CA2407102A1 - Use of syngas for the upgrading of heavy crude at the wellhead - Google Patents
Use of syngas for the upgrading of heavy crude at the wellhead Download PDFInfo
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- CA2407102A1 CA2407102A1 CA002407102A CA2407102A CA2407102A1 CA 2407102 A1 CA2407102 A1 CA 2407102A1 CA 002407102 A CA002407102 A CA 002407102A CA 2407102 A CA2407102 A CA 2407102A CA 2407102 A1 CA2407102 A1 CA 2407102A1
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- syngas
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- wellhead
- containing gas
- methane
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 101
- 239000001257 hydrogen Substances 0.000 claims abstract description 64
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 64
- 239000010779 crude oil Substances 0.000 claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 97
- 239000007789 gas Substances 0.000 claims description 69
- 230000008569 process Effects 0.000 claims description 65
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 54
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 25
- 239000001301 oxygen Substances 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- 238000000926 separation method Methods 0.000 claims description 22
- 239000001569 carbon dioxide Substances 0.000 claims description 21
- 238000007254 oxidation reaction Methods 0.000 claims description 21
- 230000003647 oxidation Effects 0.000 claims description 19
- 230000003197 catalytic effect Effects 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000000629 steam reforming Methods 0.000 claims description 9
- 238000002453 autothermal reforming Methods 0.000 claims description 7
- 238000005516 engineering process Methods 0.000 claims description 7
- 230000002349 favourable effect Effects 0.000 claims description 6
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 7
- 239000003129 oil well Substances 0.000 claims 2
- 238000002347 injection Methods 0.000 claims 1
- 239000007924 injection Substances 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 42
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000356 contaminant Substances 0.000 abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 abstract description 6
- 239000011593 sulfur Substances 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 description 41
- 229910002091 carbon monoxide Inorganic materials 0.000 description 27
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 26
- 229930195733 hydrocarbon Natural products 0.000 description 22
- 150000002430 hydrocarbons Chemical class 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 19
- 150000002431 hydrogen Chemical class 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 239000004215 Carbon black (E152) Substances 0.000 description 14
- 239000003345 natural gas Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 102100036201 Oxygen-dependent coproporphyrinogen-III oxidase, mitochondrial Human genes 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 101001021103 Homo sapiens Oxygen-dependent coproporphyrinogen-III oxidase, mitochondrial Proteins 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- -1 e.g. Natural products 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002006 petroleum coke Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000006057 reforming reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001991 steam methane reforming Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000264877 Hippospongia communis Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- XXLDWSKFRBJLMX-UHFFFAOYSA-N carbon dioxide;carbon monoxide Chemical compound O=[C].O=C=O XXLDWSKFRBJLMX-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011335 coal coke Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000011234 economic evaluation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002602 lanthanoids Chemical group 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical class [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000011269 treatment regimen Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000001993 wax 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/007—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 in the presence of hydrogen from a special source or of a special composition or having been purified by a special treatment
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
- E21B43/164—Injecting CO2 or carbonated water
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Mining & Mineral Resources (AREA)
- Fluid Mechanics (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The present system may be used to hydroprocess heavy crude oil at the wellhead, effectively lowering the viscosity and removing contaminants such as sulfur, nitrogen and metal contents. The hydrogen source for hydroprocessing is the separated hydrogen product from the methane produced from a syngas plant.
Description
USE OF SYNGAS FOR THE UPGRADING OF
HEAVY CRUDE AT THE WELLHEAD
Technical Field Of The Invention 10001] The present invention relates to a process for the preparation of synthesis gas, i.e., a mixture of carbon monoxide and hydrogen, from natural gas. More particularly, this invention relates to a method for maximizing the hydrogen production in syngas. Still more particularly, the present invention relates to upgrading crude oil at the wellhead to utilize co-produced natural gas and increase the ease of transportation of the crude by reducing the viscosity and sulfur, nitrogen, and other contaminants.
Background Of The Invention [00021 Large quantities of methane, the main component of natural gas, are available in many areas of the world, and natural gas is predicted to outlast oil reserves by a significant margin. However, most natural gas is situated in areas that are geographically remote from population and industrial centers. The costs of compression, transportation, and storage make its use economically unattractive. To improve the economics of natural gas use, much research has focused on the use of methane as a starting material for the production of higher hydrocarbons and hydrocarbon liquids, which are more easily transported and thus more economical. The conversion of methane to hydrocarbons is typically carried out in two steps. In the first step, methane is converted into a mixture of carbon monoxide and hydrogen (i.e., synthesis gas or syngas). In a second step, the syngas is converted into hydrocarbons.
10003] This first step, the preparation of synthesis gas from natural gas, is well known in the art and usually referred to as syngas conversion. The amount of hydrogen and carbon in syngas depends on the process technology, feedstock, and the operating conditions used in its manufacture. Synthesis gas can be made from a wide variety of feedstocks including natural gas, liquefied petroleum gas (LPG), oil, coal and petroleum coke.
Processes for converting these materials to syngas are steam methane reforming, COZ
reforming, auto thermal reforming and partial oxidation or gasification using either air or pure oxygen.
100041 The ratio of hydrogen to carbon monoxide can range as low as 0.6 with reforming of natural gas or partial oxidation of petroleum coke to as high as 6.5 with steam methane reforming. When hydrogen is the desired product, the reforming reaction can be followed by the well-known water gas shift reaction (WGS) shown in Equation 1.
CO + HZO c~ C02 + H2 ( 1 ) The WGS essentially converts all the carbon monoxide in the raw syngas to carbon dioxide, thereby maximizing the quantity of hydrogen produced. The shift reaction can likewise be avoided and the quantity of carbon monoxide maximized by selecting a feedstock with a higher carbon to hydrogen ratio or recycling carbon dioxide through the process. Although carbon monoxide can be maximized, hydrogen cannot be eliminated and is an inevitable by-product of the process.
(00051 Current industrial use of methane as a chemical feedstock proceeds by the initial conversion of methane to carbon monoxide and hydrogen by either steam reforming, which is the most widespread process, or by dry reforming. Steam reforming currently is the major process used commercially for the conversion of methane to synthesis gas, proceeding according to Equation 2.
CHa + HZO r~ CO + 3H2 (2) Although steam reforming has been practiced for over five decades, efforts to improve the energy efficiency and reduce the capital investment required for this technology continue.
