US3249530A - Hydrorefining of petroleum crude oil - Google Patents
Hydrorefining of petroleum crude oil Download PDFInfo
- Publication number
- US3249530A US3249530A US303158A US30315863A US3249530A US 3249530 A US3249530 A US 3249530A US 303158 A US303158 A US 303158A US 30315863 A US30315863 A US 30315863A US 3249530 A US3249530 A US 3249530A
- Authority
- US
- United States
- Prior art keywords
- crude oil
- acid
- hydrorefining
- pentane
- temperature
- 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
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- 239000010779 crude oil Substances 0.000 title description 39
- 239000003208 petroleum Substances 0.000 title description 19
- 238000000034 method Methods 0.000 claims description 39
- 238000001246 colloidal dispersion Methods 0.000 claims description 27
- 229930195733 hydrocarbon Natural products 0.000 claims description 23
- 150000002430 hydrocarbons Chemical class 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 239000004215 Carbon black (E152) Substances 0.000 claims description 19
- 239000011964 heteropoly acid Substances 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052740 iodine Inorganic materials 0.000 claims description 15
- 239000011630 iodine Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 239000012263 liquid product Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 6
- 239000011369 resultant mixture Substances 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 3
- OKJPEAGHQZHRQV-UHFFFAOYSA-N iodoform Chemical compound IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 34
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000003054 catalyst Substances 0.000 description 16
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 13
- 239000000356 contaminant Substances 0.000 description 13
- 150000002739 metals Chemical class 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 230000005484 gravity Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000008186 active pharmaceutical agent Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 239000010802 sludge Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 125000002524 organometallic group Chemical group 0.000 description 5
- 230000000737 periodic effect Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000001627 detrimental effect Effects 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 150000004694 iodide salts Chemical class 0.000 description 4
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002198 insoluble material Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001844 chromium Chemical class 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005202 decontamination Methods 0.000 description 2
- 230000003588 decontaminative effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000001066 destructive effect Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- -1 heavy cycle stocks Substances 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 230000002028 premature Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- 241000969130 Atthis Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- YNZSKFFENDBGOV-UHFFFAOYSA-N [V].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical class [V].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 YNZSKFFENDBGOV-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- RDVQTQJAUFDLFA-UHFFFAOYSA-N cadmium Chemical compound [Cd][Cd][Cd][Cd][Cd][Cd][Cd][Cd][Cd] RDVQTQJAUFDLFA-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000000727 fraction Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-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
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- C10G45/14—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 with moving solid particles
- C10G45/16—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 with moving solid particles suspended in the oil, e.g. slurries
-
- 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 involves a process for hydrorefining heavy hydrocarbon charge stocks to effect the removal of nitrogen and sulfur therefrom, and is advantageous When employed for the destructive removal of organo-metallic contaminants and particularly the conversion of pentaneinsoluble hydrocarbonaceous material.
- crude oils In addition to organo-metallic contaminants, crude oils contain greater quantities of sulfurous and nitrogenous compounds than are generally found in lighter hydrocarbon fractions such as gasoline, kerosene, light gas oil,
- lighter hydrocarbon fractions such as gasoline, kerosene, light gas oil
- a Wyoming sour crude having a gravity of 23.2 API at 60 F., contains about 2.8% by weight of sulfur and 2700 p.p.m. of total nitrogen.
- a crude tower bottoms having a gravity of 14.3 API, contains 3.08% by weight of sulfur, 10.93% by weight of pentane-insolubles, 3830 p.p.m. of nitrogen and 85 p.p.m. of metallic contaminants.
- the object of the present invention is to provide a more efficient process for hydrorefining heavier hydrocarbonaceous material, and particularly petroleum crude oil, utilizing an unsupported catalyst prepared in a particular manner.
- hydrorefining connotes the catalytic treatment, in an atmosphere of hydrogen, of a petroleum crude oil, or a hydrocarbon fraction or distillate for the purpose of eliminating and/ or reducing the concentration of the various contaminating influences previously described.
- metals are generally removed from the charge stock by deposition of the same on the catalyst employed. This increases the amount of catalyst, actively shields the catalytica-lly active surfaces and centers from the material being processed, and thereby virtually precludes the utilization of a fixed-bed catalyst system for processing such contaminated crude oil.
- the process of the present invention is particularly advantageous for effecting the conversion of sulfur-ous, nitrogenous and the organo-metallic contaminants Without significant product yield loss, while simultaneously converting a substantial quantity of pentane-insoluble material into pentane-soluble liquid hydrocarbons.
- the present invention relates to a process for hydrorefining a hydrocarbon charge stock which comprises admixing said charge stock with at least one heteropoly acid selected from the metals of Group VI-B having an atomic number greater than 24, heating the resulting mixture at a temperature less than about 310 C. and for a time sufficient to form a colloidal dispersion of said heteropoly acid, combining the colloidal dispersion with an iodine-containing compound, reacting the same with hydrogen at a temperature in excess of about 225 C. and at a pressure greater than about 500 pounds per square inch gauge, and recovering a hydrorefined liquid product.
- Another broad embodiment of the present invention encompasses a process for hydrorefining a petroleum 2 atomic number greater than 24, heating the resulting mix- The present invention ture at a temperature less than about 310 C. and for a time sufiicient to form a colloidal dispersion of said heteropoly acid, combining the colloidal dispersion with iodoform, reacting the same withhydrogen at a temperature in excess of about 225 C. and at a pressure greater than about 500 pounds per square inch gauge, and recov- 'ering said crude oil substantially free from pentane-insoluble asphaltenes.
