CN101983227B - 降低原油酸度的方法 - Google Patents
降低原油酸度的方法 Download PDFInfo
- Publication number
- CN101983227B CN101983227B CN2008801257542A CN200880125754A CN101983227B CN 101983227 B CN101983227 B CN 101983227B CN 2008801257542 A CN2008801257542 A CN 2008801257542A CN 200880125754 A CN200880125754 A CN 200880125754A CN 101983227 B CN101983227 B CN 101983227B
- Authority
- CN
- China
- Prior art keywords
- crude oil
- water
- sour
- oil
- mixture
- 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 - Fee Related
Links
- 239000010779 crude oil Substances 0.000 title claims abstract description 206
- 238000000034 method Methods 0.000 title claims abstract description 99
- 230000008569 process Effects 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 181
- 238000012545 processing Methods 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims description 71
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 239000003921 oil Substances 0.000 claims description 43
- 239000002253 acid Substances 0.000 claims description 38
- 238000011084 recovery Methods 0.000 claims description 31
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 21
- 239000005864 Sulphur Substances 0.000 claims description 20
- 150000002430 hydrocarbons Chemical class 0.000 claims description 19
- 239000004215 Carbon black (E152) Substances 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 229930195733 hydrocarbon Natural products 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims description 17
- 150000004706 metal oxides Chemical class 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- 230000003750 conditioning effect Effects 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 230000006837 decompression Effects 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 10
- 229910001385 heavy metal Inorganic materials 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003208 petroleum Substances 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 5
- 238000011144 upstream manufacturing Methods 0.000 claims description 5
- 230000005540 biological transmission Effects 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 230000036571 hydration Effects 0.000 claims description 3
- 238000006703 hydration reaction Methods 0.000 claims description 3
- 230000002045 lasting effect Effects 0.000 claims 2
- 238000012423 maintenance Methods 0.000 claims 1
- 239000008400 supply water Substances 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 abstract description 16
- -1 organic acid compounds Chemical class 0.000 abstract description 15
