Catalyst precursor for hydrocracking reaction and method for hydrocracking heavy oil by using same

Abstract

The present invention relates to a catalyst precursor for forming a molybdenum disulfide catalyst through a reaction with sulfur in heavy oil and to a method for hydrocracking heavy oil by using same. According to the present invention, the yield of a low-boiling liquid product with a high economic value in the products by heavy oil cracking can be increased, and the yield of a relatively uneconomical gas product or coke (toluene insoluble component), which is a byproduct, can be significantly lowered.

Claims

1. A catalyst precursor for a hydrocracking reaction represented by the following Chemical Formula 1, which reacts with sulfur in a heavy oil to produce a molybdenum disulfide catalyst: ##STR00005## wherein R.sup.1 to R.sup.3 are independently of one another hydrogen, hydroxy, halogen, C.sub.1-C.sub.30 alkyl, C.sub.3-C.sub.30 cycloalkyl, C.sub.6-C.sub.30 aryl, C.sub.1-C.sub.30 alkoxy, C.sub.3-C.sub.30 cycloalkyloxy, or C.sub.6-C.sub.30 aryloxy, and optionally the alkyl, alkoxy, cycloalkyl, aryl, cycloalkyloxy, or aryloxy of R.sup.1 to R.sup.3 is independently of one another further substituted by one or more substituents selected from halogen, hydroxy, cyano, C.sub.1-C.sub.30 alkyl, C.sub.3-C.sub.30 cycloalkyl, and C.sub.6-C.sub.30 aryl.

2. The catalyst precursor for a hydrocracking reaction of claim 1, wherein R.sup.1 to R.sup.3 of Chemical Formula 1 are independently of one another hydroxy, C.sub.1-C.sub.10 alkoxy, C.sub.3-C.sub.12 cycloalkyloxy, or C.sub.6-C.sub.12 aryloxy.

3. The catalyst precursor for a hydrocracking reaction of claim 1, wherein R.sup.1 to R.sup.3 of Chemical Formula 1 are independently of one another C.sub.1-C.sub.10 alkyl, C.sub.3-C.sub.12 cycloalkyl, C.sub.3-C.sub.12 cycloalkyl C.sub.1-C.sub.10 alkyl, or C.sub.1-C.sub.10 alkyl C.sub.3-C.sub.12 cycloalkyl.

4. The catalyst precursor for a hydrocracking reaction of claim 1, wherein R.sup.1 to R.sup.3 of Chemical Formula 1 are independently of one another C.sub.6-C.sub.12 aryl, C.sub.6-C.sub.12 aryl C.sub.1-C.sub.10 alkyl, or C.sub.1-C.sub.10 alkyl C.sub.6-C.sub.12 aryl.

5. A hydrocracking method of a heavy oil, the method comprising: mixing a sulfur-containing heavy oil and a catalyst precursor of the following Chemical Formula 1 to produce a molybdenum disulfide catalyst, and performing a hydrocracking reaction of the heavy oil by using the molybdenum disulfide catalyst: ##STR00006## wherein R.sup.1 to R.sup.3 are independently of one another hydrogen, hydroxy, halogen, C.sub.1-C.sub.30 alkyl, C.sub.3-C.sub.30 cycloalkyl, C.sub.6-C.sub.30 aryl, C.sub.1-C.sub.30 alkoxy, C.sub.3-C.sub.30 cycloalkyloxy, or C.sub.6-C.sub.30 aryloxy, and optionally the alkyl, alkoxy, cycloalkyl, aryl, cycloalkyloxy, or aryloxy of R.sup.1 to R.sup.3 is independently of one another further substituted by one or more substituents selected from halogen, hydroxy, cyano, C.sub.1-C.sub.30 alkyl, C.sub.3-C.sub.30 cycloalkyl, and C.sub.6-C.sub.30 aryl.

6. The hydrocracking method of a heavy oil of claim 5, wherein the molybdenum disulfide catalyst is a molybdenum disulfide catalyst doped with phosphorus (P) containing 0.001 to 0.1 atom % of a phosphorus atom, based on a total number of atoms in the molybdenum disulfide catalyst.