- a more limited embodiment of the present invention involves a process for hydrorefining a petroleum crude oil containing pentane-insoluble asphaltenes which comprises admixing said crude oil with phosphomolybdic acid, heating the resulting mixture at a temperature less than about 310 C. and for a time sufficient to form a colloidal dispersion of said phosphomolybdic acid, reacting the colloidal dispersion and a metallic iodide selected from the metals of Group II of the Periodic Table with hydrogen at a temperature within the range of from about 225 C. to about 500 C. and at a pressure of from about 500 to about 5000 pounds per square inch gauge, and recovering said crude oil substantially free from pentaneinsoluble asphaltenes.
- the method of the present invention involves the preparation of a catalyst utilizing metals selected from Group VI-B of the Periodic Table.
- the metals from Group VIB namely molybdenum and/or tungsten, have an atomic number greater than 24.
- heteropoly acids of chromium in addition to other chromium complexes, upon decomposition within the hydrocarbon charge stock, do not yield acceptable economical results, and particularly with respect to the conversion of the pentane-insoluble fraction and the organo-metallic compounds such as the nickel and/or vanadium porphyrins. Furthermore, the decomposition of such chromium complexes is effected above about 310 C., resulting in premature thermal cracking of thecrude oil.
- the catalyst is preferably prepared by dissolving heteropoly molybdic acids and/ or heteropoly tungstic acids, such as phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid and silicotungstic acid in an appropriate solvent such as alcohols containing up to and including about ten carbon atoms per molecule.
- Thesolution is added to the petroleum crude oil and the mixture distilled with stirring, at a temperature less than about 310 C., to remove the solvent and form a colloidally dispersed catalyst sus pended within the petroleum crude oil.
- the quantity of the heteropoly acid employed is such that the colloidal suspension, or dispersion, which results upon removal of the solvent, comprises from about 1.0% to about 10.0%
- Suitable heteropoly acids selected from the metals of Group VI-B having an atomic number greater than 24 include phosphomolybdic, phosphotungstic acid, silicomolybdic acid, silicotungstic acid, and mixtures thereof including phosphomolybdic acid-phosphotungstic acid, etc.
- the process is etfected, as hereinafter set forth'in specific examples, by initially dissolving the desired quantity of the heteropoly metallic acid, such as phosphomolybdic acid, in the hydrocarbon charge stock.
- the contaminating influences with the exception of asphaltenes, with the petroleum crude oil are removed to the extent that the future processing of such crude oil no longer incurs the detrimental eifects otherwise resulting from the presence of these contaminating influences.
- the conversion of asphaltenes is most difiicult to achieve; further, as the concentrations of the other contaminants increases, the degree of conversion of the asphaltenes is lessened.
- Typical of the alcohols suitable for use in preparing the solution of the desired heteropoly metallic acid include isopropyl alcohol, isopentyl alcohol, methyl'alcohol, amyl alcohol, mixtures thereof, etc.
- the mixture of the alcohol solution of the phosphomolybdic acid and the petroleum crude oil is heated at a temperaturebelow about 310 C. for the purpose of distilling the alcohol, leaving the phosphomolybdic acid as a colloidal dispersion within the crude oil. Temperatures above about 310 C. tend to result in premature cracking reactions whereby the effectiveness to convert pentane-insoluble asphaltenes becomes adversely affected.
- the colloidal dispersion of the heteropoly metallic acid and charge stock is admixed with an iodine-containing compound prior to being introduced into the reaction zone to be reacted with hydrogen therein.
- an iodine-containing compound for the purpose of distilling the solvent employed in initially preparing the colloidal dispersion, it is preferred to add the iodine-containing compound after the solvent is removed; in this way, the heavy hydrocarbonaceous charge stock will contain the desired quantity of iodine while being processed at reaction conditions.
- the iodine-containing compound is employed in an amount within the range of about 0.05% to about 5.0% by weight, calculated on the basis of the quantity of charge stock, and as the element.
- Iodine, hydrogen iodine and iodoform are the particularly preferred iodine-containing compounds utilized in combination with the desired heteropoly acid, although metallic iodides will yield acceptable results under proper operating conditions.
- Suitable metallic iodides are those selected from'the metals of Group II of the Periodic Table, and include, therefore, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium,'mercury, mixtures of tWo or more, etc.
- These metallic iodides may also be employed in combination with iodoform, iodine, and/or hydrogen iodine, maintaining the concentration of iodine within the aforesaid range.
- the colloidal dispersion is then passed into a suitable reaction zone maintained at a temperature within the range of from about 225 C. to about 500 C. and under a hydrogen pressure within the range of about 500 to about 5000 p.-s.i.g.
- the process may be conducted in a batch-type procedure or in an enclosed vessel through which the colloidal suspension is passed; When effected in a continuous manner, the process may be conducted in either upward flow or downward flow.
- the normally liquid hydrocarbons are separated from the total reaction zone eflluent by any suitable means, for example, through the use of a centrifuge or settling tanks, at. least a portion of the'resulting catalystcontaining sludge being combined with fresh petroleum crude "oil, and recycled to the reaction zone.
- a centrifuge or settling tanks In order to maintain the highest possible degree of catalytic activity, it is preferred that at least a portion of the catalyst-containing sludge be removed from the process prior to combining the remainder with fresh crude oil.
- the precise quantity of the 'catalystecontaining sludge removed from the process will be dependent upon the desired degree of contaminant removal. However, it is further desirable to add a quantity of fresh phosphomolybdic acid and the iodine-containing compound to the petroleum crude oil 1n order to compensate for that quantity of molybdenum,
- the vhydrorefining catalyst utilized in the process of the present invention exists as a colloidal dispersion within the hydrocarbonaceous charge stock being subjected to reaction with hydrogen.
