Catalytic system and process for the hydroconversion of heavy oil products

Abstract

Catalytic system which can be used in processes for the hydroconversion of heavy oils by means of hydrotreatment in slurry phase, characterized in that it comprises: a catalyst, having the function of hydrogenating agent, containing MoS.sub.2 or WS.sub.2 or mixtures thereof in lamellar form or an oil-soluble precursor thereof; a co-catalyst, having nanometric or micronic particle-sizes, selected from cracking and/or denitrogenation catalysts. The co-catalyst preferably consists of zeolites having small-sized crystals and with a low aggregation degree between the primary particles, and/or oxides or sulfides or precursors of sulfides of Ni and/or Co in a mixture with Mo and/or W.

Claims

1. A catalytic system, comprising: a catalyst, as a hydrogenating agent; and a nanometric or micronic co-catalyst, that is a cracking catalyst, a denitrogenation catalyst, or a combination thereof, wherein the catalytic system is suitable for hydroconversion of a heavy oil, wherein the catalyst consists of MoS.sub.2, WS.sub.2, or a mixture thereof, in lamellar form, or an oil-soluble precursor thereof, wherein the catalyst is not supported, and wherein the co-catalyst consists of zeolites having small-sized crystals and with a low aggregation degree between primary particles.

2. The catalytic system according to claim 1 wherein the zeolites comprise medium or large pores.

3. The catalytic system according to claim 2, wherein the zeolites are Beta, Y, or MCM-22.

4. The catalytic system according to claim 1, wherein the co-catalyst is supported on solid particles with micronic or submicronic dimensions.

5. The catalytic system according to claim 4, wherein the solid particles on which the co-catalyst is supported are alumina, silica, silico-alumina, talc, mica, or a combination thereof.

6. The catalytic system according to claim 1, wherein the catalyst and co-catalyst are in a weight ratio from 100:1 to 1:70.

7. The catalytic system according to claim 6, wherein the catalyst and co-catalyst are in a weight ratio from 75:1 to 1:50.

8. A process for hydroconversion of a heavy oil, the process comprising: sending the heavy oil to a hydrotreatment in slurry phase with a catalytic system as in claims 2-5, or 6, wherein the heavy oil is a crude oil, a heavy crude oil, a bitumen from a tar sand, a distillation residue, a heavy distillation cut, a deasphalted distillation residue, a vegetable oil, an oil deriving from coal or oil shale, an oil obtained by a process comprising thermo-decomposition of a waste product, a polymer, a biomass, a distillate, or a combination thereof.

9. The process according to claim 8, further comprising: separating an effluent stream from the hydrotreatment downstream of the hydrotreatment, thereby obtaining a heavier liquid fraction comprising dispersed catalyst and co-catalyst, and recycling the heavier liquid fraction to the hydrotreatment.

10. The process according to claim 9, wherein the sending comprises feeding hydrogenation catalyst dispersed in a feedstock, comprising the heavier liquid fraction of the recycling, to the hydrotreatment, and wherein a concentration of the hydrogenation catalyst, based on a concentration of a metal or metals, is from 100 to 30,000 ppm.

11. The process according to claim 8, wherein the hydrotreatment is at a temperature of from 350 to 480° C. and a pressure of from 80 to 220 atmospheres.

12. The process of claim 8, wherein sending the heavy oil to the hydrotreatment in slurry phase with the catalytic system comprises hydrogenating the heavy oil, demetallizing the heavy oil, and cracking and denitrogenation of the heavy oil.

Description

EXAMPLE 1

Upgrading of RV Ural in a Stirred Micro-autoclave

(1) The test, which should be considered as a reference base case, was carried out using Mo as catalyst (introduced as oil-soluble precursor together with the feedstock).

(2) A Ural vacuum residue is used as feedstock, whose main characteristics are indicated in Table I below:

(3) TABLE-US-00001 TABLE I Main properties of the RV URAL feedstock Density at 15° C. 1.0043 (g/cm.sup.3) °API 9.4 Viscosity 100° C. 1277 (cSt) CCR (wt %) 18.9 C (wt %) 86.0 H (wt %) 10.2 H/C (mol/mol) 1.4 N (wt %) 0.57 S (wt %) 2.60 Ni (ppm) 84 V (ppm) 262 Fe (ppm) 48 Mo (ppm) Absent ASF C5 (%) 16.0 IBP-170° C. (%) 0 170-350° C. (%) 0 350-500° C. (%) 6.5 500-FBP (%) 93.5
The operating conditions used for the upgrading are:

(4) TABLE-US-00002 Treated feedstock 10 g Mo concentration 6000 wppm Pressure 160 bar Reaction temperature 420° C. Reaction time 4 h
The yield to products, conversion and HDN/HDS performances are indicated hereunder:

(5) TABLE-US-00003 gas DAO C5 ASF Conv H.sub.2S C.sub.1-C.sub.4 NAP AGO VGO 500+ C5 ASF Conv. wt % wt % wt % wt % wt % wt % wt % C5 500+ HDN HDS 0.8 2.4 6.6 25.4 27.6 30.6 4.3 73 62 33 72

EXAMPLE 2

Upgrading of RV Ural in a Stirred Micro-autoclave

(6) The test was carried out on RV Ural, using Mo as catalyst (introduced as oil-soluble precursor together with the feedstock) and Beta zeolite as co-catalyst (pre-calcined at 500® C. and introduced as powder together with the Mo), operating under the same operative conditions as test 1. The average particle-size of Beta zeolite is 10 μm.