7. The hydrocracking method of a heavy oil of claim 5, wherein the catalyst precursor is added at 0.01 to 5 wt %, based on a total weight of a reactant.

8. The hydrocracking method of a heavy oil of claim 5, wherein the hydrocracking reaction is performed at a temperature of 300 to 500° C. under a 10 to 200 atm condition.

9. The hydrocracking method of a heavy oil of claim 5, wherein the molybdenum disulfide catalyst is doped with phosphorus (P).

10. The hydrocracking method of a heavy oil of claim 9, wherein the molybdenum disulfide catalyst doped with phosphorus contains 0.001 to 1.0 mol of phosphorus (P) with respect to 1 mol of a molybdenum atom.

11. The hydrocracking method of a heavy oil of claim 5, wherein the heavy oil is a hydrocarbon having a hydrogen atom/carbon atom ratio (H/C) of 1 or less and containing 0.1 wt % or more of a sulfur atom, based on a total weight.

Description

EXAMPLE 1

(1) Hydrocracking reaction using Mo(O)(O.sub.2).sub.2(PPh.sub.3).sub.2

(2) Step 1. To a 100 mL Schlenk tube substituted with argon, 1 g (6.94 mmol) of MoO.sub.3 and 2 ml of hydrogen peroxide (H.sub.2O.sub.2, 27%) were added, and stirring was performed at 65° C. for about 45 minutes. When the reactant became a yellow transparent solution, the Schlenk tube was soaked in ice water to lower the temperature of the reactant to 0° C. When the temperature of the reactant was lowered, triphenylphosphine (4 g, 15.28 mmol) was dissolved in 10 ml of tetrahydrofuran (THF) and the solution was slowly added dropwise to the Schlenk tube. After complete addition dropwise, the reaction was performed at 0° C. for 1 hour and at room temperature (23° C.) for 1 hour. After the reaction, a supernatant was removed, precipitates were washed once with distilled water and three times each with ethanol and ethyl ether and dried, thereby obtaining a catalyst precursor for a hydrocracking reaction (Mo(O)(O.sub.2).sub.2(PPh.sub.3).sub.2) (yield: 86%).

(3) .sup.1H-NMR (CD.sub.2Cl.sub.2, ppm): 7.72˜7.45 (m 15H)

(4) .sup.13C-NMR (CD.sub.2Cl.sub.2, Ppm): 133.24, 132.22, 131.98, 131.44 (Phenyl)

(5) .sup.31P-NMR (DMSO, ppm): 25.46

(6) FT-IR (cm.sup.−1): 952, 864, 662, 583

(7) Step 2. The catalyst precursor for a hydrocracking reaction (Mo(O)(O.sub.2).sub.2(PPh.sub.3).sub.2) was used to perform a hydrocracking reaction of reduced-pressure residual oil (VR) under the following conditions. Here, a reduced-pressure residual oil available from Hyundai Oilbank was used as the reduced-pressure residual oil, and the elemental component thereof and each content thereof were analyzed and shown in the following Table 1.

(8) Specifically, to a high-temperature high-pressure reactor having a capacity of 100 ml, 20 g of a reduced-pressure residual oil was added, the catalyst precursor prepared above (Mo(O)(O.sub.2).sub.2(PPh.sub.3).sub.2) was added at 250 wppm (based on a Mo element, 0.025 wt % based on the reduced-pressure residual oil), hydrogen filling and purging were repeated three or more times in the reactor, and then the reactant was prepared so that hydrogen is 80 bar at 80° C. The temperature of the prepared reactant was raised to 430° C., and then the hydrocracking reaction was performed for 1 hour simultaneously with stirring (1500 rpm).

(9) When the reaction was finished, the reactant was rapidly cooled to a room temperature state by a cooling coil, the gaseous product was captured in a tedlar bag and analyzed by gas chromatography equipped with TCD and FID, the liquid product and coke were separated depending on a solubility difference in toluene and quantified, and a viscosity distribution of the separated liquid product was analyzed according to the method of ASTM D7169 (GC-SIMDIS).