- 238000005260 corrosion Methods 0.000 abstract description 13
- 230000007797 corrosion Effects 0.000 abstract description 13
- 150000007524 organic acids Chemical class 0.000 abstract description 3
- 125000005608 naphthenic acid group Chemical class 0.000 abstract description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 239000000047 product Substances 0.000 description 16
- 239000012535 impurity Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 150000001735 carboxylic acids Chemical class 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000004939 coking Methods 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 238000009530 blood pressure measurement Methods 0.000 description 3
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000006114 decarboxylation reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 150000001282 organosilanes Chemical class 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 239000002569 water oil cream Substances 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009910 autonomic response Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/008—Processes carried out under supercritical conditions
-
- 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
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
-
- 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
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
- C10G31/08—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by treating with water
-
- 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
- C10G45/24—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 hydrogen-generating compounds
- C10G45/26—Steam or water
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/32—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions in the presence of hydrogen-generating compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP 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
-
- 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
- C10G2300/1033—Oil well production fluids
-
- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
-
- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
- C10G2300/206—Asphaltenes
-
- 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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4081—Recycling aspects
-
- 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
- C10G2300/80—Additives
- C10G2300/805—Water
Abstract
降低酸性原油的酸度以防止在原油加工,包括经由管路、油船和油罐车传输的过程中的腐蚀的方法。使具有相当大量有机酸,特别是环烷酸化合物的原油与超临界水和催化剂接触以便脱酸。该处理过的原油产物具有比原始原油低的有机酸化合物量。
Description
相关申请