HEAVY CRUDE AT THE WELLHEAD
Technical Field Of The Invention 10001] The present invention relates to a process for the preparation of synthesis gas, i.e., a mixture of carbon monoxide and hydrogen, from natural gas. More particularly, this invention relates to a method for maximizing the hydrogen production in syngas. Still more particularly, the present invention relates to upgrading crude oil at the wellhead to utilize co-produced natural gas and increase the ease of transportation of the crude by reducing the viscosity and sulfur, nitrogen, and other contaminants.
Background Of The Invention [00021 Large quantities of methane, the main component of natural gas, are available in many areas of the world, and natural gas is predicted to outlast oil reserves by a significant margin. However, most natural gas is situated in areas that are geographically remote from population and industrial centers. The costs of compression, transportation, and storage make its use economically unattractive. To improve the economics of natural gas use, much research has focused on the use of methane as a starting material for the production of higher hydrocarbons and hydrocarbon liquids, which are more easily transported and thus more economical. The conversion of methane to hydrocarbons is typically carried out in two steps. In the first step, methane is converted into a mixture of carbon monoxide and hydrogen (i.e., synthesis gas or syngas). In a second step, the syngas is converted into hydrocarbons.
10003] This first step, the preparation of synthesis gas from natural gas, is well known in the art and usually referred to as syngas conversion. The amount of hydrogen and carbon in syngas depends on the process technology, feedstock, and the operating conditions used in its manufacture. Synthesis gas can be made from a wide variety of feedstocks including natural gas, liquefied petroleum gas (LPG), oil, coal and petroleum coke.
Processes for converting these materials to syngas are steam methane reforming, COZ
reforming, auto thermal reforming and partial oxidation or gasification using either air or pure oxygen.
100041 The ratio of hydrogen to carbon monoxide can range as low as 0.6 with reforming of natural gas or partial oxidation of petroleum coke to as high as 6.5 with steam methane reforming. When hydrogen is the desired product, the reforming reaction can be followed by the well-known water gas shift reaction (WGS) shown in Equation 1.
CO + HZO c~ C02 + H2 ( 1 ) The WGS essentially converts all the carbon monoxide in the raw syngas to carbon dioxide, thereby maximizing the quantity of hydrogen produced. The shift reaction can likewise be avoided and the quantity of carbon monoxide maximized by selecting a feedstock with a higher carbon to hydrogen ratio or recycling carbon dioxide through the process. Although carbon monoxide can be maximized, hydrogen cannot be eliminated and is an inevitable by-product of the process.
(00051 Current industrial use of methane as a chemical feedstock proceeds by the initial conversion of methane to carbon monoxide and hydrogen by either steam reforming, which is the most widespread process, or by dry reforming. Steam reforming currently is the major process used commercially for the conversion of methane to synthesis gas, proceeding according to Equation 2.
CHa + HZO r~ CO + 3H2 (2) Although steam reforming has been practiced for over five decades, efforts to improve the energy efficiency and reduce the capital investment required for this technology continue.
~s2n. ova sss. ~ ssoo (0006] The catalytic partial oxidation (CPO~ of hydrocarbons, e.g., natural gas or methane to syngas is also a process known in the art. While currently limited as an industrial process, partial oxidation has recently attracted much attention due to significant inherent advantages, such as the fact that significant heat is released during the process, in contrast to steam reforming processes.
[ooo'~ In catalytic partial oxidation, natural gas is mixed with air, oxygen-enriched air, or oxygen, and introduced to a catalyst at elevated temperature and pressure.
The partial oxidation of methane yields a syngas mixture with a HZ:CO ratio of 2:1, as shown in Equation 3.
CH4 + 112 02 p CO + 2H2 (3) This ratio is more useful than the H2:C0 ratio from steam reforming for the downstream conversion of the syngas to chemicals such as methanol and to fuels. The partial oxidation is also exothermic, while the steam reforming reaction is strongly endothermic.
Furthermore, oxidation reactions are typically much faster than reforming reactions. This allows the use of much smaller reactors for catalytic partial oxidation processes. The syngas in turn may be converted to hydrocarbon products, for example, fuels boiling in the middle distillate range, such as kerosene and diesel fuel, and hydrocarbon waxes by processes such as the Fischer-Tropsch Synthesis.
looosl The selectivities of catalytic partial oxidation to the desired products, carbon monoxide and hydrogen, are controlled by several factors, but one of the most important of these factors is the choice of catalyst composition. Typically, catalyst compositions have included precious metals andlor rare earths. The large volumes of expensive catalysts needed by prior art catalytic partial oxidation processes have placed these processes generally outside the limits of economic justification.
[ooo'~ In catalytic partial oxidation, natural gas is mixed with air, oxygen-enriched air, or oxygen, and introduced to a catalyst at elevated temperature and pressure.
The partial oxidation of methane yields a syngas mixture with a HZ:CO ratio of 2:1, as shown in Equation 3.
CH4 + 112 02 p CO + 2H2 (3) This ratio is more useful than the H2:C0 ratio from steam reforming for the downstream conversion of the syngas to chemicals such as methanol and to fuels. The partial oxidation is also exothermic, while the steam reforming reaction is strongly endothermic.
Furthermore, oxidation reactions are typically much faster than reforming reactions. This allows the use of much smaller reactors for catalytic partial oxidation processes. The syngas in turn may be converted to hydrocarbon products, for example, fuels boiling in the middle distillate range, such as kerosene and diesel fuel, and hydrocarbon waxes by processes such as the Fischer-Tropsch Synthesis.
looosl The selectivities of catalytic partial oxidation to the desired products, carbon monoxide and hydrogen, are controlled by several factors, but one of the most important of these factors is the choice of catalyst composition. Typically, catalyst compositions have included precious metals andlor rare earths. The large volumes of expensive catalysts needed by prior art catalytic partial oxidation processes have placed these processes generally outside the limits of economic justification.
75277.01/1856.15500 [0009] For successful operation at commercial scale, the catalytic partial oxidation process must be able to achieve a high conversion of the methane feedstock at high gas hourly space velocities, and the selectivity of the process to the desired products of carbon monoxide and hydrogen must be high. Such high conversion and selectivity must be achieved without detrimental effects to the catalyst, such as the formation of carbon deposits ("coke") on the catalyst, which severely reduces catalyst performance.
looiol Accordingly, the economic evaluation for selection of a syngas process depends upon the required hydrogen to carbon monoxide molar ratio, availability and cost of hydrocarbon feedstocks and catalysts, availability and cost of oxygen and carbon dioxide, the cost of utilities and credits available for export steam and sale of excess hydrogen or carbon monoxide coproduct. This analysis is complex and highly site dependent.
