CA1099658A - Hydrodesulfurization of petroleum distillates - Google Patents
Hydrodesulfurization of petroleum distillatesInfo
- Publication number
- CA1099658A CA1099658A CA282,894A CA282894A CA1099658A CA 1099658 A CA1099658 A CA 1099658A CA 282894 A CA282894 A CA 282894A CA 1099658 A CA1099658 A CA 1099658A
- Authority
- CA
- Canada
- Prior art keywords
- range
- catalyst
- hydrogenating
- group
- radius
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- 239000003209 petroleum derivative Substances 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 53
- 239000011148 porous material Substances 0.000 claims abstract description 38
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- 239000011593 sulfur Substances 0.000 claims abstract description 11
- PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical group [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 10
- 239000011733 molybdenum Substances 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- 239000002131 composite material Substances 0.000 abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 238000006477 desulfuration reaction Methods 0.000 description 14
- 230000023556 desulfurization Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- -1 iron group metals Chemical class 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- ZMXPKUWNBXIACW-UHFFFAOYSA-N [Fe].[Co].[Mo] Chemical compound [Fe].[Co].[Mo] ZMXPKUWNBXIACW-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- VAWNDNOTGRTLLU-UHFFFAOYSA-N iron molybdenum nickel Chemical compound [Fe].[Ni].[Mo] VAWNDNOTGRTLLU-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
HYDRODESULFURIZATION OF PETROLEUM DISTILLATES
ABSTRACT OF THE DISCLOSURE
Sulfur-containing petroleum distillates are desulfurized in the presence of hydrogen and a catalyst composite containing a Group VI-B hydrogenating component, at least one iron group hydro-genating component and alumina, the catalyst composite being further characterized as having from 5 to 20 volume percent of the pores with a radius in the range of 100 to 300 .ANG..
ABSTRACT OF THE DISCLOSURE
Sulfur-containing petroleum distillates are desulfurized in the presence of hydrogen and a catalyst composite containing a Group VI-B hydrogenating component, at least one iron group hydro-genating component and alumina, the catalyst composite being further characterized as having from 5 to 20 volume percent of the pores with a radius in the range of 100 to 300 .ANG..
Description
~ACXGROUND OF THE INVEN~ION
The hydrode~ulfurization of petroleum distillate hydro-c~rbons employing a ca~aly~ cpmprising a supported hydrogena~ing aomponent which is at least one member of,the group con6isting of Group VI-B and Group VlII metals in a fo~m capable of promoting hydro~enating reactions is well-known in the art. Especial~y e'ffective catalysts for the purpose of such hydrodesulfurization reaction~ are those comprising molybdenum and two members of the iron group metals. Preferred cat,alysts of thi~ class are those containing nickel, cobalt and molyb,denum but other combinations of iron group metals and molybdenum such as iron-molybdenum-cobalt, nickel-molybdenum-iron, as well as combinations of ~ickel and molybdenum, cobalt and molybdenum, nickel and tungsten or ,other Group VI-B or Group VIII metal~ taken singly or in combination are sui~able, Th~ hydrogenating or desulfurizing components of such oataly~t are employed in the sulfided or unsulfided form with the ~ulfided form being preferred.
~,.
~, ~ ~ogg658 Although the desulfuri~ation processes of the prior art employing the above-identified catalyst compositions have been useful in the substantial desulfurization of petroleum distillates, improved desulfurization activity is required to satisfy anti-pollution standards being urged upon manufacturers of petroleum products. Therefore, it is desired that an improved petroleum distillate desulfurization process be provided as measured by the improved activity of the hydrodesulfurization catalyst.
SUMMARY OF THE INVENTION
An improved petroleum distillate catalytic desulfurization process is obtained by employing a catalyst composition comprising a Group VI-B hydrogenating component and at least one iron group hydrogenating component on alumina, the hydrogenating components ; being in the sulfided form, and wherein from 5 to 20 volume percent of the catalyst pores have a radius in the range of 100 to 300 A.