- the catalyst is a colloidally dispersed heteropoly acid selected from the group which has been previously described. The catalytic action exhibited by the hetero-.
- poly acid is supplemented, in a synergistic manner
- an iodine-containing compound such as iodine, hydrogen iodine, iodoform and metallic iodides from the metals of Group II of the Periodic Table.
- an iodine-containing compound such as iodine, hydrogen iodine, iodoform and metallic iodides from the metals of Group II of the Periodic Table.
- a colloid-a1 dispersion of 30 grams of phosphomolybdic acid was prepared by initially dissolving the phosphomolybdic acid in 400 grams of isopropyl alcohol and filtering to remove small traces of insoluble material. 1000 grams of the crude tower bottoms was placed in a two-liter reaction flask containing a vibromix stirrer, and the isopropyl alcohol solution added thereto in dropwise fashion. The temperature of the contents of the twoliter flask was maintained at 130 C. such that the alcohol was distilled while the solution was added to the crude tower bottoms.
- the charge stock was a Wyoming sour crude oil having a gravityof 6 28.9 API at 60 F. contained 0.97% by weight of pentane-insoluble asphaltenes.
- the former was found to have a gravity, API at 60 F.,. of 20.6, and contained 4.79% by weight of pentane-in-- soluble asphaltenes.
- Crude tower bottoms in an amount of 200 grams and 2 grams of iodoform were reacted with hydrogen at a temperature of 375 C., for a period of 5 hours, and the liquid product effluent indicated a gravity, API at 60 F., of 23.2, and contained 4.17% by weight of pentaneinsoluble asphaltenes.
- EXAMPLE III 20 0 grams of the colloidal dispersion of phosphomolybdic acid in the crude tower bottoms, described in conjunction with the foregoing Example I, and 2 grams of iodoform were placed in the 1800 milliliter rocker-type autoclave, pressured to 100 atmospheres with hydrogen and heated to a temperature of 375 C., being maintained atthis level for a period of 5 hours. Following separation of the contents into the catalyst-containing sludge and normally liquid hydrocarbons, the latter was found to have a gravity, API at 60 F., of 26.5, and contained 0.18% by weight of pentane-insoluble asphaltenes.
- a process for hydrorefining a hydrocarbon charge stock which comprises admixing said charge stock with at least one heteropoly acid containing a metal of Group VI-B having anatomic number greater than 24, heating the resulting mixture at a temperature less than about 310 C. and for a time sufiicient to form a colloidal dispersion of said heteropoly acid, commingling iodine with the colloidal dispersion, reacting the resultant mixture with hydrogen at a temperature in excess of about 225 C. and at a pressure greater than about 500 p.s.i.g., and recovering a hydrorefined liquid product.
- the process of claim 1 further characterized in that said mixture is reacted with hydrogen at a temperature within the range of from about 225 C. to about 500 C. and under a pressure of from about 500 to about 5000 .s.1.g. p 3.
- said heteropoly acid comprises phosphomolybdic acid.
- a process for hydrorefining a petroleum crude oil containing pentane-insoluble asphaltenes which comprises admixing said crude oil with at least one heteropoly acid containing a metal of Group VI-B having an atomic number greater than 24, heating the resulting mixture at a temperature less than about 310 C. and for a time sulficient to form a colloidal dispersion of said heteropoly acid, combining the colloidal dispersion with iodoform, reacting the resultant mixture with hydrogen at a temperature in excess of about 225 C. and at a pressure greater than about 500 p.s-.i.g., and recovering said crude oil substantially free from pentane-insoluble asphaltenes.
- a process for hydrorefining a petroleum crude oil containing pentane-insoluble asphaltenes which comprises admixing said crude oil with phosphomolybdic acid and iodoform, heating the resulting mixture at a temperature less than about 310 C. and for a time sufiicient to form a colloidal dispersion of said phosphomolybdic acid, reacting the colloidal dispersion with hydrogen at a temperature within the range of about 225 C. to about 500 C. and at a pressure of from about 500 to about 5000 p.s.i.g., and recovering said crude oil substantially free from pentane-insoluble asphaltenes.
- a process for hydrorefining a petroleum crude oil containing pentane-insoluble asphaltenes which comprises admixing said crude'oil with phosphomolybdic acid, heating the resulting mixture at a temperature less than about 310 C. and for a time sufficient to form a colloidal dispersion of said acid, combining the colloidal dispersion with iodoform, reacting the resultant mixture with hydrogen at a temperature in excess of about 225 C. and at a pressure greater than about 500 p.s.i.g., and recovering said crude oil substantially free from pentane-insoluble asphaltenes.
- a process for hydrorefining a hydrocarbon charge stock which comprises admixing said charge stock with phosphomolybdic acid, heating the resulting mixture at a temperature less than about 310 C. and for a time suflicient to form a colloidal dispersion of said acid, cornmingling iodoform with the colloidal dispersion, reacting the resultant mixture with hydrogen at a temperature in excess of about 225 C and at a pressure greater than about 500 p.s.i.g., and-recovering a hydrorefined liquid.
- a process for hydrorefining a hydrocarbon charge stock which comprises subjecting said charge stock to reaction with hydrogen in admixture with iodine and a colloidal dispersion of at least one heteropoly acid containing a metal of Group VIB having an atomic number greater than 24 at a temperature in excess ofabou-t 225 C. and at a pressure greater than about 500 p-.s.i.g., and recovering a hydrorefined liquid product.