Typically, petrochemical applications of syngas require a ratio of hydrogen to carbon monoxide of either 1:1 or 2:1. Commercial processes for syngas yield much higher ratios; therefore, separation technology, by-product credits and production techniques that can adjust the hydrogen to carbon monoxide ratio are important aspects of syngas production.
looiil Presently, heavy crude oil presents processing problems in refineries due to high viscosities, sulfur, nitrogen, and metal contents. Because of environmental requirements, steps are often taken at the refinery to upgrade these crude oils by reducing their viscosity and contaminants. Treatment strategies range from blending lighter crudes with heavier crudes to hydroprocessing. These strategies, though effective, are expensive because they require additional intermediates, such as hydrogen, to be produced.
Therefore, there exists a need for a method of upgrading heavy crude oil with an already existing hydrogen source.
looiol Accordingly, the economic evaluation for selection of a syngas process depends upon the required hydrogen to carbon monoxide molar ratio, availability and cost of hydrocarbon feedstocks and catalysts, availability and cost of oxygen and carbon dioxide, the cost of utilities and credits available for export steam and sale of excess hydrogen or carbon monoxide coproduct. This analysis is complex and highly site dependent.
Typically, petrochemical applications of syngas require a ratio of hydrogen to carbon monoxide of either 1:1 or 2:1. Commercial processes for syngas yield much higher ratios; therefore, separation technology, by-product credits and production techniques that can adjust the hydrogen to carbon monoxide ratio are important aspects of syngas production.
looiil Presently, heavy crude oil presents processing problems in refineries due to high viscosities, sulfur, nitrogen, and metal contents. Because of environmental requirements, steps are often taken at the refinery to upgrade these crude oils by reducing their viscosity and contaminants. Treatment strategies range from blending lighter crudes with heavier crudes to hydroprocessing. These strategies, though effective, are expensive because they require additional intermediates, such as hydrogen, to be produced.
Therefore, there exists a need for a method of upgrading heavy crude oil with an already existing hydrogen source.
75277.01l18S6.ISS00 Summary Of The Invention [o0121 The present invention relates to hydrotreating at the wellhead, using hydrogen produced from methane through the syngas process. As defined herein, the term "hydrotreating" is intended to be synonymous with the term "hydroprocessing,"
which involves the reaction of hydrocarbons at operating conditions with hydrogen, usually in the presence of a catalyst. Included within the processes intended to be encompassed by the term "hydroprocessing" are hydrocracking, aromatic hydrogenation, ring-opening, and hydrorefining, or hydrodesulfurization, hydrodenitrification, and hydrodemetalation.
As will be recognized, one common attribute of these processes, and the reactions being effected therein, is that they are all "hydrogen-consuming," and are, therefore, exothermic in nature, Although hydroprocessing may be applied to any hydrocarbon feedstock, it is particularly applicable, though less easily applicable, to heavier feedstocks such as residua, vacuum and atmospheric gas oils, coal and shale liquids, etc., since these feedstocks typically contain higher concentrations of less easily removed contaminants.
[ooi31 Additionally, the term "catalytic partial oxidation", or CPOX, when used in the context of the present syngas production methods, in addition to its usual meaning, can also refer to a net catalytic partial oxidation process, in which hydrocarbons (comprising mainly methane) and oxygen-containing gases (i.e. oxygen, oxygen-enriched air, air) are supplied as reactants and the resulting product stream is predominantly the partial oxidation products CO and HZ, rather than the complete oxidation products COz and HZO.
For example, the preferred catalysts serve in the short contact time process of the invention, which is described in more detail below, to yield a product gas mixture containing H2 and CO in a molar ratio of approximately 2:1. Although the primary reaction mechanism of the process is partial oxidation, other oxidation reactions may also ?5277.0111856.15500 occur in the reactor to a lesser or minor extent. As shown in Equation (2), the partial oxidation of methane yields H2 and CO in a molar ratio of 2:1.
100141 As explained above, syngas technology can be shifted to produce larger amounts of hydrogen by varying the H2:C0 ratio and additionally converting the remaining CO to C02 and additional H2 using the water gas shift reaction. Utilization of the hydrogen from methane allows for a use of an otherwise wasted resource. Additionally, the produced C02 from the water gas shift reaction can be injected into the formation as a COZ
flood.
100151 In a preferred embodiment of the present invention, a method for upgrading heavy crude oils at the wellhead includes producing syngas in a syngas-producing process, separating the syngas into H2 and CO streams, and injecting the H2 stream into a hydroprocessing operation located at the wellhead. A hydroprocessing operation located at the wellhead is preferably within 100 miles of the wellhead, more preferably within 10 miles of the wellhead, and most preferably within a mile of the wellhead.
[0016] In an alternate embodiment of the present invention, a method for upgrading heavy crude oils at the wellhead includes producing syngas in a syngas-producing process, separating the syngas into H2 and CO streams, running the CO stream in the presence of a water feed through a water gas shift process to produce a water gas shift product of COZ
and additional HZ, separating the water gas shift product into HZ and C02 streams, and injecting the H2 streams into a hydroprocessing process located at the wellhead.
Brief Description Of The Drawings (00171 For a more detailed understanding of the present invention, reference is now made to the accompanying figures, Figure 1 and Figure 2, which are schematic illustrations of 7527.0) / 1856.15500 first and second systems, respectively, constructed in accordance with the present invention.
Detailed Description Of The Preferred Embodiments fools] Because of the shrinking world supply of oils, oil processors are faced with the necessity of utilizing heavy feedstocks that are highly contaminated with sulfur, nitrogen and metal contents. In the processing of these feedstocks, it is very desirable to remove as much of the contaminants as early in the refining of these feedstocks as possible, so that downstream catalysts do not suffer build-up and consequent reduced activity.
Removing contaminants also makes a higher quality final product that is less corrosive and less polluting when combusted.
(0019] Referring now to Figure 1, one embodiment of the present system 100 preferably includes a syngas plant 10, a hydrogen separation unit 20, and a hydroprocessing plant 30. Methane and oxygen-containing gas stream 11 is fed into syngas plant 10 and reacts with a suitable catalyst to form a stream of hydrogen and carbon monoxide 12.
Hydrogen and carbon monoxide stream 12 is fed into hydrogen separation unit 20, where it is separated into carbon monoxide export stream 13 and hydrogen stream 14.
Hydrogen stream 14 is injected into hydroprocessing plant 30, located at the wellhead.
(0020] Referring now to Figure 2, an alternate embodiment of the present system 200 preferably includes a syngas plant 10, a first hydrogen separation unit 20, a water gas shift reactor 40, a second hydrogen separation unit 50, and a hydroprocessing plant 30.
In some embodiments, system 200 further includes a carbon dioxide compressor 60.