DESCRIPTION OF THE INVENTION
The invention is applicable to the desulfurization of petroleum distillates. As employed in the description of this invention, the term "petroleum distillates" refers to those petroleum crude oil fractions having an initial boiling point above 300F.
(148.9C.) at atmospheric pressure and containing less than 2.0 weight percent asphaltenes. Petroleum distillates obtained by con-ventional fractionation, extraction, and/or catalytic and thermal processes from crude oils normally will contain in excess of 0.7 weight percent sulfur with sulfur concentrations as high as 6.0 weight percent being conventional. The process of this invention is directed to the desulfurization of these sulfur-containing petroleum distillates.
:10996S8 The catalyst employed in the desulfurization of the sulfur-containing petroleum distillates comprises a Group VI-B
hydrogenating metal and at least one iron group hydrogenating metal on alumina, the hydrogenating metals being in the sulfided form. The total concentration of the hydrogenating metals is in the range of 8 - 25 weight percent of the catalyst composite. The weight ratio of the sum of the iron group metals to the Group VI-s metal is in the range of 0.2 - 0.5, preferably 0.25 - 0.40. When nickel and cobalt are utilized, the weight ratio of nickel to cobalt is in the range of 0.1 - 2.S, preferably 0.2 - 2Ø
In addition to alumina, the carrier or support can contain a minor contaminating proportion (less than a total of 5.0 weight percent) of one or more refractory metal oxides, other than alumina, ~uch a~, ~ilica, thoria, boria, titania, magnesia, zirconia, etc.
The pore volume of the catalyst is in the range of 0.3 to 0.7 cc per gram and the surface area of the catalyst composite should be in the range of 150 to 350 square meters per gram, preferably 175 to 300 square meters per gram. The pore radius of the catalyst composite, as employed in this application, is determined by multiplying the pore volume by 2 x 104 and dividing the result by the suxface area. The pore volume distribution is determined by nitrogen adsorption using the method described by E. V. Ballou, O. K. Kollen, in Analytical Chemistry, Volume 32, page 532, 1960.
:~,alss6ss In addition to the above characteristics, the catalyst compc)sites of this invention have a pore voiume distribution such that from 5 to 20 volume percent of the pores have a radius in the range from 100 to 300 A. Preferably, the percent of the pores having a radius in the range of 100 to 300 A is in the range of S to 15 volume percent.
The catalyst composites of this invention can be prepared by methods known in the art. Typically, the alumina support having the required pore volume distribution, is dried and calcined at a temperature in the range from 800 to 1,600F. (426.7 to 853.4C.) in an oxygen-containing atmosphere, such as air, for a period ranging from 1 to 24 hours.
In preparation of a nickel-cobalt-molybdenum-on-alumina catalygt composite, for example, extruded calcined alumina pellets can be impregnated with an ammonium monomolybdate solution so as to obtain a catalyst composite containing from 5.0 to 15.0 weight percent of the molybdenum. The impregnated alumina can then be dried at, for example, a temperature of 250F. (121C.) for 24 hours.
The alumina support impregnated with molybdenum can thereafter be contacted with an aqueous solution of nickel nitrate and cobalt nitrate to provide a catalyst composite containing the desired concentrations of molybdenum, nickel,-and cobalt. The wet catalyst composite can then be dried in a second drying stage, followed by calcining under conditions previously described.
i(3996S~
The catalyst composition can then be subjected to a presulfiding step for conversion of the hydrogenation metals to the sulfided form. This procedure can comprise treating the calcined catalyst composite with hydrogen sulfide or preferably a mixture of hydrogen and hydrogen sulfide at a temperature normally in the range from about 300 to 750F. (149 to 399C.) or more and at a pressure ranging from atmospheric to 3,000 psig (211 kg/cm2). When employing a mixture of hydrogen and a hydrogen sulfide as a presulfiding gaseous mixture, the concentration of hydrogen sulfide will normally range from about 5 to about 20 percent by volume.
