: 540+ (TIE: Initial boiling temperature; TFE: Final boiling temperature)

EXAMPLE 5

[0042] 5 g of liquid catalyst formulated with nickel is impregnated in 250 g of ground rock of magnesites (MgCO3) and diatomites (SiO2—H2O) in mesh 40, the stirring is constant for 2 hours to achieve its perfect homogenization, and is left to rest for 4 hours. Subsequently, the crude oil was saturated at 24% (heavy crude). The continuous flow reactor is loaded with 325 g of the mixture of fluid composed of heavy crude oil -ground rock- catalyst, compacting it in the reactor evenly, then pressing the reactor with nitrogen to verify its watertightness, after 30 minutes the nitrogen is replaced by hydrogen at 100 Kg/cm2. Heating starts at a speed of 20° C./min, to reach the temperature from the ambient to 380° C. Once the temperature has reached the reaction after two hours, then the reactor is cooled to the ambient temperature. The amount of crude oil in the separator is quantified to determine the index of conversion and physicochemical properties.

EXAMPLE 6

[0043] 5 g of a liquid catalyst formulated with nickel in 250 g are impregnated with ground rock of outcrop analogous to the carbonated deposit with mesh 40, then left to rest for 4 hours. Then the saturation of the rock core was performed with crude 24% (heavy crude). This impregnated core is loaded into a continuous flow reactor; 325 g of the mixture of heavy crude-ground rock-catalyst, are compacted in the reactor evenly, the reactor is pressed with nitrogen to verify its tightness, and after 30 min the nitrogen is replaced by hydrogen at 100 Kg/cm.sup.2. Heating starts at a speed of 20° C./min, to reach the temperature from the environment up to 350° C. Once the temperature is reached, the reaction takes place for two hours, then the reactor cools to room temperature to start recovery. The recovered product is quantified for the amount of crude in the separator to determine the recovery rate and physical and chemical analyses are performed.

TABLE-US-00004 TABLE 4 Loading properties and reaction products in the porous medium (ground rock) Properties Crude Example 5 Example 6 Temperature, ° C. — 380 350 Pressure kq/cm2 — 100 100 Gravity ° API 12.5 17 18 Recovery, % — 80 65 SimDis TIE 73 59 70  5.0/10 154/219 180/237 170/222   15/20 269/310 281/317 263/298   25/30 347/382 350/387 329/359   35/40 415/445 414/442 390/419   45/50 477/506 473/500 448/480   55/60 530/550 524/543 507/530 +65/70 569/591 560/578 547/565   75/80 614/680 600/619 586/607   90/95 691/518 665/693 657/686 TFE 744 716 715 Gasoline: TIE-221: Diesel: 221-343: Heavy diesel: 343-540: Waste: 540+ (TIE: Initial boiling temperature: TFE: Final boiling temperature)

EXAMPLE 7

[0044] The homogeneous catalyst made from Ni in congenital water, was supported in gamma alumina (ABET s 225 m2/g, Pore volume s 0.40 cm3/g, average pore radius x 3.2 nm, particle size 0.20-0.32 mm). In a batch reactor with a capacity of 500 mL, 200 g of heavy crude and 2.5 g of liquid catalyst were placed, the ambient temperature is increased up to 380° C. at a speed of 5° C./min. Subsequently, hydrogen is fed, reaching the pressure of 100 Kg/cm2 in the system. Once the previous conditions are stabilized, the reaction time was one hour, the cooling of the reactor starts, and the hydrotreated.

XAMPLE 8

[0045] The homogeneous catalyst made from Ni in congenital water, was supported in mesoporous material (ABET s 1200 m2/g, Pore volume 0.42 cm3/g, average pore diameter s 2 nm, particle size 0.3 mm). In a batch reactor with a capacity of 500 mL, 200 g of heavy crude and 2.5 g of liquid catalyst were placed, the ambient temperature is increased up to 380° C. at a speed of 5° C./min. Subsequently, hydrogen is fed, reaching the pressure of 100 Kg/cm2 in the system. Once the previous conditions are stabilized, the reaction time was one hour, the cooling of the reactor starts, and the hydrotreated crude is recovered.

TABLE-US-00005 TABLE 5 Load properties and catalyst reaction products supported in alumina and mesoporous material Properties Residue Example 7 Example 8 Temperature, ° C. — 380 350 Pressure kq/cm.sup.2 — 100 100 Gravity API 15.5° C. 4.0 12 10 Viscosity, cSt 322900 270 545 Sulfur total, ppm 5.64 3.26 4.42 Nitrogen total, ppm 760 381 478 SimDis TIE 117 90 97 5.0/10 194/229 190/216 211/224  15/20 269/310 245/320 249/342  25/30 351/387 340/367 363/378  35/40 415/445 387/407 402/420  45/50 477/506 426/446 439/460  55/60 530/550 469/490 481/501  65/70 569/591 511/533 522/542  75/80 619/670 556/571 563/589  90/95 687/698 630/669 641/670 TFE 744 713 715 Gasoline: TIE-221; Diesel: 221-343: Heavy diesel : 343-540: Residue 540+ (TIE: Initial boiling temperature; TFE: Final boiling temperature)