Methane and oxygen stream 11 is fed into syngas plant 10 and reacts with a suitable catalyst to form a stream of hydrogen and carbon monoxide 12. Hydrogen and carbon monoxide stream 12 is fed into first hydrogen separation unit 20, where it is separated 75277.0111856.15500 into carbon monoxide stream 13 and hydrogen stream 14. Carbon monoxide stream may either exit system 200 as export steam 13b or comprise carbon monoxide feed stream 13a for water gas shift reactor 40. In the latter embodiment, carbon monoxide stream 13a is recycled into water gas shift reactor with water feed 21 under water gas shift favorable conditions to produce hydrogen and carbon dioxide stream 22.
Hydrogen and carbon dioxide stream 22 is fed into second hydrogen separation unit 50, where it is separated into carbon dioxide stream 23 and hydrogen stream 24. Hydrogen streams 14 and 24 are injected into hydroprocessing plant 30, located at the wellhead.
Carbon dioxide stream 23 may either exit system 200 as export steam 23b or comprise carbon dioxide feed stream 23a for carbon dioxide compressor 60. The compressed COZ
may then be injected into the wellhead to further upgrade the heavy oil.
[0021] In some embodiments, system 200 may include a syngas plant 10, a hydrogen separation unit 20, a water gas shift reactor 40, and a hydroprocessing plant 30. In these embodiments, the hydrogen separation unit separates both the hydrogen-carbon monoxide and the hydrogen-carbon dioxide streams into a hydrogen stream and a carbon monoxide-carbon dioxide stream. A carbon dioxide removal process such as membrane separation or an amine system may be utilized to separate the carbon monoxide from the carbon dioxide.
[0022] In some embodiments, the methane from the methane and oxygen-containing stream is associated gas. Associated gas is herein defined as gas co-produced from the same oil field or same wellhead being treated. In other embodiments, the methane from the methane and oxygen-containing stream is supplied via pipeline from other sources.
Process o~fProducin~Svngas 75277.01 / 1856.15500 [0023] A feed stream comprising a hydrocarbon feedstock and an oxygen-containing gas is contacted with a suitable syngas catalysts in a reaction zone maintained at partial oxidation-promoting conditions of temperature, pressure and flowrate, effective to produce an effluent stream comprising carbon monoxide and hydrogen. Preferably a millisecond contact time reactor is employed. The hydrocarbon feedstock may be any gaseous hydrocarbon having a low boiling point, such as methane, natural gas, associated gas, or other sources of light hydrocarbons having from 1 to 5 carbon atoms.
The hydrocarbon feedstock may be a gas arising from naturally occurring reserves of methane which contain carbon dioxide. Preferably, the feed comprises at least 50% by volume methane, more preferably at least 75% by volume, and most preferably at least 80% by volume methane.
[0024] The hydrocarbon feedstock is in the gaseous phase when contacting the catalyst.
The hydrocarbon feedstock is contacted with the catalyst as a mixture with an oxygen-containing gas, preferably pure oxygen. The oxygen-containing gas may also comprise steam and/or COZ in addition to oxygen. Alternatively, the hydrocarbon feedstock is contacted with the catalyst as a mixture with a gas comprising steam and/or COz.
[0025] Preferably, the methane-containing feed and the oxygen-containing gas are mixed in such amounts to give a carbon (i.e., carbon in methane) to oxygen (i.e., atomic oxygen) ratio from about 1.25:1 to about 3.3:1, more preferably, from about 1.3:1 to about 2.2:1, and most preferably from about 1.5:1 to about 2.2:1, especially the stoichiometric ratio of 2:1.
[0026] The process is operated at atmospheric or superatmospheric pressures, the latter being preferred. The pressures may be from about I00 kPa to about 12,500 kPa, preferably from about 130 kPa to about 10,000 kPa.
75277.01/1856.15500 [0o2~] The process is preferably operated at catalyst temperatures of from about 600°C
to about 1,200°C, preferably from about 700°C to about 1,100°C. The hydrocarbon feedstock and the oxygen-containing gas are preferably pre-heated before contact with the catalyst.
[oo2s] It will be understood that the selection of a catalyst or catalyst system requires many technical and economic considerations. The process of selecting a precious metal catalyst can be broken down into components. Key catalyst properties include high activity, high selectivity, high recycle capability and filterability.
Catalyst performance is determined mainly by the precious metal component. A metal is chosen based both on its ability to complete the desired reaction and its inability to complete an unwanted reaction. Typical catalysts used in CPOX include metals from Group 6B, 7B, &
8B of the periodic table associated with promoters from Groups 1B through 8B, Groups through SA, and metals from the Lanthanide group.
[0029] Generally, catalysts are supported on a carrier material or support.
The catalyst support may be any of a variety of materials that a catalytically active material is coated on. The catalyst support preferably allows for a high degree of metal dispersion. The choice of support is largely determined by the nature of the reaction system.
The support catalyst is preferably stable under reaction and regeneration conditions.
Further, it preferably does not adversely react with solvent, reactants, or reaction products.
[0030] Suitable supports include activated carbon, alumina, silica, silica-alumina, silicon carbide, carbon black, Ti02, Zr02, CaC03, and BaS04, or stabilized forms of the aforementioned materials. Preferably, the catalytically active material is supported on either zirconia, stabilized zirconia, or alumina.
75277.01/1856.15500 [0031] It will be understood that alternative choices of support may be made without departing from the preferred embodiments of the present invention by one of ordinary skill in the art. A support preferably favorably influences any of the catalyst activity, selectivity, recycling, refining, material handling reproducibility and the like. Properties of a support include surface area, pore volume, pore size, distribution, particle size, attrition resistance, acidity, basicity, impurity levels, and the ability to promote metal-support interactions. Metal dispersion increases with surface support area.
Support porosity influences metal dispersion and distribution, metal sintering resistance, and intraparticle diffusion of reactants, products and poisons. Smaller support particle size increases catalytic activity but decreases filterability. The support preferably has desirable mechanical properties, attrition resistance and hardness. For example, an attrition resistant support allows for multiple catalyst recycling and rapid filtration.
Further, support impurities preferably are inert. Alternatively, the support may contain promoters that enhance catalyst selectivity.
[0032] The catalysts used may be prepared by any of the methods known to those skilled in the art. By way of illustration and not limitation, such methods include impregnating the catalytically active compounds or precursors onto a support, extruding one or more catalytically active compounds or precursors together with support material to prepare catalyst extrudates, and/or precipitating the catalytically active compounds or precursors onto a support. Accordingly, supported catalysts may be used in the form of powders, particles, pellets, monoliths, honeycombs, packed beds, foams, and aerogels.
