US2929776A - Process for removal of sulfur, metals and asphalt from petroleum crudes - Google Patents
Process for removal of sulfur, metals and asphalt from petroleum crudes Download PDFInfo
- Publication number
- US2929776A US2929776A US573106A US57310656A US2929776A US 2929776 A US2929776 A US 2929776A US 573106 A US573106 A US 573106A US 57310656 A US57310656 A US 57310656A US 2929776 A US2929776 A US 2929776A
- Authority
- US
- United States
- Prior art keywords
- oil
- sulfur
- asphalt
- sulfur compounds
- organo metallic
- 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
- 238000000034 method Methods 0.000 title claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 13
- 229910052717 sulfur Inorganic materials 0.000 title claims description 13
- 239000011593 sulfur Substances 0.000 title claims description 13
- 230000008569 process Effects 0.000 title claims description 12
- 239000010426 asphalt Substances 0.000 title claims description 11
- 239000003208 petroleum Substances 0.000 title description 5
- 229910052751 metal Inorganic materials 0.000 title description 2
- 239000002184 metal Substances 0.000 title description 2
- 150000002739 metals Chemical class 0.000 title description 2
- 239000003921 oil Substances 0.000 claims description 24
- 150000003464 sulfur compounds Chemical class 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 238000007670 refining Methods 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000000571 coke Substances 0.000 claims description 7
- 239000000295 fuel oil Substances 0.000 claims description 7
- 238000005345 coagulation Methods 0.000 claims description 5
- 230000015271 coagulation Effects 0.000 claims description 5
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- 239000002480 mineral oil Substances 0.000 claims description 4
- 125000002524 organometallic group Chemical group 0.000 description 11
- 239000002956 ash Substances 0.000 description 8
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 208000007101 Muscle Cramp Diseases 0.000 description 1
- 208000005392 Spasm Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical class O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000010763 heavy fuel oil Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 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
-
- 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
- C10G71/00—Treatment by methods not otherwise provided for of hydrocarbon oils or fatty oils for lubricating purposes
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
Definitions
- the present invention relates to a new method for refining petroleum crudes in order to improve the properties of crudes and of products therefrom derived. 'Ihis method meets 'in the same time the increased requirements of improved petroleum fractions and the need of refining low-grade petroleum crudes for removing asphaltic material, mineral matter (ash) and sulfur compounds.
- one object of the present invention is the production of residual fuel oils characterized by low asphalt content (very reduced values of Conradson carbon residues), by reduced viscosity, by lower sulfur content and by strongly reduced content of ashes vana- The so obtained residual as fuels in gas turbines, in domestic burners and in low and medium speed diesel-engines.
- Another object of the present invention is to make possible or easier and more efiicient the use of catalysts which are liable to be poisoned by the action of the above said components, in subsequent operations of reforming, cracking and refining hydrogenation.
- Another object of the present invention is the great decrease of refinery equipment corrosion, and the reduced cost of the equipment maintenance and of expenses involved with treatment of the single products.
- a further object is the recovery of most of the sulfur contained in the crude as hydrogen sulfide, elemental sulfur, sulfuric acid.
- Another object is the recovery of mineral matter which is contained in the crude (particularly of the vanadium), as these materials are concentrated in a narrow fraction which can be easily handled.
- a further object is the reduction of air and liquid efiluents pollution in refining area, caused by sulfur compounds and by liquids which contain these compounds.
- porphyrins are decomposed and the asphaltic material coagulated as substances which can be easily filtered and decanted, including the mineral constituents, so allowing the subsequent separation by filtering, by centrifuging, by solvent extraction, by redistillation or by the other known methods.
- the so refined crude oil, separated from asphaltic compounds, ashes and, eventually, also from high boiling fractions leaving as residue, fuel oils of high quality may be treated, before the fractionation, or after the fractionation, by conventional processes of refining or by catalytic refining hydrogenation, so finely obtaining fractions of particular value of different volatility and boiling range.
- the mixed-phase products coming out of the contact zone have been condensed and separated in a liquid phase and in a gas-vapor phase.
- the liquid phase has been separated by filtration from the solid residues constituted by modified asphaltic products and by mineral substances and one portion of the filtered liquid has been fractionated, while another part, together with'the gases and light vapors separated in the above mentioned con"- densation, has been sent to a second reaction zone containing a catalyst having hydrogenating properties, which was able to improve and complete the transformation of residual sulfur compounds into hydrogen sulfide, and to operate a further refining of the hydrocarbons.
- the volumetric yields of the first treatment were more than and those of second treatment (catalytic hydrogenation) were more than 98%.
- the analytical data on separated products have been 7 quite similar to those of the first example: particularly the pounds and containing organo metalliccomplexes and other ash-forming compounds, for producing highquality fuel oil having low viscosity and low content of asphalt, ashes and sulfur, comprising passing the oil at a temperature between 600 and 1060 F. and at a pressure between 70 to 710 p.s.i.
- a process forrefining crude and topped crude mineral oils having high contents of asphalt and sulfur compounds and containing organo metallic complexes and other ash-forming compounds, for producing high quality fuel oil having low viscosity and low content of asphalt, ashes and sulfur comprising passing the oil at a tempera! ture between 785 and 825 F. and at a pressure between spasms 425 to 500 p.s.i.
- a process for refining crude and topped crude mineral oils having. high contents of asphalt and sulfur compounds and 'containing'organo metallic complexes and other ash-forming compounds, for producing high quality fuel oil having low viscosity and low content of asphalt, ashes and sulfur comprising passing the oil at a temperature between 600 and 1060 F. and at a pressure between 70 to 710 psi. into a?