- a process for hydrorefining a hydrocarbon charge stock which comprises subjecting said charge stock to reaction with hydrogen in admixture With iodoform and a colloidal dispersion of phosphomolybdic acid at a temperature in excess of about 225 C. and at a pressure greater than about 500 p.s.i.g., and recovering a hydrorefined liquid product.
Description
- etc.
United States Patent 3,249,530 HYDROREFINING 0F PETROLEUM CRUDE OIL John G. Gatsis, Des Plaines, Ill., assignor to Universal Oil Products Company, Des Plaines, 111., a corporation of Delaware No Drawing. Filed Aug. 19, 1963, Ser. No. 303,158 14 Claims. '(Cl. 208264) The present invention relates to the use of a novel catalyst in the hydrorefining of petroleum crude oils, heavy vacuum gas oils, heavy cycle stocks, crude oil residuum, topped crude oils, etc. More specifically, the present invention involves a process for hydrorefining heavy hydrocarbon charge stocks to effect the removal of nitrogen and sulfur therefrom, and is advantageous When employed for the destructive removal of organo-metallic contaminants and particularly the conversion of pentaneinsoluble hydrocarbonaceous material.
Petroleum crude oil, and the heavier hydrocarbon fractions and/or d-istillates obtained therefrom, particularly heavy vacuum gas oils and topped crudes, contain-ni trogenous and sulfurous compounds in large quantities. In addition, petroleum crude oils generally contain det rimental quantities of organo-metallic contaminants which exert deleterious effects upon the catalyst utilized in various processes to which the crude oil, topped crude oil, or heavy hydrocarbon fraction may ultimately be subjected. The more common of such metallic contaminants are nickel and vanadium, often existing in concentrations in excess of 50 p.p.m., although other metals including iron, copper, etc., may be present. Although metallic contaminants, existing as oxide or sulfide scale, may be removed, at least in part, by a relatively simple filtering technique, and water-soluble salts are at least in part removable by washing and a subsequent dehydration procedure, a much more severe treatment is required to effect the destructive removal of organo-metallic compounds, such -as metal porphyrins, particularly to the degree necessary to produce a crude oil or heavy hydrocar-bon fraction which is suitable for further processing.
In addition to organo-metallic contaminants, crude oils contain greater quantities of sulfurous and nitrogenous compounds than are generally found in lighter hydrocarbon fractions such as gasoline, kerosene, light gas oil, For example, a Wyoming sour crude, having a gravity of 23.2 API at 60 F., contains about 2.8% by weight of sulfur and 2700 p.p.m. of total nitrogen. A crude tower bottoms, having a gravity of 14.3 API, contains 3.08% by weight of sulfur, 10.93% by weight of pentane-insolubles, 3830 p.p.m. of nitrogen and 85 p.p.m. of metallic contaminants. The nitrogenous and sulfurous compounds are converted, upon being subjected to a catalytic hydrorefining process, into hydrocarbons, ammonia and hydrogen sulfide; the reduction in the concentration of the organo-metallic contaminants is not as easily achieved, and to the extent that the same no longer exert a detrimental effect, particularly in regard to further processing of the crude oil. When a hydrocarbon charge stock containing metals in excess of about 3.0 p.p.m., is subjected to a cracking process for'the purpose of producing lower-boiling components, the metals become deposited upon the catalyst employed, steadily increasing in quantity until such time as the composition of the catalytic composite is changed to the extent that undesirable results are obtained.
However, in addition to the foregoing contaminating influences, crude oils and other heavier hydrocarbon frac tions contain excessive quantities of pentane-insoluble material. For example, the Wyoming sour crude described above consists of about 8.3% by weight of pentane-insolu-b-le asphaltenes. These are hydrocarbonaceous com- Patented May 3, 1966 "ice and surfaces thereof from the material being processed.
The conversion of these pentane-insoluble asphaltenes is that function of the catalyst most diflicult to achieve, and not withstanding an acceptable degree of elimination of the other contaminants, the liquid product efiluent may contain a detrimental amount of this material.
The object of the present invention is to provide a more efficient process for hydrorefining heavier hydrocarbonaceous material, and particularly petroleum crude oil, utilizing an unsupported catalyst prepared in a particular manner. The term hydrorefining, as employed herein, connotes the catalytic treatment, in an atmosphere of hydrogen, of a petroleum crude oil, or a hydrocarbon fraction or distillate for the purpose of eliminating and/ or reducing the concentration of the various contaminating influences previously described. As hereinabove set forth, metals are generally removed from the charge stock by deposition of the same on the catalyst employed. This increases the amount of catalyst, actively shields the catalytica-lly active surfaces and centers from the material being processed, and thereby virtually precludes the utilization of a fixed-bed catalyst system for processing such contaminated crude oil. Various moving-bed processes, employing catalytically active metals deposited upon a carrier material consisting, for example, of silica and/or alumina, or other refractory inorganic oxide materials, are extremely erosive, causing plant maintenance to become difiicult and expensive. teaches the preparation of a colloidally dispersed, unsupported catalytic material useful in a slurry process, which catalytic material will not effect extensive erosion or corrosion of the reaction system. The present process yields a liquid hydrocarbon product which is more suitable for further processing without experiencing the difficulties otherwise resulting from the presence of the foregoing contaminants. The process of the present invention is particularly advantageous for effecting the conversion of sulfur-ous, nitrogenous and the organo-metallic contaminants Without significant product yield loss, while simultaneously converting a substantial quantity of pentane-insoluble material into pentane-soluble liquid hydrocarbons.