本专利申请要求2008年11月28日提交的美国临时专利申请序号No.60/990,670;60/990,641;60/990,662;60/990,648;和60/990,658的优先权,它们都全文经此引用并入本文。
发明领域
本发明涉及通过在金属氧化物催化剂存在下用超临界水处理来降低高酸原油的酸度的方法。本发明更特别涉及高酸原油的脱酸法以降低运输、储存和通过传统精炼法加工的过程中的金属表面腐蚀趋势。本发明还实现:粘度降低、密度降低(如减粘裂化(vis-breaking))、除硫、除氮和除金属。有利地,将原油改质和改进API比重。
相关技术描述
对石油原料的日益提高的要求和可得原油的日益降低的品质要求将要通过目前可用的精炼工艺加工的低品质原油改质。特别地,必须加工高酸原油以应对快速提高的对烃源的要求。
由于其强腐蚀趋势,高酸原油在运输、储存和精炼过程中产生许多问题。金属表面的腐蚀要求频繁更换被腐蚀的部件或使用昂贵的耐火金属。通过腐蚀析出的金属化合物也在管道中造成严重的堵塞问题。
代表性的有机酸化合物已知是在具有环戊烷的长链烷烃的烃分子上具有羧酸官能团的环烷酸。但是,酸性原油中所含的酸性化合物的详细分析表明酸性化合物的化学组成和结构的宽泛变化。它们大多数具有羧酸官能团。
因此,含有大量有机酸的原油由于难以加工而具有低经济价值。
通过用氢氧化钾滴定以评估以滴定1克原油所需的KOH毫克数计的总酸值(“TAN”),测量原油的酸度。TAN超过0.3的原油通常被视为酸性原油。这一定义会随国家而变,或可以为最终产品规定更低的TAN。本发明针对原油中的酸,因此在要减少酸时通常有用。
水的临界点为374℃和22.1MPa。在这些条件之上,其变成超临界,且液体和气体之间的相界消失。超临界水具有与亚临界水不同的各种不寻常的性质。超临界水具有对有机化合物的极高溶解度和与气体的无限混溶性。
已经提出许多方法将酸性石油脱酸。添加碱性化合物以中和石油的酸度。也使用具有足以捕集或中和原油中的酸性化合物的碱度的聚合化合物来降低原油的酸度。环烷酸化合物——其是原油中存在的代表性酸性化合物——也可以通过在存在或不存在催化剂的情况下与醇化合物反应来转化成酯化合物。萃取分离法已知用于从石油中分离有机酸性化合物,包括环烷酸化合物。尝试使用各种溶剂以分离有机酸性化合物,如盐和含有浓缩环烷酸化合物的水-油乳状液。也已经评估了催化法,通常使用温和反应条件。类似地,已知方法倾向于仅处理原油物流的某馏分而非全原油物流。为了防止金属表面腐蚀,可以在接触酸性原油之前使用缓蚀剂钝化金属表面。有机聚硫化物或亚磷酸盐/酯或磷酸被提出具有良好性能以在金属表面上形成保护膜。
需要可以在现场生产设施处或在井口附近将酸性原油脱酸的方法。提出处理全原油物流而非仅处理原油进料的某馏分的方法是有利的。
美国专利No.6,325,921 B1(Andersen)公开了通过在固体催化剂存在下用超临界水加工原油的特定馏分来除去重质石油原料中所含的金属杂质的方法。Andersen教导了分馏以制造常压渣油,其随后用氧化锆催化剂处理。通常在炼油厂内而非在产地进行分馏。因此,Andersen要将腐蚀性酸性原油运至炼油地。此外,Andersen教导了分馏塔暴露在酸性原油中,由此造成昂贵的精炼法。最后,该Andersen方法受困于淤渣生成和成焦,这会迅速堵塞管道。
美国专利No.4,840,725(Paspek等人)公开了在不存在催化剂的情况下用超临界条件的水将高沸点烃转化至低沸点石油的方法。Paspek没有教导酸性化合物的脱除,Paspek教导的方法也未除去这类化合物。此外,Paspek没有教导在现场生产设施处处理原油,因此Paspek中指定的原油必须运输,这在该原油是酸性时会造成腐蚀。最后,Paspek的方法受困于成焦,尽管生成量低于传统方法。
美国专利No.4,818,370(Gregoli等人)公开了在盐水存在下用超临界水将重质烃,如焦油和沥青转化成轻质烃的方法。
如相关技术描述部分中所述,有许多与酸性原油的简单脱酸相关的问题。代表性的有机酸性酸是在烃上具有羧酸官能团的环烷酸化合物。通过用碱性化学品中和、经由与醇的反应转化成酯和使用极性溶剂萃取分离,可以降低或除去这类酸性化合物的酸度。在存在或不存在氢的情况下用催化剂处理这类酸性官能团也可有效除去羧酸的强酸度。但是,现有技术中公开的高酸原油的脱酸法需要原始原油中不存在的特殊化学品或不能在现场生产设施处进行的复杂方法。另外,现有技术中公开的方法会降低原油的品质或不会显著改进或提升原油的其它品质,如粘度、密度以及硫和金属含量。
添加碱性化合物以中和石油的酸度。也使用具有足以捕集或中和环烷酸的碱度的聚合化合物来降低原油的酸度。但是,这些方法要求使用不容易从脱酸产物中回收的昂贵的中和剂。
环烷酸化合物——其是原油中存在的代表性酸性化合物——也可以通过在存在或不存在催化剂的情况下与醇化合物的已知反应来转化成酯化合物。该技术具有消耗醇以及与经由水解转化成羧酸化合物相关的该酯化合物的不稳定性的缺点。
萃取分离法也已知从石油中分离环烷酸化合物。已经使用各种溶剂来分离环烷酸化合物或其衍生物,如盐和含有浓缩环烷酸化合物的水-油乳状液。但溶剂萃取需要大量不容易再循环的溶剂,因为溶剂对有机酸性化合物具有高亲合力。也充分除去环烷化合物,包括有价值的烃部分以及溶解到该溶剂中的其它有价值的烃组分。
为了防止金属表面腐蚀,提出缓蚀剂以钝化金属表面。有机聚硫化物或亚磷酸盐/酯或磷酸被提出提供良好性能以在金属表面上形成保护膜。该技术受困于注射和再注射抑制剂以保持充足的保护膜厚度的花费。也必须使接触该酸性原油的各金属制品与可操作量的缓蚀剂接触以便被处理,而非仅从原油中除去有问题的官能团。
这些和其它技术在本领域中已知用于将酸性原油脱酸或用于防止设备被酸性原油腐蚀。脱酸过程一般在炼油厂进行。在炼油厂,氢往往易得。由于许多脱酸法需要氢,这要求这类方法在炼油厂而非在产地进行。但是,这在管道和运输车辆以及在生产井和炼油厂之间的所有接触设备中造成腐蚀问题。在生产设施现场除去酸性官能团是有利的。脱酸的许多已知应用包括使用氢。由于氢在产地通常不可得,在产地在不存在外加氢的情况下脱酸是有利的。
