US2837465A - Hydrocatalytic desulfurization of petroleum hydrocarbons - Google Patents
Hydrocatalytic desulfurization of petroleum hydrocarbons Download PDFInfo
- Publication number
- US2837465A US2837465A US501168A US50116855A US2837465A US 2837465 A US2837465 A US 2837465A US 501168 A US501168 A US 501168A US 50116855 A US50116855 A US 50116855A US 2837465 A US2837465 A US 2837465A
- Authority
- US
- United States
- Prior art keywords
- hydrocarbons
- desulfurization
- sulfur
- hydrocatalytic
- hydrogen sulfide
- 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 - Lifetime
Links
- 229930195733 hydrocarbon Natural products 0.000 title claims description 21
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 21
- 238000006477 desulfuration reaction Methods 0.000 title claims description 11
- 230000023556 desulfurization Effects 0.000 title claims description 11
- 239000003208 petroleum Substances 0.000 title claims description 10
- 238000000034 method Methods 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 11
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 15
- 239000003921 oil Substances 0.000 description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- UJHLGDUCOCXGBW-UHFFFAOYSA-N oxocobalt trioxomolybdenum Chemical compound O=[Co].O=[Mo](=O)=O UJHLGDUCOCXGBW-UHFFFAOYSA-N 0.000 description 1
- 235000020004 porter Nutrition 0.000 description 1
- 230000001172 regenerating effect Effects 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
Definitions
- This invention relates to the hydrocatalytic desulfurization of petroleum hydrocarbons and is more particularly concerned with the treatment of gas oils.
- the hydrocatalytic desulfurization of gas oils in the vapor phase is well known and the process is usually carried out at a pressure of 500-1000 p. s. i. ga., a temperature of 750-820 F., and a high recycle rate e. g. of the order of 4000 S. C. F./B. It is known also to treat gas oils in the liquid phase by allowing the oils to flow in a thin layer over the catalyst at a temperature above 200 C. and a pressure of-at least atmospheres. Typical conditions are a temperature of 350 C. and a pressure of 50 atmospheres. It has been suggested that under such conditions, low recycle rates of the order of 250-1250 cu. ft./bbl. are possible.
- a process for the hydrocatalytic desulfurization of petroleum hydrocarbons is carried out at a temperature of 750820 F a pressure of above 300 p. s. i. ga. and preferably within the range 500-1000 p. s. i. ga., a space velocity of the liquid feedstock of 0.5-20 v./v./hr., and a hydrogen recycle rate not exceeding 2000 S. C. F./B.
- the preferred catalyst consists of or comprises the oxides of cobalt and molybdenum, either as such or in combined form, incorporated with a metal oxide support, preferably alumina.
- the process is particularly suitable for the desulfurization of gas oils and the preferred recycle rate is of the order of 1000 S. C. F./B.
- the process of the invention has an advantage over the conventional liquid phase process since a higher space velocity can be employed due to the higher temperature.
- the process of the invention is also superior to the conventional vapor phase process in that the reduction in recycle rate from 4000 S. C. F./ B. results in a reduction in the capital cost of the plant.
- Example 1 A straight-run Middle East gas oil containing 1.25% wt. sulfur was desulfurized at 8 v./v./hr., 780 F., 1000 p. s. i. ga. pressure, and 1250 S. C. F./B. gas recycle over a cobalt oxidemolybdenum oxide on alumina catalyst, using catalytic reformer exit gases containing 70% mol. hydrogen.
- the product contained 0.1% wt. sulfur and the hydrogen consumption was 130 S. C. F./B.
- the catalyst only required regenerating at intervals of 12 months.
- Example 2 A blend of by volume straight-run Middle East gas oil and 20% by volume Middle East catalytic cracker light cycle oil, containing 1.6% wt. sulfur, was desulfurizated at 8 v./v./hr., 780 F, 1000 p. s. i. ga. pressure and 1250 S. C. F./B. gas recycle over a Co-Mo oxide on alumina catalyst, using catalytic reformer exit gases containing 70% mol. hydrogen. The product contained 0.1% Wt. sulfur and the hydrogen consumption was 200 S. C. F./B. The catalyst only requiredregenerating at intervals of 6 months.
- a process for the hydrocatalytic desulfurization of petroleum hydrocarbons boiling in the gas oil range which comprises passing the hydrocarbons at a space velocity of the liquid feedstock within the range 0.5 to 20 v./v./ hr. and in admixture-with up to 2000 S. C. F./ B. of hydrogen over a sulfur-resistant hydrogenation catalyst at a temperature of 750-820 F. and a pressure of above 500 p. s. i. ga. and not exceeding 1000 p. s. i. ga., whereby organically combined sulfur in the hydrocarbons is converted into hydrogen sulfide, and removing hydrogen sulfide from the treated hydrocarbons.
- a process for the hydrocatalytic desulfurization of petroleum hydrocarbons boiling in the gas oil range which comprises passing the hydrocarbons at a space velocity of the liquid feedstock within the range 0.5 to 20 v./v./hr. and in admixture with up to 2000 S. C. F./B. of hydrogen over a catalyst consisting of the oxides of cobalt and molybdenum incorporated with a metal oxide.