- contact chamber together with hydrogen in the presence of a mass of high porosity having a large surface area selected from the group consisting of granulated activated carbon and granulated activated metallurgical coke, maintainingthe space velocity of the oil fed to the contact chamber between 0.5 and 5.0 volumes of liquid/hour/volumeof contact mass, and maintaining a hydrogen recirculation at about 3.2 to 16 standard cu. ft./lb. of oil to promote decomposition of the organo metallic complexes and sulfur compounds and the coagulation of the asphaltenes contained in the oil, and recycling a portion of the refined oil through the contact chamber.
- a process for refining crude and topped crude mineral oils having high contents of asphalt and sulfur compounds and containing organo metallic complexes and other ash-forming compounds, for producing high quality fuel oil having low viscosity and low content of asphalt, ashes and sulfur comprising passing the oil at a tentperature between 600 and 1060 F. and at a pressure between 70 to 710 p.s.i. into a contact chamber together with hydrogen in the presence of a mass of high porosity having a large surface area selected from the group con sisting of granulated activated carbon and granulated activated metallurgical coke, maintaining the space velocity of the oil fed to the contact chamber between 0.5 and 5.0 volumes of liquid/hour/volume of contact mass, and
Landscapes
- 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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT830923X | 1955-04-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2929776A true US2929776A (en) | 1960-03-22 |
Family
ID=11319705
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US573106A Expired - Lifetime US2929776A (en) | 1955-04-02 | 1956-03-22 | Process for removal of sulfur, metals and asphalt from petroleum crudes |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US2929776A (en(2012)) |
| BE (1) | BE546564A (en(2012)) |
| FR (1) | FR1144970A (en(2012)) |
| GB (1) | GB830923A (en(2012)) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3087888A (en) * | 1960-06-15 | 1963-04-30 | Gulf Research Development Co | Determination of vanadium content of hydrocarbon oils by electron paramagnetic resonance spectrometry |
| US4988434A (en) * | 1989-12-13 | 1991-01-29 | Exxon Research And Engineering Company | Removal of metallic contaminants from a hydrocarbonaceous liquid |
| US4992163A (en) * | 1989-12-13 | 1991-02-12 | Exxon Research And Engineering Company | Cat cracking feed preparation |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3748261A (en) * | 1971-12-14 | 1973-07-24 | Universal Oil Prod Co | Two-stage desulfurization with solvent deasphalting between stages |
| WO2009073436A2 (en) | 2007-11-28 | 2009-06-11 | Saudi Arabian Oil Company | Process for catalytic hydrotreating of sour crude oils |
| US9260671B2 (en) | 2008-07-14 | 2016-02-16 | Saudi Arabian Oil Company | Process for the treatment of heavy oils using light hydrocarbon components as a diluent |
| US8372267B2 (en) | 2008-07-14 | 2013-02-12 | Saudi Arabian Oil Company | Process for the sequential hydroconversion and hydrodesulfurization of whole crude oil |
| EP2445997B1 (en) | 2009-06-22 | 2021-03-24 | Saudi Arabian Oil Company | Demetalizing and desulfurizing virgin crude oil for delayed coking |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1859514A (en) * | 1932-05-24 | Certificate of correction | ||
| US2002902A (en) * | 1932-01-08 | 1935-05-28 | Gulf Refining Co | Process for removing gum and gum forming constituents from cracked petroleum distillates |
| US2608521A (en) * | 1948-01-06 | 1952-08-26 | Shell Dev | Process for refining carbonaceous material |
| US2614066A (en) * | 1949-05-10 | 1952-10-14 | Gulf Oil Corp | Hydrodesulfurization of petroleum hydrocarbons |
| US2620362A (en) * | 1948-07-07 | 1952-12-02 | Du Pont | Method of catalytically removing sulfur |
| US2769758A (en) * | 1951-03-20 | 1956-11-06 | British Petroleum Co | Removal of sodium and vanadium from petroleum hydrocarbons followed by catalytic desulphurisation of said petroleum hydrocarbons |
-
0
- BE BE546564D patent/BE546564A/xx unknown
-
1956
- 1956-03-22 US US573106A patent/US2929776A/en not_active Expired - Lifetime
- 1956-03-29 GB GB9982/56A patent/GB830923A/en not_active Expired
- 1956-03-30 FR FR1144970D patent/FR1144970A/fr not_active Expired
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1859514A (en) * | 1932-05-24 | Certificate of correction | ||
| US2002902A (en) * | 1932-01-08 | 1935-05-28 | Gulf Refining Co | Process for removing gum and gum forming constituents from cracked petroleum distillates |
| US2608521A (en) * | 1948-01-06 | 1952-08-26 | Shell Dev | Process for refining carbonaceous material |
| US2620362A (en) * | 1948-07-07 | 1952-12-02 | Du Pont | Method of catalytically removing sulfur |
| US2614066A (en) * | 1949-05-10 | 1952-10-14 | Gulf Oil Corp | Hydrodesulfurization of petroleum hydrocarbons |
| US2769758A (en) * | 1951-03-20 | 1956-11-06 | British Petroleum Co | Removal of sodium and vanadium from petroleum hydrocarbons followed by catalytic desulphurisation of said petroleum hydrocarbons |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3087888A (en) * | 1960-06-15 | 1963-04-30 | Gulf Research Development Co | Determination of vanadium content of hydrocarbon oils by electron paramagnetic resonance spectrometry |
| US4988434A (en) * | 1989-12-13 | 1991-01-29 | Exxon Research And Engineering Company | Removal of metallic contaminants from a hydrocarbonaceous liquid |
| US4992163A (en) * | 1989-12-13 | 1991-02-12 | Exxon Research And Engineering Company | Cat cracking feed preparation |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1144970A (fr) | 1957-10-21 |
| GB830923A (en) | 1960-03-23 |
| BE546564A (en(2012)) |
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