(10) In addition, the components of the hydrocracked reduced-pressure residual oil and the components obtained after the hydrocracking reaction were subjected to fractional distillation and are shown in Table 1. Table 2 shows the results of analyzing coke components produced after the hydrocracking reaction of a vacuum residual oil using a (Mo(O)(O.sub.2).sub.2(PPh.sub.3).sub.2) precursor by XPS.

(11) In addition, the analysis results of the products produced after the hydrocracking reaction of the vacuum residual oil in each of Examples 1 to 5 and Comparative Examples 1 and 2 are shown in the following Table 3.

(12) TABLE-US-00001 TABLE 1 Elemental component and content of Classification reduced-pressure residual oil Elemental C 84 wt % analysis H 10.71 wt % S 4.84 wt % N 0.14 wt % Others 0.31 wt % Total 100 wt % H/C mole fraction 1.45 Metal Ni 36.4 ppm component V 151 ppm analysis Fe 38.3 ppm Ca 25 ppm Si 198 ppm SARA Saturate 4 wt % analysis Aromatic 61 wt % Resin 18 wt % Asphaltene 17 wt % Total 100 wt % Fractional Room temperature 0.05 wt % distillation to 150° C. 150 to 220° C. 0.01 wt % 220 to 343° C. 4.59 wt % 343 to 450° C. 45.82 wt % 450 to 550° C. 34.06 wt % 550 to 900° C. 2.01 wt % Residual oil 3.46 wt % Total 100 wt %

(13) TABLE-US-00002 TABLE 2 Component Content (atom %) C 88.88 O 6.61 P 0.06 S 2.92 Mo 1.53

(14) As shown in the above Table 2, it was confirmed that the catalyst precursor for a hydrocracking reaction according to the present invention (Mo(O)(O.sub.2).sub.2(PPh.sub.3).sub.2) may produce a molybdenum disulfide catalyst (MoS.sub.2) by a reaction with sulfur in the heavy oil. Specifically, it was confirmed that the produced molybdenum disulfide catalyst was doped with 0.06 atom % of phosphorus (P).

EXAMPLE 2

(15) Hydrocracking reaction using Mo(O)(O.sub.2).sub.2(P(OEt).sub.3).sub.2

(16) Step 1. A catalyst precursor for a hydrocracking reaction (Mo(O)(O.sub.2).sub.2(P(OEt).sub.3).sub.2) was prepared under the same reaction conditions as Step 1 of Example 1, by using triethylphosphite instead of triphenylphosphine, as a ligand having a coordination number of 1 in Step 1 of Example 1.

(17) .sup.1H-NMR (DMSO-d.sub.6, ppm): 1.23 (m, 18H), 3.98 (m, 12H)

(18) .sup.13C-NMR (DMSO-d.sub.6, ppm): 15.90, 15.96, 63.01, 63.07

(19) FT-IR (cm.sup.−1): 942, 983, 911, 803

(20) Step 2. A hydrocracking reaction was performed under the same reaction condition as Step 2 of Example 1, by using the catalyst precursor for a hydrocracking reaction (Mo(O)(O.sub.2).sub.2(P(OEt).sub.3).sub.2).

(21) In addition, each product was analyzed according to the evaluation method of each step performed in Example 1, and the analysis results of the product produced after the hydrocracking reaction are shown in the following Table 3.

EXAMPLE 3

(22) Hydrocracking Reaction Using Mo(O)(O.sub.2).sub.2(PCy.sub.3).sub.2

(23) Step 1. A catalyst precursor for a hydrocracking reaction (Mo(O)(O.sub.2).sub.2(PCy.sub.3).sub.2) was prepared under the same reaction conditions as Step 1 of Example 1, by using tricyclohexanephosphine instead of triphenylphosphine, as a ligand having a coordination number of 1 in Step 1 of Example 1.