Other methods can be employed to presulfide the catalyst composite. For example, the catalyst composition can be contacted with a mercaptan or carbon disulfide contained in an inert solvent or contained in the petroleum distillate feed to the hydrodesulfur-ization process. Normally, the concentration of the mercaptan or carbon disulfide in the solvent or feed will be in the range of 0.001 to 3.0 weight percent.
It is also within the scope of this invention to convert the hydrogenation metals to the sulfided form by employing the sulfur contained in the petroleum distillate feed. A suitable method is described in U. S. Letters Patent 3,948,763, w~s~-~s .~-inaorporatod he~ein by ro~enGo thoroto. As descri~ed in the subject patent, the catalyst composite is sulfided with the sulfur-containing petroleum distillate at a temperature in excess of 660F.
(349C.) and thereafter the desulfurization process is conducted at a temperature less than 650F. (343C.).
109965~
The desulfurization reactions are effected by contacting the defined catalyst with the petroleum distillate feed in the pre~ence of uncombined hydrogen pressures in the range of about 200 to 4,000 psig ~14 to 280 kg/cm ). Hydrogen gas is circulated through the reactor at a rate between about 400 to 12 ! 000 standard cubic feet (scf) per barrel of feed (7.12 to 213.6 SCM/100 L).
The hydrogen purity of the circulating gas can vary from about 60 to 100 volume percent.
The hydrodesulfurization reaction can be conducted in the liquid or vapor phase and at a liquid hourly space velocity in the range of 0.25 to 10. Total reaction zone pressures in the range of 200 to 4,000 psig (14 to 280 kg/cm2), preferabl~ in the range of 300 to 1,000 p~ig (21 to 70 kg/cm2) are maintained in the desulfur-lzation zone. The hydrodesulfurization reactions effected pursuant to the process of this invention are conducted at a temperature that is maintained, after the relevantly rapid elevation of temperature upon start-up, in the range of about 550 to 800F. (287.8 to 426.7C.).
The following examples are presented to demonstrate the objects and advantages of the invention. It is not intended, however, to limit the invention to the specific embodiment presented therein.
~(~99658 EXAMPLE I
In this Example, the criticality of employing a catalyst composite having from 5 to 20 percent of the volume of pores with a radius in the range of 100 to 300 A is demonstrated for catalyst composites comprising 1.0 weight percent nickel, 3.0 weight percent cobalt, and 12.0 weight percent molybdenum on alumina. 23.4 percent of the volume of pores of Catalyst A had a radius in the range of 100 to 300 A, 18.7 volume percent of the pores of Catalyst B had a radius in the range of 100 to 300 A, and 9.6 volume percent of the pores of Catalyst C had a radius in the ran~e of 100 to 300 A. The surface area, average pore radius, pore volume and pore size distribu-tion for each of the named catalysts are presented below in Table I:
TABLE I
Catalyst A Catalyst B Catalyst C
Surface Area: m2/g204.6 182.5 246.2 Pore Volume: cc/g0.46 0.39 0.46 Avg. Pore Radius ~2V/A): A 45.1 42.7 37.3 Pore Size Distribution:
% of Pore Volume 250-300 A Radius 0.8 0.7 0.6 - 200-250 1.6 1.4 1.1 : 150-200 2.6 2.8 1.8 100-150 18.4 13.8 6.1 90-100 6.7 5.2 2.6 80- 90 8.4 6.9 4.2 70- 80 8.5 8.0 7.8 60- 70 8.9 9.3 10.1 50- 60 8.5 9.5 11.3 45- 50 4.9 5.6 .6.9 40- 45 4.6 6.3 7.3 35- 40 5.1 5.6 7.5 30- 35 4.2 6.0 7.6 25- 30 5.5 6.7 8.5 20- 25 5.7 5.7 8.1 15- 20 5.7 6.6 8.2 10- 15 0.1 0.0 0.4 7- 10 0.0 0.0 0-0 lW9658 Each of the catalysts was separately employed in the hydro-desulfurization of a Kuwait vacuum gas oil which was characterized as follows:
Gravity: API 24.1 Sulfur: wt. % 2.60 Nitrogen: wt. ~ 0.069 Aniline Pt.: F. (C) 174 (79.1) ASTM Distillation: ASTM D 1160 Method, F. (C) 5~ 637 (336~
682 (361) 750 (399) 810 (432) 887 (475) go 961 (516) EP 1,011 (544) The hydrodeaulfurization conditions employed in each of the runs comprised a hydrogen partial pressure of 650 pounds per square inch (45.50 kg/cm ), a liquid hourly space velocity of 2.0 and a desulfurization temperature of 720F. (382.2C.). The relative desulfurization activity of each of the aatalysts was determined by the following relationship:
k = L (l/S - l/So) where:
k = second order desulfurization rate constant for the catalyst.