In a 'broad embodiment, the present invention relates to a process for hydrorefining a hydrocarbon charge stock which comprises admixing said charge stock with at least one heteropoly acid selected from the metals of Group VI-B having an atomic number greater than 24, heating the resulting mixture at a temperature less than about 310 C. and for a time sufficient to form a colloidal dispersion of said heteropoly acid, combining the colloidal dispersion with an iodine-containing compound, reacting the same with hydrogen at a temperature in excess of about 225 C. and at a pressure greater than about 500 pounds per square inch gauge, and recovering a hydrorefined liquid product.
Another broad embodiment of the present invention encompasses a process for hydrorefining a petroleum 2 atomic number greater than 24, heating the resulting mix- The present invention ture at a temperature less than about 310 C. and for a time sufiicient to form a colloidal dispersion of said heteropoly acid, combining the colloidal dispersion with iodoform, reacting the same withhydrogen at a temperature in excess of about 225 C. and at a pressure greater than about 500 pounds per square inch gauge, and recov- 'ering said crude oil substantially free from pentane-insoluble asphaltenes.
, A more limited embodiment of the present invention involves a process for hydrorefining a petroleum crude oil containing pentane-insoluble asphaltenes which comprises admixing said crude oil with phosphomolybdic acid, heating the resulting mixture at a temperature less than about 310 C. and for a time sufficient to form a colloidal dispersion of said phosphomolybdic acid, reacting the colloidal dispersion and a metallic iodide selected from the metals of Group II of the Periodic Table with hydrogen at a temperature within the range of from about 225 C. to about 500 C. and at a pressure of from about 500 to about 5000 pounds per square inch gauge, and recovering said crude oil substantially free from pentaneinsoluble asphaltenes.
From the foregoing embodiments, it is noted that the method of the present invention involves the preparation of a catalyst utilizing metals selected from Group VI-B of the Periodic Table. Reference is herein made to the Periodic Chart of the Elements, pages 448 and 449, 43rd edition of Handbook of Chemistry and Physics. It is further noted that the metals from Group VIB, namely molybdenum and/or tungsten, have an atomic number greater than 24. It has been found that heteropoly acids of chromium, in addition to other chromium complexes, upon decomposition within the hydrocarbon charge stock, do not yield acceptable economical results, and particularly with respect to the conversion of the pentane-insoluble fraction and the organo-metallic compounds such as the nickel and/or vanadium porphyrins. Furthermore, the decomposition of such chromium complexes is effected above about 310 C., resulting in premature thermal cracking of thecrude oil. Briefly, the catalyst is preferably prepared by dissolving heteropoly molybdic acids and/ or heteropoly tungstic acids, such as phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid and silicotungstic acid in an appropriate solvent such as alcohols containing up to and including about ten carbon atoms per molecule. Thesolution is added to the petroleum crude oil and the mixture distilled with stirring, at a temperature less than about 310 C., to remove the solvent and form a colloidally dispersed catalyst sus pended within the petroleum crude oil. The quantity of the heteropoly acid employed is such that the colloidal suspension, or dispersion, which results upon removal of the solvent, comprises from about 1.0% to about 10.0%
by Weight, calculated, however, as the elemental metal.
' Suitable heteropoly acids, selected from the metals of Group VI-B having an atomic number greater than 24 include phosphomolybdic, phosphotungstic acid, silicomolybdic acid, silicotungstic acid, and mixtures thereof including phosphomolybdic acid-phosphotungstic acid, etc. The process is etfected, as hereinafter set forth'in specific examples, by initially dissolving the desired quantity of the heteropoly metallic acid, such as phosphomolybdic acid, in the hydrocarbon charge stock. When the phosphomolybdic acid is initially dissolved in an alcohol containing up to and including about ten carbon atoms per molecule, the contaminating influences, with the exception of asphaltenes, with the petroleum crude oil are removed to the extent that the future processing of such crude oil no longer incurs the detrimental eifects otherwise resulting from the presence of these contaminating influences. As previously set forth, the conversion of asphaltenes is most difiicult to achieve; further, as the concentrations of the other contaminants increases, the degree of conversion of the asphaltenes is lessened. Typical of the alcohols suitable for use in preparing the solution of the desired heteropoly metallic acid include isopropyl alcohol, isopentyl alcohol, methyl'alcohol, amyl alcohol, mixtures thereof, etc. The mixture of the alcohol solution of the phosphomolybdic acid and the petroleum crude oil is heated at a temperaturebelow about 310 C. for the purpose of distilling the alcohol, leaving the phosphomolybdic acid as a colloidal dispersion within the crude oil. Temperatures above about 310 C. tend to result in premature cracking reactions whereby the effectiveness to convert pentane-insoluble asphaltenes becomes adversely affected. It is further noted, from the foregoing embodiments, that the colloidal dispersion of the heteropoly metallic acid and charge stock is admixed with an iodine-containing compound prior to being introduced into the reaction zone to be reacted with hydrogen therein. For the purpose of distilling the solvent employed in initially preparing the colloidal dispersion, it is preferred to add the iodine-containing compound after the solvent is removed; in this way, the heavy hydrocarbonaceous charge stock will contain the desired quantity of iodine while being processed at reaction conditions.