(24) .sup.1H-NMR (CD.sub.2Cl.sub.2, ppm): 1.99 (m, 9H), 1.81 (d, 6H), 1.68 (s, 3H), 1.51 (t, 6H), 1.26 (s, 9H)

(25) .sup.13C-NMR (CD.sub.2Cl.sub.2, ppm): 217.19 (Mo—CO), 37.72 (P—C—), 30.43 (—CH.sub.2—)

(26) Step 2. A hydrocracking reaction was performed under the same reaction condition as Step 2 of Example 1, by using the catalyst precursor for a hydrocracking reaction (Mo(O)(O.sub.2).sub.2(PCy.sub.3).sub.2).

(27) In addition, each product was analyzed according to the evaluation method of each step performed in Example 1, and the analysis results of the product produced after the hydrocracking reaction are shown in the following Table 3.

EXAMPLE 4

(28) Hydrocracking Reaction Using Mo(C.sub.0).sub.4(TOP).sub.2

(29) Step 1. To a 100 mL Schlenk tube substituted with argon, 1 g (3.8 mmol) of Mo(CO).sub.6 and trioctylphosphine were dissolved in 10 ml of diethylene glycol dimethyl ether, and the reaction was performed at 150° C. for 20 hours. After the reaction, a supernatant was removed, and precipitates were washed once with distilled water and three times each with ethanol and ethyl ether and dried, thereby preparing a catalyst precursor for a hydrocracking reaction (Mo(CO).sub.4(TOP).sub.2).

(30) .sup.1H-NMR (CDCl.sub.3, ppm): 1.64 (m 6H), 1.40 (m, 36H), 0.88 (t, 9H)

(31) .sup.13C-NMR (CDCl.sub.3, ppm): 212.79 (M-CO), 31.93, 31.29, 29.37, 27.69, 26.10, 23.94, 22.78 (—CH.sub.2—), 14.21 (—CH.sub.2CH.sub.3)

(32) FT-IR: 2922.4, 2853.3 (Octyl), 1877.4 cm.sup.−1 (Mo—CO)

(33) Step 2. A hydrocracking reaction was performed under the same reaction condition as Step 2 of Example 1, by using the catalyst precursor for a hydrocracking reaction (Mo(CO).sub.4(TOP).sub.2).

(34) In addition, each product was analyzed according to the evaluation method of each step performed in Example 1, and the analysis results of the product produced after the hydrocracking reaction are shown in the following Table 3.

EXAMPLE 5

(35) Hydrocracking Reaction Using Mo(CO).sub.4(TCyHP).sub.2

(36) Step 1. A catalyst precursor for a hydrocracking reaction (Mo(CO).sub.4(TCyHP).sub.2) was prepared under the same reaction conditions as Step 1 of Example 4, by using tricyclohexanephosphine instead of triphenylphosphine, as a ligand having a coordination number of 1 in Step 1 of Example 4.

(37) .sup.1H-NMR (CD.sub.2Cl.sub.2, ppm) 2.04 (m, 12H), 1.87 (m, 6H), 1.68 (s, 3H), 1.48 (m, 3H), 1.26 (s, 9H)

(38) .sup.13C-NMR (CD.sub.2Cl.sub.2, ppm): 217.19 (Mo—CO), 37.72 (P—C—), 30.43, 28.36, 27.016

(39) Step 2. A hydrocracking reaction was performed under the same reaction condition as Step 2 of Example 1, by using the catalyst precursor for a hydrocracking reaction (Mo(CO).sub.4(TCyHP).sub.2).

(40) In addition, each product was analyzed according to the evaluation method of each step performed in Example 1, and the analysis results of the product produced after the hydrocracking reaction are shown in the following Table 3.

COMPARATIVE EXAMPLE 1

(41) Hydrocracking Reaction Using Molybdenum 2-ethylenehexanoate

(42) Step 1. According to the method of the patent KR 1396181, 30.0 g of a molybdic acid (Aldrich, MoO.sub.3≥85.0%) and 102.2 g of 2-ethylhexanoic acid (Aldrich, 99%) were mixed together in a 300 ml flask and then heated at 200° C. for 1 hour while being purged with N.sub.2 at 100 ml/min with stirring. Purging was replaced with a mixture of 20% H.sub.2 and 80% N.sub.2 and maintained at 200° C. for 12 hours. The reaction yielded molybdenum 2-ethylhexanoate having 14.7 wt % of Mo.