(00331 The hydrocarbon feedstock and the oxygen-containing gas may be passed over the catalyst at any of a variety of space velocities. Space velocities for the process (weight hourly space velocity), stated as normal liters of gas per kilogram of catalyst per 75277.01/1856.15500 hour, are from about 20,000 to about 100,000,000 NL/kg/h, preferably from about 50,000 to about 50,000,000 NL/kg/h. It is preferred that the residence time on the catalyst is about 10 milliseconds or less. Although, for ease in comparing with other syngas production systems, space velocities at standard conditions have been used to describe the present invention, it is well recognized in the art that residence time is the inverse of space velocity and that the disclosure of high space velocities equates to low residence times on the catalyst. Under these operating conditions a flow rate of reactant gases is preferably maintained sufficient to ensure a residence time of no more than 10 milliseconds with respect to each portion of reactant gas in contact with the catalyst. The product gas mixture emerging from the reactor is harvested and directly routed into hydrogen separation unit.
Process o~SeParatin~Hydrogen from S~rrgaslWGS Product (0034] A preferred method for hydrogen separation employs pressure swing adsorption.
At a high partial pressure, solid molecular sieves can absorb a greater quantity of certain gaseous components than others and absorb some compounds more strongly than others.
For example, hydrogen is adsorbed less strongly than carbon monoxide and carbon dioxide, and the strength of adsorption of carbon monoxide and carbon dioxide increases with increasing molecular weight. As a result, at elevated pressures, hydrocarbons and other impurities are absorbed from a hydrogen-rich stream and most of the hydrogen passes through the system, leaving the impurities behind. Very high purity hydrogen can be produced this way. The hydrogen-rich stream can then be piped to a hydroprocessing unit. When the pressure on the system is reduced, the impurities adsorbed at high pressure are released from the solid adsorbent and purged.
Process oaf Upgrading Heav~0i1 75277.01/1856.15500 [0035] In some embodiments of the present invention, hydrodesulfurization is the preferred process for removing undesirable compounds. In hydrodesulfurization, oil is combined with high-purity hydrogen, vaporized, and then passed over a catalyst such as tungsten, nickel, or a mixture of cobalt and molybdenum oxides supported on a carrier material such as alumina. Hydrodesulfurization is performed according to methods known to one of ordinary skill in the art. A general description of major considerations involved in performing hydrodesulfurization, and more generally hydrorefining, is given by W. S. Bland and R. L. Davidson, Petroleum Processing Handbook, Chapter 3 (1967).
Operating temperatures are usually between 260° C and 425° C
(500° F and 800° F) at pressures of 14 to 70 kilograms per square centimeter (200 to 1,000 pounds per square inch). Operating conditions are set to facilitate the desired level of sulfur removal without promoting any change to the other properties of the oil.
[00361 The sulfur in the oil is converted to hydrogen sulfide, which is removed from the circulating hydrogen stream by absorption in a solution such as diethanolamine. The solution can then be heated to remove the sulfide and reused. The hydrogen sulfide recovered is useful for manufacturing elemental sulfur of high purity.
[00371 Hydrodenitrification, a common process for removing nitrogen compounds and hydrodemetalation, a common process for removing metal contents, generally follow the same requirements as hydrodesulfurization.
CO~ Flooding [oo3s1 According to some embodiments of the present invention, the CO product stream is fed into a water gas shift plant in the presence of water and operated at water gas shift favorable conditions. After the CO product has gone through the WGS, there will be C02 remaining. This COZ can be used to additionally upgrade the heavy oil; it is known 75277.0!/1856.15500 to inject carbon dioxide, either alone or in conjunction with natural gas, either at high pressure or containing sufficient petroleum gases in the vapor phase to perform tertiary oil recovery. The carbon dioxide can greatly improve tertiary recovery, but the effort is not economical unless very large quantities of carbon dioxide are available at a reasonable price. Conventionally, most of the successful projects of this type depend on tapping and transporting (by pipeline) carbon dioxide from underground reservoirs.
However, because C02 is a biproduct of our desired method to maximize hydrogen content, the cost is essentially the cost of separation of the hydrogen from the C02.
100391 While the preferred embodiments of the invention have been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit and teachings of the invention. The embodiments described herein are exemplary only, and are not intended to be limiting. For example, while CPOX
is preferably employed to produce syngas, any syngas-producing technology such as autothermal reforming (ATR) and steam reforming could be utilized. Many variations and modifications of the invention disclosed herein are possible and are within the scope of the invention. Accordingly, the scope of protection is not limited by the description set out above, but is only limited by the claims which follow, that scope including all equivalents of the subject matter of the claims. The disclosures of all patents, patent applications, and publications cited herein are incorporated by reference.
75277.01/1856.15500
which involves the reaction of hydrocarbons at operating conditions with hydrogen, usually in the presence of a catalyst. Included within the processes intended to be encompassed by the term "hydroprocessing" are hydrocracking, aromatic hydrogenation, ring-opening, and hydrorefining, or hydrodesulfurization, hydrodenitrification, and hydrodemetalation.
As will be recognized, one common attribute of these processes, and the reactions being effected therein, is that they are all "hydrogen-consuming," and are, therefore, exothermic in nature, Although hydroprocessing may be applied to any hydrocarbon feedstock, it is particularly applicable, though less easily applicable, to heavier feedstocks such as residua, vacuum and atmospheric gas oils, coal and shale liquids, etc., since these feedstocks typically contain higher concentrations of less easily removed contaminants.
[ooi31 Additionally, the term "catalytic partial oxidation", or CPOX, when used in the context of the present syngas production methods, in addition to its usual meaning, can also refer to a net catalytic partial oxidation process, in which hydrocarbons (comprising mainly methane) and oxygen-containing gases (i.e. oxygen, oxygen-enriched air, air) are supplied as reactants and the resulting product stream is predominantly the partial oxidation products CO and HZ, rather than the complete oxidation products COz and HZO.
For example, the preferred catalysts serve in the short contact time process of the invention, which is described in more detail below, to yield a product gas mixture containing H2 and CO in a molar ratio of approximately 2:1. Although the primary reaction mechanism of the process is partial oxidation, other oxidation reactions may also ?5277.0111856.15500 occur in the reactor to a lesser or minor extent. As shown in Equation (2), the partial oxidation of methane yields H2 and CO in a molar ratio of 2:1.