- a process for the hydrocatalytic desulfurization of petroleum hydrocarbons boiling in the gas oil range which comprises passing the hydrocarbons at .a space velocity of the liquid feedstock of the order of 8 v./v./hr. and in admixture with approximately 1000 S. C. F./B. of hydrogen over a catalyst consisting of the oxides of cobalt and molybdenum incorporated with a support consisting essentially of alumina, at a temperature of 750- 820 F. and a pressure of about 1000 p. s. i. ga., whereby organically combined sulfur in the hydrocarbons is converted into hydrogen sulfide, and removing hydrogen sulfide from the treated hydrocarbons.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Description
HYDROCATALYTEC DESULFURIZATION OF PETROLEUM HYDROCONS Frederick William Berharn Porter and Roy Purdy Northcott, Sunbury-on-Thames, England, assignors to The British Petroleum Company Limited, London, England, a British joint-stock corporation No Drawing. Application April 13, 1955 Serial No. 501,168
Claims priority, application Great Britain April 14, 1954 4 Claims. (Cl. 19624) This invention relates to the hydrocatalytic desulfurization of petroleum hydrocarbons and is more particularly concerned with the treatment of gas oils.
The hydrocatalytic desulfurization of gas oils in the vapor phase is well known and the process is usually carried out at a pressure of 500-1000 p. s. i. ga., a temperature of 750-820 F., and a high recycle rate e. g. of the order of 4000 S. C. F./B. It is known also to treat gas oils in the liquid phase by allowing the oils to flow in a thin layer over the catalyst at a temperature above 200 C. and a pressure of-at least atmospheres. Typical conditions are a temperature of 350 C. and a pressure of 50 atmospheres. It has been suggested that under such conditions, low recycle rates of the order of 250-1250 cu. ft./bbl. are possible.
It has now been found that it is advantageous to operate at the higher temperatures normally associated with vapor phase operation and with lower recycle rates than are customary at such temperatures.
According to the present invention, a process for the hydrocatalytic desulfurization of petroleum hydrocarbons is carried out at a temperature of 750820 F a pressure of above 300 p. s. i. ga. and preferably within the range 500-1000 p. s. i. ga., a space velocity of the liquid feedstock of 0.5-20 v./v./hr., and a hydrogen recycle rate not exceeding 2000 S. C. F./B.
The preferred catalyst consists of or comprises the oxides of cobalt and molybdenum, either as such or in combined form, incorporated with a metal oxide support, preferably alumina.
The process is particularly suitable for the desulfurization of gas oils and the preferred recycle rate is of the order of 1000 S. C. F./B. When desulfurizing gas oils under such conditions a considerable portion of the oil in the reactor is in the liquid phase, but the process of the invention has an advantage over the conventional liquid phase process since a higher space velocity can be employed due to the higher temperature. The process of the invention is also superior to the conventional vapor phase process in that the reduction in recycle rate from 4000 S. C. F./ B. results in a reduction in the capital cost of the plant.
The invention will be illustrated by the following examples:
Example 1 A straight-run Middle East gas oil containing 1.25% wt. sulfur was desulfurized at 8 v./v./hr., 780 F., 1000 p. s. i. ga. pressure, and 1250 S. C. F./B. gas recycle over a cobalt oxidemolybdenum oxide on alumina catalyst, using catalytic reformer exit gases containing 70% mol. hydrogen. The product contained 0.1% wt. sulfur and the hydrogen consumption was 130 S. C. F./B. The catalyst only required regenerating at intervals of 12 months.
"ice
Example 2 A blend of by volume straight-run Middle East gas oil and 20% by volume Middle East catalytic cracker light cycle oil, containing 1.6% wt. sulfur, was desulfurizated at 8 v./v./hr., 780 F, 1000 p. s. i. ga. pressure and 1250 S. C. F./B. gas recycle over a Co-Mo oxide on alumina catalyst, using catalytic reformer exit gases containing 70% mol. hydrogen. The product contained 0.1% Wt. sulfur and the hydrogen consumption was 200 S. C. F./B. The catalyst only requiredregenerating at intervals of 6 months.
We claim:
1. A process for the hydrocatalytic desulfurization of petroleum hydrocarbons boiling in the gas oil range, which comprises passing the hydrocarbons at a space velocity of the liquid feedstock within the range 0.5 to 20 v./v./ hr. and in admixture-with up to 2000 S. C. F./ B. of hydrogen over a sulfur-resistant hydrogenation catalyst at a temperature of 750-820 F. and a pressure of above 500 p. s. i. ga. and not exceeding 1000 p. s. i. ga., whereby organically combined sulfur in the hydrocarbons is converted into hydrogen sulfide, and removing hydrogen sulfide from the treated hydrocarbons.
2. A process for the hydrocatalytic desulfurization of petroleum hydrocarbons boiling in the gas oil range, which comprises passing the hydrocarbons at a space velocity of the liquid feedstock within the range 0.5 to 20 v./v./hr. and in admixture with up to 2000 S. C. F./B. of hydrogen over a catalyst consisting of the oxides of cobalt and molybdenum incorporated with a metal oxide.
support, at a temperature of 750-820 F. and a pressure of above 500 p. s. i. ga. and not exceeding 1000 p. s. i. ga., whereby organically combined sulfur in the hydrocarbons is converted into hydrogen sulfide, and gemoving hydrogen sulfide from the treated hydrocarons.