L = liquid hourly space velocity S = sulfur in the product, weight percent SO = sulfur in the feed, weight percent Employing the above relationship, it was determined that for each run conducted for a period of at least 18 hours and at most 36 hours the rate constant (k) was 1.5, 1.7, and 2.2, respectively. Therefore, by reducing the percent volume of pores having a radius in the range of 100 to 300 A to below 20 the activity of Catalyst B was 13 percent higher and by reducing the volume of pores to the preferred range (5 to 15 percent) the activity of Catalyst C was improved by 46 percent when compared to the activity of Catalyst A.
~(~99~$8 EXAMPLE II
In this Example, the criticality of employing a catalyst composite having from 5 to 20 percent of the volume of pores with a radius in the range of 100 to 300 A is demonstrated for catalyst composites comprising 2.5 weight percent nickel, 1.25 weight percent cobalt, and 11.0 weight percent molybdenum on alumina. 25.0 percent of the volume of pores of Catalyst D had a radius in the range of 100 to 300 A and 9.3 volume percent of the pores of Catalyst E had a radius in the range of 100 to 300 A. The surface area, average pore radius, pore volume and pore size distribution for each of the named catalysts are presented below in Table II.
TABLE II
Cataly8t D Catalyst E
Surface Area: m2/g214.4 286.8 Pore Volume: cc/g 0.51 0.44 Avg. Pore Radius (2V/A): A 47.4 30.7 Pore Size Distribution:
% of Pore Volume 250-300 A Radius 0.8 0.9 200-250 1.7 1.4 150-200 4.6 2.3 100-lS0 19.1 4.7 90-100 6.5 1.5 80- 90 8.5 2.3 70- 80 8.9 2.9 60- 70 8.7 4.7 50- 60 8.5 6.3 45- 50 4.7 4.6 40- 45 4.5 S.9 35- 40 4.6 8.0 30- 35 4.2 9.5 25- 30 4.5 13.8 20- 25 4.8 15.2 15- 20 5.4 14.3 10- 15 0.0 1.7 _ g _ ~(999658 Each of Catalysts D and E was separately employed in the hydrodesulfurization of the Kuwait vacuum gas oil of Example I
employing the hydrodesulfurization conditions in each of the runs set forth in Example I. Utilizing the method for determining desulfurization activity of the catalysts described in Example I, the rate constant for the run utilizing Catalyst D was 1.1 and the rate constant for the run employing Catalyst E was 1.4. Therefore, by reducing the percent volume of pores having a radius in the range of 100 to 300 A to below 20 the activity of Catalyst E was 27 percent greater than the activity of Catalyst D.
Although the invention has been described with reference to specific embodiments, references, and details, various modifica-tions and changes will be apparent to one skilled in the art and are contemplated to be embraced in this invention.