100141 As explained above, syngas technology can be shifted to produce larger amounts of hydrogen by varying the H2:C0 ratio and additionally converting the remaining CO to C02 and additional H2 using the water gas shift reaction. Utilization of the hydrogen from methane allows for a use of an otherwise wasted resource. Additionally, the produced C02 from the water gas shift reaction can be injected into the formation as a COZ
flood.
100151 In a preferred embodiment of the present invention, a method for upgrading heavy crude oils at the wellhead includes producing syngas in a syngas-producing process, separating the syngas into H2 and CO streams, and injecting the H2 stream into a hydroprocessing operation located at the wellhead. A hydroprocessing operation located at the wellhead is preferably within 100 miles of the wellhead, more preferably within 10 miles of the wellhead, and most preferably within a mile of the wellhead.
[0016] In an alternate embodiment of the present invention, a method for upgrading heavy crude oils at the wellhead includes producing syngas in a syngas-producing process, separating the syngas into H2 and CO streams, running the CO stream in the presence of a water feed through a water gas shift process to produce a water gas shift product of COZ
and additional HZ, separating the water gas shift product into HZ and C02 streams, and injecting the H2 streams into a hydroprocessing process located at the wellhead.
Brief Description Of The Drawings (00171 For a more detailed understanding of the present invention, reference is now made to the accompanying figures, Figure 1 and Figure 2, which are schematic illustrations of 7527.0) / 1856.15500 first and second systems, respectively, constructed in accordance with the present invention.
Detailed Description Of The Preferred Embodiments fools] Because of the shrinking world supply of oils, oil processors are faced with the necessity of utilizing heavy feedstocks that are highly contaminated with sulfur, nitrogen and metal contents. In the processing of these feedstocks, it is very desirable to remove as much of the contaminants as early in the refining of these feedstocks as possible, so that downstream catalysts do not suffer build-up and consequent reduced activity.
Removing contaminants also makes a higher quality final product that is less corrosive and less polluting when combusted.
(0019] Referring now to Figure 1, one embodiment of the present system 100 preferably includes a syngas plant 10, a hydrogen separation unit 20, and a hydroprocessing plant 30. Methane and oxygen-containing gas stream 11 is fed into syngas plant 10 and reacts with a suitable catalyst to form a stream of hydrogen and carbon monoxide 12.
Hydrogen and carbon monoxide stream 12 is fed into hydrogen separation unit 20, where it is separated into carbon monoxide export stream 13 and hydrogen stream 14.
Hydrogen stream 14 is injected into hydroprocessing plant 30, located at the wellhead.
(0020] Referring now to Figure 2, an alternate embodiment of the present system 200 preferably includes a syngas plant 10, a first hydrogen separation unit 20, a water gas shift reactor 40, a second hydrogen separation unit 50, and a hydroprocessing plant 30.
In some embodiments, system 200 further includes a carbon dioxide compressor 60.
Methane and oxygen stream 11 is fed into syngas plant 10 and reacts with a suitable catalyst to form a stream of hydrogen and carbon monoxide 12. Hydrogen and carbon monoxide stream 12 is fed into first hydrogen separation unit 20, where it is separated 75277.0111856.15500 into carbon monoxide stream 13 and hydrogen stream 14. Carbon monoxide stream may either exit system 200 as export steam 13b or comprise carbon monoxide feed stream 13a for water gas shift reactor 40. In the latter embodiment, carbon monoxide stream 13a is recycled into water gas shift reactor with water feed 21 under water gas shift favorable conditions to produce hydrogen and carbon dioxide stream 22.
Hydrogen and carbon dioxide stream 22 is fed into second hydrogen separation unit 50, where it is separated into carbon dioxide stream 23 and hydrogen stream 24. Hydrogen streams 14 and 24 are injected into hydroprocessing plant 30, located at the wellhead.
Carbon dioxide stream 23 may either exit system 200 as export steam 23b or comprise carbon dioxide feed stream 23a for carbon dioxide compressor 60. The compressed COZ
may then be injected into the wellhead to further upgrade the heavy oil.
[0021] In some embodiments, system 200 may include a syngas plant 10, a hydrogen separation unit 20, a water gas shift reactor 40, and a hydroprocessing plant 30. In these embodiments, the hydrogen separation unit separates both the hydrogen-carbon monoxide and the hydrogen-carbon dioxide streams into a hydrogen stream and a carbon monoxide-carbon dioxide stream. A carbon dioxide removal process such as membrane separation or an amine system may be utilized to separate the carbon monoxide from the carbon dioxide.
[0022] In some embodiments, the methane from the methane and oxygen-containing stream is associated gas. Associated gas is herein defined as gas co-produced from the same oil field or same wellhead being treated. In other embodiments, the methane from the methane and oxygen-containing stream is supplied via pipeline from other sources.
Process o~fProducin~Svngas 75277.01 / 1856.15500 [0023] A feed stream comprising a hydrocarbon feedstock and an oxygen-containing gas is contacted with a suitable syngas catalysts in a reaction zone maintained at partial oxidation-promoting conditions of temperature, pressure and flowrate, effective to produce an effluent stream comprising carbon monoxide and hydrogen. Preferably a millisecond contact time reactor is employed. The hydrocarbon feedstock may be any gaseous hydrocarbon having a low boiling point, such as methane, natural gas, associated gas, or other sources of light hydrocarbons having from 1 to 5 carbon atoms.
The hydrocarbon feedstock may be a gas arising from naturally occurring reserves of methane which contain carbon dioxide. Preferably, the feed comprises at least 50% by volume methane, more preferably at least 75% by volume, and most preferably at least 80% by volume methane.
[0024] The hydrocarbon feedstock is in the gaseous phase when contacting the catalyst.
The hydrocarbon feedstock is contacted with the catalyst as a mixture with an oxygen-containing gas, preferably pure oxygen. The oxygen-containing gas may also comprise steam and/or COZ in addition to oxygen. Alternatively, the hydrocarbon feedstock is contacted with the catalyst as a mixture with a gas comprising steam and/or COz.
[0025] Preferably, the methane-containing feed and the oxygen-containing gas are mixed in such amounts to give a carbon (i.e., carbon in methane) to oxygen (i.e., atomic oxygen) ratio from about 1.25:1 to about 3.3:1, more preferably, from about 1.3:1 to about 2.2:1, and most preferably from about 1.5:1 to about 2.2:1, especially the stoichiometric ratio of 2:1.
[0026] The process is operated at atmospheric or superatmospheric pressures, the latter being preferred. The pressures may be from about I00 kPa to about 12,500 kPa, preferably from about 130 kPa to about 10,000 kPa.