(7) TABLE-US-00004 Treated feedstock 10 g Mo concentration 6000 wppm Co-catalyst concentration 4% wt Pressure 160 bar Reaction temperature 420° C. Reaction time 4 h
The yield to products, conversion and HDN/HDS performances are indicated hereunder:

(8) TABLE-US-00005 gas DAO C5 ASF Conv H.sub.2S C.sub.1-C.sub.4 NAP AGO VGO 500+ C5 ASF Conv. wt % wt % wt % wt % wt % wt % wt % C5 500+ HDN HDS 1.0 3.4 6.3 26.5 26.9 30.1 3.8 76 63 42 72

(9) An increase is observed in the HDN performances and for the conversion of the asphaltenes.

EXAMPLE 3

Upgrading of RV Ural in a Stirred Batch Micro-autoclave

(10) The test was carried out on RV Ural, under the same operative conditions as test 1, using MCM-22 zeolite as co-catalyst. The average particle-size of MCM-22 zeolite is 10 μm.

(11) The yield to products, conversion and HDN/HDS performances are indicated hereunder:

(12) TABLE-US-00006 gas DAO C5 ASF Conv H.sub.2S C.sub.1-C.sub.4 NAP AGO VGO 500+ C5 ASF Conv. wt % wt % wt % wt % wt % wt % wt % C5 500+ HDN HDS 1.0 3.3 6.9 25.2 26.7 30.9 3.7 77 63 43 72

(13) The results obtained show in all cases a similar distribution of the products and HDS activity, whereas, as far as the HDN activity and asphaltene conversion are concerned, increased performances were observed for the tests carried out in the presence of co-catalyst.

EXAMPLE 4

Upgrading of VB-tar in a Pilot Plant

(14) The test was carried out in a pilot unit with a slurry reactor in continuous, operating according to the typical scheme with recycling of the non-converted heavy fraction containing the catalyst, using Mo (introduced as oil-soluble precursor together with the feedstock) and Beta zeolite as co-catalyst (pre-calcined at 500° C. and introduced as a dispersion in a suitable hydrocarbon matrix). The average particle-size of Beta zeolite is 10 μm.

(15) A visbreaking tar was used as feedstock, whose main characteristics are indicated in Table II below:

(16) TABLE-US-00007 TABLE II Main properties of the VB-tar feedstock Density at 15° C. (g/cm.sup.3) 1.056 Viscosity 140° C. (cSt) 146.1 CCR (wt %) 32.5 C (wt %) 85.4 H (wt %) 8.8 H/C (mol/mol) 1.24 N (wt %) 0.5 S (wt %) 5.8 Ni (ppm) 77.7 V (ppm) 209 Fe (ppm) 31 Mo (ppm) 11.5 ASF C5 (%) 20 THFI (%) 0.2 IP-170° C. (%) — 170-350° C. (%) — 350-500° C. (%) 9.8 500-FBP (%) 70.0
The operative conditions used for the test are:

(17) TABLE-US-00008 Treated feedstock 2500 g/h Mo concentration 6000 wppm Co-catalyst concentration 4% wt Pressure 144 bar Reaction temperature 420° C.

(18) An evaluation of the performances of the plant under stationary conditions, in the presence of the co-catalyst, was effected over a useful period of 10 hours, comparing the quality and distribution of the yields of SCO (Synthetic Crude Oil) obtained with the data obtained under comparable running conditions.

(19) TABLE-US-00009 Conv Beta DAO Conv ASF Mo zeolite gas C5 ASF 500+ C5 HDS HDN ppmw wt % H.sub.2S C1-C4 NAP AGO VGO 500+ C5 % % % % 3000 0 4.5 10.1 5.3 31.3 36.3 6.1 0.1 92.3 99.5 79 32 10000 0 5.8 10.2 5.2 35.7 35.7 3.5 0.1 95.7 99.5 90 51 4600 4 5.8 9.2 6.8 39.1 33.2 2.9 0.1 96.5 99.8 91 64

(20) As far as the product distribution is concerned, a tendency is observed towards a lightening of the system, with an increase in the AGO content to the detriment of the heavier fractions. The quality of the product also appears to have positive effects, showing a significant reduction in the S and N contents, comparable to the results obtained when operating in the presence of higher concentrations of Mo (12,000 wppm).

EXAMPLE 5

Upgrading of RV Ural in a Stirred Batch Micro-autoclave with a Catalyst Based on Ni/Mo

(21) The test was carried out on RV Ural, using Mo as catalyst (introduced as oil-soluble precursor together with the feedstock) and a hydroconversion catalyst based on Ni—Mo (15% wt of Mo and 5% wt of Ni) supported on alumina as co-catalyst, operating under the same operative conditions as test 1. The average particle-size of the co-catalyst is 30 μm.

(22) The operative conditions used are:

(23) TABLE-US-00010 Treated feedstock 10 g Mo concentration 6000 wppm Co-catalyst concentration 4% wt Pressure 160 bar Reaction temperature 420° C. Reaction time 4 h
The yield to products, conversion and HDN/HDS performances are indicated below:

(24) TABLE-US-00011 DAO gas C5 ASF Conv H.sub.2S C.sub.1-C.sub.4 NAP AGO VGO 500+ C5 ASF Conv. wt % wt % wt % wt % wt % wt % wt % C5 500+ HDN HDS 0.8 2.4 6.3 26.3 27.2 30.5 3.5 78 64 40 81

(25) The results obtained show a product distribution and conversion of the heavy fractions similar to the base case (example 1), whereas there is an improvement in the HDN and HDS performances and conversion of the heavy 500° C.+ fraction.