The hydrode~ulfurization of petroleum distillate hydro-c~rbons employing a ca~aly~ cpmprising a supported hydrogena~ing aomponent which is at least one member of,the group con6isting of Group VI-B and Group VlII metals in a fo~m capable of promoting hydro~enating reactions is well-known in the art. Especial~y e'ffective catalysts for the purpose of such hydrodesulfurization reaction~ are those comprising molybdenum and two members of the iron group metals. Preferred cat,alysts of thi~ class are those containing nickel, cobalt and molyb,denum but other combinations of iron group metals and molybdenum such as iron-molybdenum-cobalt, nickel-molybdenum-iron, as well as combinations of ~ickel and molybdenum, cobalt and molybdenum, nickel and tungsten or ,other Group VI-B or Group VIII metal~ taken singly or in combination are sui~able, Th~ hydrogenating or desulfurizing components of such oataly~t are employed in the sulfided or unsulfided form with the ~ulfided form being preferred.
~,.
~, ~ ~ogg658 Although the desulfuri~ation processes of the prior art employing the above-identified catalyst compositions have been useful in the substantial desulfurization of petroleum distillates, improved desulfurization activity is required to satisfy anti-pollution standards being urged upon manufacturers of petroleum products. Therefore, it is desired that an improved petroleum distillate desulfurization process be provided as measured by the improved activity of the hydrodesulfurization catalyst.
SUMMARY OF THE INVENTION
An improved petroleum distillate catalytic desulfurization process is obtained by employing a catalyst composition comprising a Group VI-B hydrogenating component and at least one iron group hydrogenating component on alumina, the hydrogenating components ; being in the sulfided form, and wherein from 5 to 20 volume percent of the catalyst pores have a radius in the range of 100 to 300 A.
DESCRIPTION OF THE INVENTION
The invention is applicable to the desulfurization of petroleum distillates. As employed in the description of this invention, the term "petroleum distillates" refers to those petroleum crude oil fractions having an initial boiling point above 300F.
(148.9C.) at atmospheric pressure and containing less than 2.0 weight percent asphaltenes. Petroleum distillates obtained by con-ventional fractionation, extraction, and/or catalytic and thermal processes from crude oils normally will contain in excess of 0.7 weight percent sulfur with sulfur concentrations as high as 6.0 weight percent being conventional. The process of this invention is directed to the desulfurization of these sulfur-containing petroleum distillates.
:10996S8 The catalyst employed in the desulfurization of the sulfur-containing petroleum distillates comprises a Group VI-B
hydrogenating metal and at least one iron group hydrogenating metal on alumina, the hydrogenating metals being in the sulfided form. The total concentration of the hydrogenating metals is in the range of 8 - 25 weight percent of the catalyst composite. The weight ratio of the sum of the iron group metals to the Group VI-s metal is in the range of 0.2 - 0.5, preferably 0.25 - 0.40. When nickel and cobalt are utilized, the weight ratio of nickel to cobalt is in the range of 0.1 - 2.S, preferably 0.2 - 2Ø
In addition to alumina, the carrier or support can contain a minor contaminating proportion (less than a total of 5.0 weight percent) of one or more refractory metal oxides, other than alumina, ~uch a~, ~ilica, thoria, boria, titania, magnesia, zirconia, etc.
The pore volume of the catalyst is in the range of 0.3 to 0.7 cc per gram and the surface area of the catalyst composite should be in the range of 150 to 350 square meters per gram, preferably 175 to 300 square meters per gram. The pore radius of the catalyst composite, as employed in this application, is determined by multiplying the pore volume by 2 x 104 and dividing the result by the suxface area. The pore volume distribution is determined by nitrogen adsorption using the method described by E. V. Ballou, O. K. Kollen, in Analytical Chemistry, Volume 32, page 532, 1960.
:~,alss6ss In addition to the above characteristics, the catalyst compc)sites of this invention have a pore voiume distribution such that from 5 to 20 volume percent of the pores have a radius in the range from 100 to 300 A. Preferably, the percent of the pores having a radius in the range of 100 to 300 A is in the range of S to 15 volume percent.