The iodine-containing compound is employed in an amount within the range of about 0.05% to about 5.0% by weight, calculated on the basis of the quantity of charge stock, and as the element. Iodine, hydrogen iodine and iodoform are the particularly preferred iodine-containing compounds utilized in combination with the desired heteropoly acid, although metallic iodides will yield acceptable results under proper operating conditions. Suitable metallic iodides are those selected from'the metals of Group II of the Periodic Table, and include, therefore, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium,'mercury, mixtures of tWo or more, etc. These metallic iodides may also be employed in combination with iodoform, iodine, and/or hydrogen iodine, maintaining the concentration of iodine within the aforesaid range. The colloidal dispersion is then passed into a suitable reaction zone maintained at a temperature within the range of from about 225 C. to about 500 C. and under a hydrogen pressure within the range of about 500 to about 5000 p.-s.i.g. The process may be conducted in a batch-type procedure or in an enclosed vessel through which the colloidal suspension is passed; When effected in a continuous manner, the process may be conducted in either upward flow or downward flow. The normally liquid hydrocarbons are separated from the total reaction zone eflluent by any suitable means, for example, through the use of a centrifuge or settling tanks, at. least a portion of the'resulting catalystcontaining sludge being combined with fresh petroleum crude "oil, and recycled to the reaction zone. In order to maintain the highest possible degree of catalytic activity, it is preferred that at least a portion of the catalyst-containing sludge be removed from the process prior to combining the remainder with fresh crude oil. The precise quantity of the 'catalystecontaining sludge removed from the process will be dependent upon the desired degree of contaminant removal. However, it is further desirable to add a quantity of fresh phosphomolybdic acid and the iodine-containing compound to the petroleum crude oil 1n order to compensate for that quantity of molybdenum,
calculated as the elemental metal, removed from thecatalyst containing sludge.
As hereinabove set forth, the vhydrorefining catalyst utilized in the process of the present invention, exists as a colloidal dispersion within the hydrocarbonaceous charge stock being subjected to reaction with hydrogen. Thus, the catalyst is a colloidally dispersed heteropoly acid selected from the group which has been previously described. The catalytic action exhibited by the hetero-.
poly acid is supplemented, in a synergistic manner,
through the utilization of an iodine-containing compound such as iodine, hydrogen iodine, iodoform and metallic iodides from the metals of Group II of the Periodic Table. As hereinafter indicated by specific example, the
utilization of a combination of the iodine-containing compound and the heteropoly acid results in a significantly greater degree of contaminant removal than when either one is employed in the absence of the other. Surprisingly, there exists the synergistic effect that the greater degree of decontamination of the charge stock can be effected at a significantly lower temperature level. Of itself, as recognized by those possessing skill within the art of petroleum refining operations, this one simple factor affords a great degree of economic benefit in the design and operation of the unit. For example, by permitting operation at a lower temperature level, the residence time or space velocity, or charge stock to catalyst weight ratio, can be economically adjusted to achieve the same degree of decontamination than when either compound is utilized in the absence of the other. The deposition of coke and other carbonaceous material is lessened, and the degree of thermal cracking, resulting in the production of gaseous light paraffins such as methane, ethane and propane, is significantly minimized.
These and numerous other advantages will be readily apparent to those having knowledge of petroleum refinery operations and the economic considerations involved therewith.
The following examples are given to illustrate the process of the present invention and the effectiveness thereof in converting pentane-insoluble asphaltenes into pentane-soluble, lower-boiling liquid hydrocarbon products.
EXAMPLE I The crude oil employed to illustrate the benefits afforded through the utilization of the present invention was a crude tower bottoms having a gravity, AP-I at 60 F., of 14.3, containing about 3.0% by weight of sulfur, 3830 ppm. of nitrogen and consisting of 10.93% by weight of pentane-insoluble asphaltenes. These and other analyses of the charge stock are indicated in the following table.'
Crude tower bottoms analysis Gravity, ABI 60 F. 14.3 Volume distilled F.:
Sulfur, wt. percent 3.08 Total nitrogen, p.p.rn. 3830 Metals contamination, p.p.rn. 91 Pentane-insolubles, wt. percent 10.93
A colloid-a1 dispersion of 30 grams of phosphomolybdic acid was prepared by initially dissolving the phosphomolybdic acid in 400 grams of isopropyl alcohol and filtering to remove small traces of insoluble material. 1000 grams of the crude tower bottoms was placed in a two-liter reaction flask containing a vibromix stirrer, and the isopropyl alcohol solution added thereto in dropwise fashion. The temperature of the contents of the twoliter flask was maintained at 130 C. such that the alcohol was distilled while the solution was added to the crude tower bottoms.
200 grams of the colloidal dispersion were placed in an 1800-milliliter, rocker-type autoclave, and pressured to 100 atmospheres with hydrogen. The autoclave was heated to a temperature of 350 C., and maintained at this temperature level for a period of 5 hours. The contents of the autoclave were cooled to room temperature removed therefrom and subjected to centrifugal action to separate the normally liquid product from the catalystcontaining sludge. In this instance, the normally liquid product indicated a gravity, API at 60 F., of 16.4 and contained 1.54% by weight of pentane-i-nsoluble asphaltenes.
For this portion of the example, the charge stock was a Wyoming sour crude oil having a gravityof 6 28.9 API at 60 F. contained 0.97% by weight of pentane-insoluble asphaltenes.
Notwithstanding the lesser degree of contamination of the sour crude oil, as well as the more severe operating temperature, it will be noted that the degree of Crude tower bottoms in an amount of 200 grams and 2 grams of iodoform were placed in the 1800 milliliter rocker-type autoclave, pressured to atmospheres with hydrogen and heated to a temperature of 350 C., being maintained at this level for a period of 5 hours. Upon separation of the liquid product efiluent from the sludge,
the former was found to have a gravity, API at 60 F.,. of 20.6, and contained 4.79% by weight of pentane-in-- soluble asphaltenes.