2. A process for the hydrocatalytic desulfurization of petroleum hydrocarbons boiling in the gas oil range,
which comprises passing the hydrocarbons at a space velocity of the liquid feedstock of the order of 8 v./v./hr. and in admixtunre with up to 2000 S. C. F B. of hydrogen over a catalyst consisting of the oxides of cobalt and molybdenum incorporated with a support consisting essentially of alumina, at a temperature of 750820 F. and a pressure of about 1000 p. s. i. ga., whereby organically combined sulfur in the hydrocarbons is converted into hydrogen sulfide, and removing hydrogen sulfide from the treated hydrocarbons.
4. A process for the hydrocatalytic desulfurization of petroleum hydrocarbons boiling in the gas oil range, which comprises passing the hydrocarbons at .a space velocity of the liquid feedstock of the order of 8 v./v./hr. and in admixture with approximately 1000 S. C. F./B. of hydrogen over a catalyst consisting of the oxides of cobalt and molybdenum incorporated with a support consisting essentially of alumina, at a temperature of 750- 820 F. and a pressure of about 1000 p. s. i. ga., whereby organically combined sulfur in the hydrocarbons is converted into hydrogen sulfide, and removing hydrogen sulfide from the treated hydrocarbons.
References Cited in the file of this patent UNITED STATES PATENTS 2,567,252 Strang Sept. 11, 1951 2,577,823 Stine Dec. 11, 1951 2,636,843 Arnold et a1. Apr. 28, 1953 2,697,683 Engel et al. Dec. 21,1954
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent N0e 2 837 465 June 3 .1958
Frederick William Bertram Porter et a1,
It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
Column 2,, lines 5 and 6 for "desulfurizated" read desulphurised line 38 for "20 A process" read 30 A process same column 2 line 412 for "admixtunre" read admixture I Signed and sealed this 23rd day of August 1960 (SEAL) Attest:
KARL Ht AXLINE ROBERT c. WATSON Attesting Officer Commissioner of Patents
Claims (1)
1. A PROCESS FOR THE HYDROCATALYTIC DESULFURIZATION OF PETROLEUM HYDROCARBONS BOILING IN THE GAS OIL RANGE, WHICH COMPRISES PASSING THE HYDROCARBONS AT A SPACE VELOCITY OF THE LIQUID FEEDSTOCK WITHIN THE RANGE 0.5 TO 20 Y./V./HR. AND IN ADMIXTURE WITH UP TO 2000 S.C.F./B. OF HYDROGEN OVER A SULFUR-RESISTANT HYDROGENATION CATALYST AT A TEMPERATURE OF 750-820*F. AND A PRESSURE OF ABOVE 500 P.S.I.GA. AND NOT EXCEEDING 1000 P.S.I.GA., WHEREBY ORGANICALLY COMBINED SULFUR IN THE HYDROCARBONS IS CONVERTED INTO HYDROGEN SULFIDE, AND REMOVING HYDROGEN SULFIDE FROM THE TREATED HYDROCARTONS.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB2837465X | 1954-04-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2837465A true US2837465A (en) | 1958-06-03 |
Family
ID=10916255
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US501168A Expired - Lifetime US2837465A (en) | 1954-04-14 | 1955-04-13 | Hydrocatalytic desulfurization of petroleum hydrocarbons |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2837465A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2900332A (en) * | 1955-04-06 | 1959-08-18 | British Petroleum Co | Hydrocatalytic desulfurization of gas oil |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2567252A (en) * | 1949-07-20 | 1951-09-11 | Anglo Iranian Oil Co Ltd | Refining of hydrocarbons |
| US2577823A (en) * | 1948-02-06 | 1951-12-11 | Standard Oil Co | Hydrodesulfurization of sulfurcontaining hydrocarbon fractions |
| US2636843A (en) * | 1950-10-09 | 1953-04-28 | Standard Oil Co | Cracked naphtha desulfurization |
| US2697683A (en) * | 1950-02-27 | 1954-12-21 | Shell Dev | Treatment of hydrocarbon oils |
-
1955
- 1955-04-13 US US501168A patent/US2837465A/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2577823A (en) * | 1948-02-06 | 1951-12-11 | Standard Oil Co | Hydrodesulfurization of sulfurcontaining hydrocarbon fractions |
| US2567252A (en) * | 1949-07-20 | 1951-09-11 | Anglo Iranian Oil Co Ltd | Refining of hydrocarbons |
| US2697683A (en) * | 1950-02-27 | 1954-12-21 | Shell Dev | Treatment of hydrocarbon oils |
| US2636843A (en) * | 1950-10-09 | 1953-04-28 | Standard Oil Co | Cracked naphtha desulfurization |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2900332A (en) * | 1955-04-06 | 1959-08-18 | British Petroleum Co | Hydrocatalytic desulfurization of gas oil |
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