75277.01/1856.15500 [0o2~] The process is preferably operated at catalyst temperatures of from about 600°C
to about 1,200°C, preferably from about 700°C to about 1,100°C. The hydrocarbon feedstock and the oxygen-containing gas are preferably pre-heated before contact with the catalyst.
[oo2s] It will be understood that the selection of a catalyst or catalyst system requires many technical and economic considerations. The process of selecting a precious metal catalyst can be broken down into components. Key catalyst properties include high activity, high selectivity, high recycle capability and filterability.
Catalyst performance is determined mainly by the precious metal component. A metal is chosen based both on its ability to complete the desired reaction and its inability to complete an unwanted reaction. Typical catalysts used in CPOX include metals from Group 6B, 7B, &
8B of the periodic table associated with promoters from Groups 1B through 8B, Groups through SA, and metals from the Lanthanide group.
[0029] Generally, catalysts are supported on a carrier material or support.
The catalyst support may be any of a variety of materials that a catalytically active material is coated on. The catalyst support preferably allows for a high degree of metal dispersion. The choice of support is largely determined by the nature of the reaction system.
The support catalyst is preferably stable under reaction and regeneration conditions.
Further, it preferably does not adversely react with solvent, reactants, or reaction products.
[0030] Suitable supports include activated carbon, alumina, silica, silica-alumina, silicon carbide, carbon black, Ti02, Zr02, CaC03, and BaS04, or stabilized forms of the aforementioned materials. Preferably, the catalytically active material is supported on either zirconia, stabilized zirconia, or alumina.
75277.01/1856.15500 [0031] It will be understood that alternative choices of support may be made without departing from the preferred embodiments of the present invention by one of ordinary skill in the art. A support preferably favorably influences any of the catalyst activity, selectivity, recycling, refining, material handling reproducibility and the like. Properties of a support include surface area, pore volume, pore size, distribution, particle size, attrition resistance, acidity, basicity, impurity levels, and the ability to promote metal-support interactions. Metal dispersion increases with surface support area.
Support porosity influences metal dispersion and distribution, metal sintering resistance, and intraparticle diffusion of reactants, products and poisons. Smaller support particle size increases catalytic activity but decreases filterability. The support preferably has desirable mechanical properties, attrition resistance and hardness. For example, an attrition resistant support allows for multiple catalyst recycling and rapid filtration.
Further, support impurities preferably are inert. Alternatively, the support may contain promoters that enhance catalyst selectivity.
[0032] The catalysts used may be prepared by any of the methods known to those skilled in the art. By way of illustration and not limitation, such methods include impregnating the catalytically active compounds or precursors onto a support, extruding one or more catalytically active compounds or precursors together with support material to prepare catalyst extrudates, and/or precipitating the catalytically active compounds or precursors onto a support. Accordingly, supported catalysts may be used in the form of powders, particles, pellets, monoliths, honeycombs, packed beds, foams, and aerogels.
(00331 The hydrocarbon feedstock and the oxygen-containing gas may be passed over the catalyst at any of a variety of space velocities. Space velocities for the process (weight hourly space velocity), stated as normal liters of gas per kilogram of catalyst per 75277.01/1856.15500 hour, are from about 20,000 to about 100,000,000 NL/kg/h, preferably from about 50,000 to about 50,000,000 NL/kg/h. It is preferred that the residence time on the catalyst is about 10 milliseconds or less. Although, for ease in comparing with other syngas production systems, space velocities at standard conditions have been used to describe the present invention, it is well recognized in the art that residence time is the inverse of space velocity and that the disclosure of high space velocities equates to low residence times on the catalyst. Under these operating conditions a flow rate of reactant gases is preferably maintained sufficient to ensure a residence time of no more than 10 milliseconds with respect to each portion of reactant gas in contact with the catalyst. The product gas mixture emerging from the reactor is harvested and directly routed into hydrogen separation unit.
Process o~SeParatin~Hydrogen from S~rrgaslWGS Product (0034] A preferred method for hydrogen separation employs pressure swing adsorption.
At a high partial pressure, solid molecular sieves can absorb a greater quantity of certain gaseous components than others and absorb some compounds more strongly than others.
For example, hydrogen is adsorbed less strongly than carbon monoxide and carbon dioxide, and the strength of adsorption of carbon monoxide and carbon dioxide increases with increasing molecular weight. As a result, at elevated pressures, hydrocarbons and other impurities are absorbed from a hydrogen-rich stream and most of the hydrogen passes through the system, leaving the impurities behind. Very high purity hydrogen can be produced this way. The hydrogen-rich stream can then be piped to a hydroprocessing unit. When the pressure on the system is reduced, the impurities adsorbed at high pressure are released from the solid adsorbent and purged.
Process oaf Upgrading Heav~0i1 75277.01/1856.15500 [0035] In some embodiments of the present invention, hydrodesulfurization is the preferred process for removing undesirable compounds. In hydrodesulfurization, oil is combined with high-purity hydrogen, vaporized, and then passed over a catalyst such as tungsten, nickel, or a mixture of cobalt and molybdenum oxides supported on a carrier material such as alumina. Hydrodesulfurization is performed according to methods known to one of ordinary skill in the art. A general description of major considerations involved in performing hydrodesulfurization, and more generally hydrorefining, is given by W. S. Bland and R. L. Davidson, Petroleum Processing Handbook, Chapter 3 (1967).
Operating temperatures are usually between 260° C and 425° C
(500° F and 800° F) at pressures of 14 to 70 kilograms per square centimeter (200 to 1,000 pounds per square inch). Operating conditions are set to facilitate the desired level of sulfur removal without promoting any change to the other properties of the oil.
[00361 The sulfur in the oil is converted to hydrogen sulfide, which is removed from the circulating hydrogen stream by absorption in a solution such as diethanolamine. The solution can then be heated to remove the sulfide and reused. The hydrogen sulfide recovered is useful for manufacturing elemental sulfur of high purity.
[00371 Hydrodenitrification, a common process for removing nitrogen compounds and hydrodemetalation, a common process for removing metal contents, generally follow the same requirements as hydrodesulfurization.
CO~ Flooding [oo3s1 According to some embodiments of the present invention, the CO product stream is fed into a water gas shift plant in the presence of water and operated at water gas shift favorable conditions. After the CO product has gone through the WGS, there will be C02 remaining. This COZ can be used to additionally upgrade the heavy oil; it is known 75277.0!/1856.15500 to inject carbon dioxide, either alone or in conjunction with natural gas, either at high pressure or containing sufficient petroleum gases in the vapor phase to perform tertiary oil recovery. The carbon dioxide can greatly improve tertiary recovery, but the effort is not economical unless very large quantities of carbon dioxide are available at a reasonable price. Conventionally, most of the successful projects of this type depend on tapping and transporting (by pipeline) carbon dioxide from underground reservoirs.