Crude tower bottoms in an amount of 200 grams and 2 grams of iodoform were reacted with hydrogen at a temperature of 375 C., for a period of 5 hours, and the liquid product effluent indicated a gravity, API at 60 F., of 23.2, and contained 4.17% by weight of pentaneinsoluble asphaltenes.
This example illustrates the fact that the use of iodoform, in the absence of the phosphomolybdic acid, although resulting in a substantial conversion of the tower bottoms into lower-boiling hydrocarbon products, obviously does not result in an acceptable degree of conversion of the pentane-insoluble asphaltenes.
EXAMPLE III 20 0 grams of the colloidal dispersion of phosphomolybdic acid in the crude tower bottoms, described in conjunction with the foregoing Example I, and 2 grams of iodoform were placed in the 1800 milliliter rocker-type autoclave, pressured to 100 atmospheres with hydrogen and heated to a temperature of 375 C., being maintained atthis level for a period of 5 hours. Following separation of the contents into the catalyst-containing sludge and normally liquid hydrocarbons, the latter was found to have a gravity, API at 60 F., of 26.5, and contained 0.18% by weight of pentane-insoluble asphaltenes. This example indicates the synergistic effect resulting through the utilization and the combination of the phosphomolybdic acid and iodoform. As indicated by the data presented in Example II, it would be presumed that the addition of iodoform to the phosphomolybdic acid colloidal dispersion would not have the effect of decreasing the concentration of pentane-insoluble asphaltenes in the liquid product eflluent; at best, it might be expected that there would be no effect whatsoever. To the contrary, it has been shown that the addition of the iodoform significantly improves the catalytic action exhibited by the phosphomolybdic acid.
The foregoing specification and examples indicate the method of the present invention, and illustrate the benefits to be afforded through the utilization thereof. It is not intended that the present invention be limited unduly to the reagents, operating conditions and/or concentrations employed therein, beyond the scope and spirit of the appended claims.
I claim as my invention:
1. A process for hydrorefining a hydrocarbon charge stock which comprises admixing said charge stock with at least one heteropoly acid containing a metal of Group VI-B having anatomic number greater than 24, heating the resulting mixture at a temperature less than about 310 C. and for a time sufiicient to form a colloidal dispersion of said heteropoly acid, commingling iodine with the colloidal dispersion, reacting the resultant mixture with hydrogen at a temperature in excess of about 225 C. and at a pressure greater than about 500 p.s.i.g., and recovering a hydrorefined liquid product.
'2. The process of claim 1 further characterized in that said mixture is reacted with hydrogen at a temperature within the range of from about 225 C. to about 500 C. and under a pressure of from about 500 to about 5000 .s.1.g. p 3. The process of claim 1 further characterized in that said heteropoly acid comprises phosphomolybdic acid.
4. The process of claim 1 further characterized in that said heteropoly acid comprises phosphotungstic acid.
5. A process for hydrorefining a petroleum crude oil containing pentane-insoluble asphaltenes which comprises admixing said crude oil with at least one heteropoly acid containing a metal of Group VI-B having an atomic number greater than 24, heating the resulting mixture at a temperature less than about 310 C. and for a time sulficient to form a colloidal dispersion of said heteropoly acid, combining the colloidal dispersion with iodoform, reacting the resultant mixture with hydrogen at a temperature in excess of about 225 C. and at a pressure greater than about 500 p.s-.i.g., and recovering said crude oil substantially free from pentane-insoluble asphaltenes.
6. The process of claim 5 further characterized in that said heteropoly acid comprises phosphotungstic acid.
7. The process of claim 5 further characterized in that said heteropoly acid comprises silicomolybdic acid.
8. The process of claim 5 further characterized in that said heteropoly acid comprises silicotungstic acid.
9. A process for hydrorefining a petroleum crude oil containing pentane-insoluble asphaltenes which comprises admixing said crude oil with phosphomolybdic acid and iodoform, heating the resulting mixture at a temperature less than about 310 C. and for a time sufiicient to form a colloidal dispersion of said phosphomolybdic acid, reacting the colloidal dispersion with hydrogen at a temperature within the range of about 225 C. to about 500 C. and at a pressure of from about 500 to about 5000 p.s.i.g., and recovering said crude oil substantially free from pentane-insoluble asphaltenes.
10. A process for hydrorefining a petroleum crude oil containing pentane-insoluble asphaltenes which comprises admixing said crude'oil with phosphomolybdic acid, heating the resulting mixture at a temperature less than about 310 C. and for a time sufficient to form a colloidal dispersion of said acid, combining the colloidal dispersion with iodoform, reacting the resultant mixture with hydrogen at a temperature in excess of about 225 C. and at a pressure greater than about 500 p.s.i.g., and recovering said crude oil substantially free from pentane-insoluble asphaltenes.
11. A process for hydrorefining a hydrocarbon charge stock which comprises admixing said charge stock with phosphomolybdic acid, heating the resulting mixture at a temperature less than about 310 C. and for a time suflicient to form a colloidal dispersion of said acid, cornmingling iodoform with the colloidal dispersion, reacting the resultant mixture with hydrogen at a temperature in excess of about 225 C and at a pressure greater than about 500 p.s.i.g., and-recovering a hydrorefined liquid.
product. 12. A process for hydrorefining a hydrocarbon charge stock which comprises subjecting said charge stock to reaction with hydrogen in admixture with iodine and a colloidal dispersion of at least one heteropoly acid containing a metal of Group VIB having an atomic number greater than 24 at a temperature in excess ofabou-t 225 C. and at a pressure greater than about 500 p-.s.i.g., and recovering a hydrorefined liquid product.