The catalyst composites of this invention can be prepared by methods known in the art. Typically, the alumina support having the required pore volume distribution, is dried and calcined at a temperature in the range from 800 to 1,600F. (426.7 to 853.4C.) in an oxygen-containing atmosphere, such as air, for a period ranging from 1 to 24 hours.
In preparation of a nickel-cobalt-molybdenum-on-alumina catalygt composite, for example, extruded calcined alumina pellets can be impregnated with an ammonium monomolybdate solution so as to obtain a catalyst composite containing from 5.0 to 15.0 weight percent of the molybdenum. The impregnated alumina can then be dried at, for example, a temperature of 250F. (121C.) for 24 hours.
The alumina support impregnated with molybdenum can thereafter be contacted with an aqueous solution of nickel nitrate and cobalt nitrate to provide a catalyst composite containing the desired concentrations of molybdenum, nickel,-and cobalt. The wet catalyst composite can then be dried in a second drying stage, followed by calcining under conditions previously described.
i(3996S~
The catalyst composition can then be subjected to a presulfiding step for conversion of the hydrogenation metals to the sulfided form. This procedure can comprise treating the calcined catalyst composite with hydrogen sulfide or preferably a mixture of hydrogen and hydrogen sulfide at a temperature normally in the range from about 300 to 750F. (149 to 399C.) or more and at a pressure ranging from atmospheric to 3,000 psig (211 kg/cm2). When employing a mixture of hydrogen and a hydrogen sulfide as a presulfiding gaseous mixture, the concentration of hydrogen sulfide will normally range from about 5 to about 20 percent by volume.
Other methods can be employed to presulfide the catalyst composite. For example, the catalyst composition can be contacted with a mercaptan or carbon disulfide contained in an inert solvent or contained in the petroleum distillate feed to the hydrodesulfur-ization process. Normally, the concentration of the mercaptan or carbon disulfide in the solvent or feed will be in the range of 0.001 to 3.0 weight percent.
It is also within the scope of this invention to convert the hydrogenation metals to the sulfided form by employing the sulfur contained in the petroleum distillate feed. A suitable method is described in U. S. Letters Patent 3,948,763, w~s~-~s .~-inaorporatod he~ein by ro~enGo thoroto. As descri~ed in the subject patent, the catalyst composite is sulfided with the sulfur-containing petroleum distillate at a temperature in excess of 660F.
(349C.) and thereafter the desulfurization process is conducted at a temperature less than 650F. (343C.).
109965~
The desulfurization reactions are effected by contacting the defined catalyst with the petroleum distillate feed in the pre~ence of uncombined hydrogen pressures in the range of about 200 to 4,000 psig ~14 to 280 kg/cm ). Hydrogen gas is circulated through the reactor at a rate between about 400 to 12 ! 000 standard cubic feet (scf) per barrel of feed (7.12 to 213.6 SCM/100 L).
The hydrogen purity of the circulating gas can vary from about 60 to 100 volume percent.
The hydrodesulfurization reaction can be conducted in the liquid or vapor phase and at a liquid hourly space velocity in the range of 0.25 to 10. Total reaction zone pressures in the range of 200 to 4,000 psig (14 to 280 kg/cm2), preferabl~ in the range of 300 to 1,000 p~ig (21 to 70 kg/cm2) are maintained in the desulfur-lzation zone. The hydrodesulfurization reactions effected pursuant to the process of this invention are conducted at a temperature that is maintained, after the relevantly rapid elevation of temperature upon start-up, in the range of about 550 to 800F. (287.8 to 426.7C.).
The following examples are presented to demonstrate the objects and advantages of the invention. It is not intended, however, to limit the invention to the specific embodiment presented therein.