However, because C02 is a biproduct of our desired method to maximize hydrogen content, the cost is essentially the cost of separation of the hydrogen from the C02.
100391 While the preferred embodiments of the invention have been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit and teachings of the invention. The embodiments described herein are exemplary only, and are not intended to be limiting. For example, while CPOX
is preferably employed to produce syngas, any syngas-producing technology such as autothermal reforming (ATR) and steam reforming could be utilized. Many variations and modifications of the invention disclosed herein are possible and are within the scope of the invention. Accordingly, the scope of protection is not limited by the description set out above, but is only limited by the claims which follow, that scope including all equivalents of the subject matter of the claims. The disclosures of all patents, patent applications, and publications cited herein are incorporated by reference.
75277.01/1856.15500
Claims (26)
- What is claimed is:
A method for upgrading heavy crude oils at the wellhead comprising:
producing syngas in a syngas-producing process;
separating the syngas into H2 and CO streams; and injecting the H2 stream into a hydroprocessing operation located at the wellhead. - 2. The method according to claim 1 wherein the syngas-producing operation is of a type selected from the group consisting of CPOX (catalytic partial oxidation), ATR
(autothermal reforming), and steam reforming processes. - 3. The method according to claim 2 wherein the syngas-producing process is CPOX.
- 4. The method according to claim 3 wherein a methane-containing gas and oxygen-containing gas feed is supplied to the CPOX process.
- 5. The method according to claim 4 wherein the methane-containing gas is associated gas co-produced from the oil well.
- 6. The method according to claim 4 wherein the methane-containing gas is supplied via pipeline from other sources.
- 7. The method according to claim 1 wherein a hydrogen separation process separates the syngas into H2 and CO streams and optionally co-existing nitrogen streams.
- 8. The method according to claim 7 wherein the hydrogen separation process employs membrane separation technology.
- 9. The method according to claim 1 wherein the hydroprocessing operation is of a type selected from the group consisting of hydrogenation, hydrocracking, hydrodenitrogenation, hydrodemetalization, and hydrodesulfurization processes.
- 10. The method according to claim 9 wherein the hydroprocessing operation is hydrodesulfurization.
- 11. A method for upgrading heavy crude oils at the wellhead comprising:
producing syngas in a syngas-producing process;
separating the syngas into H2 and CO streams;
running the CO stream in the presence of a water feed through a water gas shift process to produce a Water gas shift product comprising CO2 and additional H2;
separating the water gas shift product into H2 and CO2 streams; and injecting the H2 streams into a hydroprocessing process located at the wellhead. - 12. The method according to claim 11 wherein the syngas-producing process is of a type selected from the group consisting of CPOX (catalytic partial oxidation), ATR
(autothermal reforming), and steam reforming processes. - 13. The method according to claim 12 wherein the syngas-producing process is CPOX.
- 14. The method according to claim 13 wherein a methane-containing gas and oxygen-containing gas feed is supplied to the CPOX process.
- 15. The process according to claim 14 wherein the methane-containing gas is associated gas co-produced from the oil well.
- 16. The process according to claim 14 wherein the methane-containing gas is supplied via pipeline from other sources.
- 17. The method according to claim 11 wherein a hydrogen separation process separates the syngas into H2 and CO streams and optionally co-existing nitrogen streams.
- 18. The method according to claim 17 wherein the hydrogen separation process employs membrane separation technology.
- 19. The method according to claim 11 wherein the hydroprocessing process is of a type selected from the group consisting of hydrogenation, hydrocracking, hydrodenitrogenation, hydrodemetalization, and hydrodesulfurization processes.
- 20. The method according to claim 19 wherein the hydroprocessing process comprises a hydrodesulfurization process.
- 21. The method according to claim 11 further comprising feeding the product into a carbon dioxide compressor.
- 22. The method according to claim 21 wherein the compressed CO2 is injected into the formation via injection wells to facilitate movement of the crude oil to the producing wellhead.
- 23. A method for upgrading heavy crude oils at the wellhead comprising:
producing syngas in a syngas-producing process running at CPOX favorable conditions with a methane-containing gas and oxygen-containing gas feed;
separating the syngas into H2 and CO streams; and injecting the H2 stream into a hydroprocessing process located at the wellhead. - 24. A method for upgrading heavy crude oils at the wellhead comprising:
producing syngas in a syngas-producing process running at CPOX favorable conditions with a methane-containing gas and oxygen-containing gas feed;
separating the syngas into H2 and CO streams;
running the CO stream in the presence of a water feed through a water gas shift process to produce a water gas shift product comprising CO2 and additional H2;
separating the water gas shift product into H2 and CO2 streams; and injecting the H2 streams into a hydroprocessing process located at the wellhead. - 25. A system for upgrading heavy crude oils at the wellhead comprising:
providing a syngas-producing process running at CPOX favorable conditions with a methane-containing gas and oxygen-containing gas feed to produce syngas;
providing a hydrogen separation process, wherein the syngas is separated into and CO streams; and providing a hydroprocessing process located at the wellhead, wherein the H2 stream is injected. - 26. A system for upgrading heavy crude oils at the wellhead comprising:
providing a syngas-producing process running at CPOX favorable conditions with a methane-containing gas and oxygen-containing gas feed to produce syngas;
providing a first hydrogen separation process, wherein the syngas is separated into H2 and CO streams;
providing a water gas shift process with a water feed and a recycle means for running the CO stream to the water gas shift process, wherein the water gas shift process produces a water gas shift product comprising additional H2 and CO2;
providing a second hydrogen separation process, wherein the water gas shift product is separated into additional H2 and CO2 streams; and providing a hydroprocessing process located at the wellhead, wherein the H2 streams are injected.
Applications Claiming Priority (4)
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US32967301P | 2001-10-15 | 2001-10-15 | |
US60/329,673 | 2001-10-15 | ||
US10/153,144 US20030070808A1 (en) | 2001-10-15 | 2002-05-21 | Use of syngas for the upgrading of heavy crude at the wellhead |
US10/153,144 | 2002-05-21 |
Publications (1)
Publication Number | Publication Date |
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CA2407102A1 true CA2407102A1 (en) | 2003-04-15 |
Family
ID=26850215
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CA002407102A Abandoned CA2407102A1 (en) | 2001-10-15 | 2002-10-09 | Use of syngas for the upgrading of heavy crude at the wellhead |
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US (1) | US20030070808A1 (en) |
CA (1) | CA2407102A1 (en) |
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