13. The process of claim 12 further characterized in that said iodine is introduced to the charge stock in the form of iodoform.
14. A process for hydrorefining a hydrocarbon charge stock which comprises subjecting said charge stock to reaction with hydrogen in admixture With iodoform and a colloidal dispersion of phosphomolybdic acid at a temperature in excess of about 225 C. and at a pressure greater than about 500 p.s.i.g., and recovering a hydrorefined liquid product.
References Cited by the Examiner UNITED STATES PATENTS 3,165,463 1/1965 Gleim et al. 208-264 3,166,494 1/1965 Gatis et a1. 208264 PAUL M. COUGHLAN, Primary Examiner.
S.-P. JONES, Assistant Examiner.
Claims (1)
1. A PROCESS FOR HYDROREFINING A HYDROCARBON CHARGE STOCK WHICH COMPRISES ADMIXING SAID CHARGE STOCK WITH AT LEAST ONE HETEROPOLY ACID CONTAINING A METAL OF GROUP VI-B HAVING AN ATOMIC NUMBER GREATER THAN 24, HEATING THE RESULTING MIXTURE AT A TEMPERATURE LESS THAN ABOUT 310*C. AND FOR A TIME SUFFICIENT TO FORM A COLLOIDAL DISPERSION OF SAID HETEROPOLY ACID, COMMINGLING IODINE WITH THE COLLODAL DISPERSION, REACTING TH RESULTANT MIXTURE WITH HYDROGEN AT A TEMPERATURE IN EXCESS OF ABOUT 225*C. AND AT A PRESSURE GREATER THAN ABOUT 500 P.S.I.G., AND RECOVERING A HYDROREFINED LIQUID PRODUCT.
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US303158A US3249530A (en) | 1963-08-19 | 1963-08-19 | Hydrorefining of petroleum crude oil |
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US303158A US3249530A (en) | 1963-08-19 | 1963-08-19 | Hydrorefining of petroleum crude oil |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4285804A (en) * | 1979-05-18 | 1981-08-25 | Institut Francais Du Petrole | Process for hydrotreating heavy hydrocarbons in liquid phase in the presence of a dispersed catalyst |
EP0093809A1 (en) * | 1982-05-06 | 1983-11-16 | Exxon Research And Engineering Company | Process for the hydroconversion of carbonaceous and/or hydrocarbonaceous feeds |
US4655905A (en) * | 1984-10-24 | 1987-04-07 | Institut Francais Du Petrole | Process for catalytic hydrotreatment of heavy hydrocarbons, in fixed or moving bed, with injection of a metal compound into the charge |
US10308880B2 (en) | 2017-08-21 | 2019-06-04 | Saudi Arabian Oil Company | Non-solvent asphaltene removal from crude oil using solid heteropoly compounds |
US10954454B2 (en) | 2017-08-21 | 2021-03-23 | Saudi Arabian Oil Company | Non-solvent crude oil heavy oil stream de-asphalting process |
US11225617B1 (en) | 2020-06-25 | 2022-01-18 | Saudi Arabian Oil Company | Continuous catalytic deasphalting process |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3165463A (en) * | 1962-07-02 | 1965-01-12 | Universal Oil Prod Co | Hydrorefining of crude oil and catalyst therefor |
US3166494A (en) * | 1962-08-17 | 1965-01-19 | Universal Oil Prod Co | Hydrorefining of petroleum crude oil and catalyst therefor |
-
1963
- 1963-08-19 US US303158A patent/US3249530A/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3165463A (en) * | 1962-07-02 | 1965-01-12 | Universal Oil Prod Co | Hydrorefining of crude oil and catalyst therefor |
US3166494A (en) * | 1962-08-17 | 1965-01-19 | Universal Oil Prod Co | Hydrorefining of petroleum crude oil and catalyst therefor |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4285804A (en) * | 1979-05-18 | 1981-08-25 | Institut Francais Du Petrole | Process for hydrotreating heavy hydrocarbons in liquid phase in the presence of a dispersed catalyst |
EP0093809A1 (en) * | 1982-05-06 | 1983-11-16 | Exxon Research And Engineering Company | Process for the hydroconversion of carbonaceous and/or hydrocarbonaceous feeds |
US4655905A (en) * | 1984-10-24 | 1987-04-07 | Institut Francais Du Petrole | Process for catalytic hydrotreatment of heavy hydrocarbons, in fixed or moving bed, with injection of a metal compound into the charge |
US10308880B2 (en) | 2017-08-21 | 2019-06-04 | Saudi Arabian Oil Company | Non-solvent asphaltene removal from crude oil using solid heteropoly compounds |
US10800979B2 (en) | 2017-08-21 | 2020-10-13 | Saudi Arabian Oil Company | Non-solvent asphaltene removal from crude oil using solid heteropoly compounds |
US10800980B2 (en) | 2017-08-21 | 2020-10-13 | Saudi Arabian Oil Company | Non-solvent asphaltene removal from crude oil using solid heteropoly compounds |
US10954454B2 (en) | 2017-08-21 | 2021-03-23 | Saudi Arabian Oil Company | Non-solvent crude oil heavy oil stream de-asphalting process |
US11254879B2 (en) | 2017-08-21 | 2022-02-22 | Saudi Arabian Oil Company | Non-solvent crude oil heavy oil stream de-asphalting process |
US11225617B1 (en) | 2020-06-25 | 2022-01-18 | Saudi Arabian Oil Company | Continuous catalytic deasphalting process |
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