~(~99658 EXAMPLE I
In this Example, the criticality of employing a catalyst composite having from 5 to 20 percent of the volume of pores with a radius in the range of 100 to 300 A is demonstrated for catalyst composites comprising 1.0 weight percent nickel, 3.0 weight percent cobalt, and 12.0 weight percent molybdenum on alumina. 23.4 percent of the volume of pores of Catalyst A had a radius in the range of 100 to 300 A, 18.7 volume percent of the pores of Catalyst B had a radius in the range of 100 to 300 A, and 9.6 volume percent of the pores of Catalyst C had a radius in the ran~e of 100 to 300 A. The surface area, average pore radius, pore volume and pore size distribu-tion for each of the named catalysts are presented below in Table I:
TABLE I
Catalyst A Catalyst B Catalyst C
Surface Area: m2/g204.6 182.5 246.2 Pore Volume: cc/g0.46 0.39 0.46 Avg. Pore Radius ~2V/A): A 45.1 42.7 37.3 Pore Size Distribution:
% of Pore Volume 250-300 A Radius 0.8 0.7 0.6 - 200-250 1.6 1.4 1.1 : 150-200 2.6 2.8 1.8 100-150 18.4 13.8 6.1 90-100 6.7 5.2 2.6 80- 90 8.4 6.9 4.2 70- 80 8.5 8.0 7.8 60- 70 8.9 9.3 10.1 50- 60 8.5 9.5 11.3 45- 50 4.9 5.6 .6.9 40- 45 4.6 6.3 7.3 35- 40 5.1 5.6 7.5 30- 35 4.2 6.0 7.6 25- 30 5.5 6.7 8.5 20- 25 5.7 5.7 8.1 15- 20 5.7 6.6 8.2 10- 15 0.1 0.0 0.4 7- 10 0.0 0.0 0-0 lW9658 Each of the catalysts was separately employed in the hydro-desulfurization of a Kuwait vacuum gas oil which was characterized as follows:
Gravity: API 24.1 Sulfur: wt. % 2.60 Nitrogen: wt. ~ 0.069 Aniline Pt.: F. (C) 174 (79.1) ASTM Distillation: ASTM D 1160 Method, F. (C) 5~ 637 (336~
682 (361) 750 (399) 810 (432) 887 (475) go 961 (516) EP 1,011 (544) The hydrodeaulfurization conditions employed in each of the runs comprised a hydrogen partial pressure of 650 pounds per square inch (45.50 kg/cm ), a liquid hourly space velocity of 2.0 and a desulfurization temperature of 720F. (382.2C.). The relative desulfurization activity of each of the aatalysts was determined by the following relationship:
k = L (l/S - l/So) where:
k = second order desulfurization rate constant for the catalyst.
L = liquid hourly space velocity S = sulfur in the product, weight percent SO = sulfur in the feed, weight percent Employing the above relationship, it was determined that for each run conducted for a period of at least 18 hours and at most 36 hours the rate constant (k) was 1.5, 1.7, and 2.2, respectively. Therefore, by reducing the percent volume of pores having a radius in the range of 100 to 300 A to below 20 the activity of Catalyst B was 13 percent higher and by reducing the volume of pores to the preferred range (5 to 15 percent) the activity of Catalyst C was improved by 46 percent when compared to the activity of Catalyst A.
~(~99~$8 EXAMPLE II
In this Example, the criticality of employing a catalyst composite having from 5 to 20 percent of the volume of pores with a radius in the range of 100 to 300 A is demonstrated for catalyst composites comprising 2.5 weight percent nickel, 1.25 weight percent cobalt, and 11.0 weight percent molybdenum on alumina. 25.0 percent of the volume of pores of Catalyst D had a radius in the range of 100 to 300 A and 9.3 volume percent of the pores of Catalyst E had a radius in the range of 100 to 300 A. The surface area, average pore radius, pore volume and pore size distribution for each of the named catalysts are presented below in Table II.