(43) .sup.1H-NMR (CDCl.sub.3, ppm): 2.256 (m, 1H), 1.620 (m, 4H), 1.283 (m, 4H), 0.910 (m, 6H)

(44) .sup.13C-NMR (CDCl.sub.3, ppm): 183.38, 47.31, 31.58, 29.66, 25.28, 22.74, 13.90, 11.74

(45) Step 2. A hydrocracking reaction was performed under the same reaction condition as Step 2 of Example 1, by using the molybdenum 2-ethylhexanoate.

(46) In addition, each product was analyzed according to the evaluation method of each step performed in Example 1, and the analysis results of the product produced after the hydrocracking reaction are shown in the following Table 3.

COMPARATIVE EXAMPLE 2

(47) To the molybdenum 2-ethylhexanoate precursor synthesized in Step 1 of Comparative Example 1, 1 equivalent of triphenylphosphine (Pph3).sub.3) was added, and a hydrocracking reaction was performed under the same reaction conditions as Step 2 of Comparative Example 1.

(48) In addition, each product was analyzed according to the evaluation method of each step performed in Example 1, and the analysis results of the product produced after the hydrocracking reaction are shown in the following Table 3.

(49) TABLE-US-00003 TABLE 3 Comparative Comparative Example Example Example Example Example Example Example Classification 1 2 3 4 5 1 2 {circle around (1)} Gaseous 5.22 5.34 5.73 5.50 5.30 6.70 5.44 product (%) {circle around (2)} Liquid product (%) Naphtha 14.44 15.04 10.79 15.77 14.71 4.50 7.21 (IPB-177° C.) M.D..sup.a 21.42 23.94 24.42 24.10 23.57 27.00 19.56 (177-343° C.) Gas oil 37.62 31.88 35.28 38.87 31.50 34.40 36.77 (343-524° C.) {circle around (3)} Residue (%) (524° C.-FBP) 20.55 23.00 22.83 14.80 23.97 24.10 28.90 {circle around (4)} Coke (%).sup.d 0.75 0.80 0.95 0.96 0.95 3.30 2.12 Liquid yield (%).sup.b 73.48 70.86 70.49 78.74 69.78 65.90 63.54 Conversion (%).sup.c 78.70 76.2 76.22 84.24 75.08 72.60 71.10 .sup.aM.D.: Middle distillate .sup.b100%-{circle around (1)}-{circle around (3)}-{circle around (4)} .sup.c100%-3 .sup.dToluene-insoluble component (%)

(50) As shown in Table 3, it was confirmed that when the molybdenum disulfide catalyst prepared from the catalyst precursor according to the present invention was used, a content of a liquid product was high and a production amount of coke (toluene-insoluble component) which is a by-product was significantly low.

(51) Specifically, the molybdenum disulfide catalyst prepared from the catalyst precursor according to the present invention may implement 10 wt % or more of selectivity to the low-boiling point liquid product, of course, and provide a high-quality light oil (such as gasoline and diesel) having 1 wt % or less of a toluene-insoluble component (coke) which is a by-product. Besides, the above-described effect is expected as a synergistic effect generated by doping the molybdenum disulfide catalyst prepared from the catalyst precursor according to the present invention with phosphorus (P). That is, it is noted that the above-described effect showed a different aspect of the effect from the case of simply separately adding a compound containing phosphorus (P) to the molybdenum disulfide catalyst later.

(52) Specifically, when the catalyst precursor including oxodiperoxy molybdenum derived from molybdenum oxide according to the present invention is used, it is also commercially useful in that the molybdenum disulfide catalyst may be provided under the very economical conditions.

(53) As described above, though the exemplary embodiments of the present invention have been described in detail, a person skilled in the art may make various variations of the present invention without departing from the spirit and the scope of the present invention, as defined in the claims which follow. Accordingly, any modification of the following Examples of the present invention may not depart from the technique of the present invention.