TABLE II
Cataly8t D Catalyst E
Surface Area: m2/g214.4 286.8 Pore Volume: cc/g 0.51 0.44 Avg. Pore Radius (2V/A): A 47.4 30.7 Pore Size Distribution:
% of Pore Volume 250-300 A Radius 0.8 0.9 200-250 1.7 1.4 150-200 4.6 2.3 100-lS0 19.1 4.7 90-100 6.5 1.5 80- 90 8.5 2.3 70- 80 8.9 2.9 60- 70 8.7 4.7 50- 60 8.5 6.3 45- 50 4.7 4.6 40- 45 4.5 S.9 35- 40 4.6 8.0 30- 35 4.2 9.5 25- 30 4.5 13.8 20- 25 4.8 15.2 15- 20 5.4 14.3 10- 15 0.0 1.7 _ g _ ~(999658 Each of Catalysts D and E was separately employed in the hydrodesulfurization of the Kuwait vacuum gas oil of Example I
employing the hydrodesulfurization conditions in each of the runs set forth in Example I. Utilizing the method for determining desulfurization activity of the catalysts described in Example I, the rate constant for the run utilizing Catalyst D was 1.1 and the rate constant for the run employing Catalyst E was 1.4. Therefore, by reducing the percent volume of pores having a radius in the range of 100 to 300 A to below 20 the activity of Catalyst E was 27 percent greater than the activity of Catalyst D.
Although the invention has been described with reference to specific embodiments, references, and details, various modifica-tions and changes will be apparent to one skilled in the art and are contemplated to be embraced in this invention.
Claims (5)
1. A process which comprises contacting a sulfur-containing petroleum distillate with a catalyst under hydrodesulfurization conditions, said catalyst comprising a Group VI-B hydrogenating metal and at least one iron group hydrogenating metal on alumina, the hydrogenating metals being in the sulfided form and the concen-tration of hydrogenating metals being in the range of 8-25 weight percent of said catalyst, the nitrogen pore volume of said catalyst being in the range of 0.3 to 0.7 cc per gram and 5-20 volume percent of the pores having a radius in the range of 100 to 300 .ANG., and recovering therefrom a desulfurized petroleum distillate product.
2. The process of Claim 1 wherein the weight ratio of the iron group hydrogenating metal to the Group VI-B hydrogenating component is in the range of 0.2 to 0.5.
3. The process of Claim 1 wherein the Group VI-B hydrogenating metal comprises molybdenum and the iron group hydrogenating metals comprise nickel and cobalt.
4. The process of Claim 1 wherein the nitrogen pore volume is in the range of 0.35 to 0.60 cc per grams and wherein 5-15 volume percent of the pores have a radius in the range of 100 to 300 .ANG..
5. The process of Claim 3 wherein the weight ratio of nickel to cobalt is in the range of 0.1 to 2.5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US71658676A | 1976-08-23 | 1976-08-23 | |
| US716,586 | 1976-08-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1099658A true CA1099658A (en) | 1981-04-21 |
Family
ID=24878615
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA282,894A Expired CA1099658A (en) | 1976-08-23 | 1977-07-15 | Hydrodesulfurization of petroleum distillates |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS5326802A (en) |
| CA (1) | CA1099658A (en) |
| NL (1) | NL7709286A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5573617U (en) * | 1978-11-14 | 1980-05-21 | ||
| JPS5660826U (en) * | 1979-10-18 | 1981-05-23 | ||
| US4443558A (en) * | 1982-04-08 | 1984-04-17 | Chevron Research Company | Highly stable hydroprocessing catalyst |
-
1977
- 1977-07-15 CA CA282,894A patent/CA1099658A/en not_active Expired
- 1977-08-22 JP JP10038477A patent/JPS5326802A/en active Pending
- 1977-08-23 NL NL7709286A patent/NL7709286A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5326802A (en) | 1978-03-13 |
| NL7709286A (en) | 1978-02-27 |
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