已知技术也通常处理烃物流的馏分。尽管这可降低要进行酸度处理的体积,但其通过容易腐蚀的分离处理(即分馏塔)造成额外资本费用。处理全原油有助于将资本成本、加工成本和腐蚀暴露降至尽量低。在运输和通过传统精炼法加工之前将该烃物流脱酸是有利的。
因此,有许多与酸性原油的脱酸相关的缺点。酸度是原油的最有挑战性的性质之一。石油的脱酸需要昂贵的中和化学品、使用溶剂并增加石油中的杂质。此外,现有技术中公开的大多数方法不以任何其它方式改进原油并通常造成有价值的添加剂或原油的永久损失。中和然后溶剂萃取造成有价值的石油的损失。单独的原油或原油馏分在升高的温度下的催化处理容易在催化剂表面上形成焦,这极快降低催化活性。
发明概述
因此,现场生产设施需要能用有效和简单的方法将高酸原油脱酸以降低在酸性原油的运输和加工过程中常遇到的与该原油接触的金属表面的腐蚀。
根据本发明,使用超临界水和金属氧化物催化剂降低酸性原油的酸度,特别是通过在金属氧化物催化剂存在下的脱羧基作用。
本文所述的方法降低酸性原油的酸度以防止原油加工(包括:经由管路、油船和油罐车转移)过程中的腐蚀。使具有显著量有机酸,特别是环烷酸化合物的原油与超临界水和金属氧化物催化剂接触以便脱酸。该处理过的原油产物具有比原始酸性原油更低的有机酸化合物量。
相应地,本发明的一个实施方案包括使高酸原油与超临界水在金属氧化物催化剂存在下接触以分解该高酸原油中所含的有机酸性化合物。另外,也除去酸性原油中所含的杂质,如硫、氮和金属化合物。此外,本发明使API比重改进至更轻和中间范围馏出物。更进一步,也降低该处理过的原油的粘度。
本发明的一个实施方案是降低酸性原油的酸度的方法,包括获得TAN为至少大约0.3的酸性原油的石油储层供应源。酸性油通常被视为TAN等于或高于0.3的油。值得注意地,本发明降低TAN不高于0.3的油的酸度,只要脱除仍被视为合意。有利地,本发明的方法可以在现场生产设施处在石油储层附近实施。
该实施方案包括以大约10∶1至大约1∶50,或更优选10∶1至大约1∶10的重量比(在室温下测得)混合酸性原油与水,以形成原油/水混合物。可以将该原油/水混合物加热至大约10℃至大约150℃的原油/水温度以形成可泵送原油/水混合物。随后将该可泵送原油/水混合物泵抽至至少大约22.1MPa的压力以形成加压的原油/水混合物。该可泵送原油/水混合物的目标压力等于或高于水的临界压力。优选在加热区中将该加压的原油/水混合物加热至大约150℃至大约400℃或更优选150℃至350℃的加压温度。该加压的原油/水混合物随后在反应区中与金属氧化物催化剂接触,其中该反应区包括具有内部部分的主反应器,并加热至大约374℃至大约600℃的反应温度范围。在一个优选实施方案中,在加热区中进行加热,然后在反应区中加热,但这些区域可以合并成一个元件。该反应区中的温度通常等于或高于超临界水的温度,其中400℃-500℃的范围是优选的。压力保持在等于或高于至少大约22.1MPa,这是水的临界压力。使该加压的原油/水混合物与催化剂接触可操作为产生与酸性原油的TAN相比具有显著降低的TAN的处理过的原油的反应期。根据最终产物的TAN规格,这一停留时间可以为数秒或数分钟。在一个优选实施方案中,该停留时间不超过大约90分钟。
在压力下和在高温下从该反应区中取出处理过的原油。该处理过的原油可以在冷却器中冷却并使压力降低或施以减压以产生减压的处理过的混合物。可以使用本领域已知的任何压力调节设备。本发明中可用的压力调节设备可以是本领域已知的设备,其中阀是一种实施方案,背压调节器是另一示例性设备。在一个实施方案中,并联使用两个或更多个压力调节设备。这有利地在其它压力调节设备停工时留下一个运行。
使用本领域公知的方式将该减压的处理过的混合物分离成气体部分和液体部分。该液体部分发生进一步分离以产生回收的水和低酸油。可以用已知的油-水分离器或分离设施,如油气分离站(GOSP)实施油-水分离。从该油-水分离步骤收集低酸油。所得低酸油可表现出多种益处。除酸度的降低外,由该方法产生改质原油。此外,该低酸油与酸性原油相比也能够具有降低量的含沥青质、硫、氮或金属的物质。
本发明的反应区可以是现有技术中已知的任何反应区。在一个实施方案中,该反应区包括主反应器,其中该主反应器具有大致垂直取向且该加压的原油/水混合物向下流经该大致垂直取向的反应器。由此,流动可以是重力辅助的,并且也清扫催化剂以保持该催化剂的活性。大致垂直取向的反应器区内的流型不同于其它取向中的流型。
该减压的处理过的混合物在该物流中含有显著量的水。在一个实施方案中,将该酸性原油与水以大约10∶1至大约1∶10的重量比混合以形成原油/水混合物。
该制造低酸原油的方法可以有利地在不外部供应氢的情况下进行。在一个实施方案中,本发明中可用的金属氧化物催化剂是ZrO2。除了减少酸性官能团以产生低酸原油外,在本发明的方法中可以获得密度和粘度益处。该酸性原油的石油储层供应源具有初始密度和粘度以及初始浓度的硫和重金属。由本发明的方法制成的低酸油可具有比酸性原油的密度和粘度更低的密度和粘度。有利地,该低酸油中硫和重金属的浓度也可低于该酸性原油中硫和重金属的浓度。
在本发明的另一实施方案中,通过将至少一部分回收的水与构成水进料(其与酸性原油合并以形成原油/水混合物)的水合并,使该回收的水再循环。该回收的水可直接用于补充水进料或其可进一步处理以除去该回收的水中的某些杂质,特别是烃。在一个实施方案中,将该回收的水泵抽或以其它方式加压至等于或高于超临界水的压力。也将该回收的水加热至等于或高于超临界水的温度。向该回收的水中加入氧源以使该回收的水与氧在氧化反应器中在等于或高于超临界下反应以产生清洁的回收水物流,从而使该清洁的回收水物流含有明显比该回收的水更低的烃含量。该氧化反应器释放热能。在一个实施方案中,该热能用在该方法的其它地方以提高效率。该热能或其一部分在所述降低酸性原油的酸度的方法上游经由热交换传递。实例是向水进料所用的水、酸性原油或该方法中的任何加热器供热。示例性氧源包括空气、液化氧、过氧化氢、有机过氧化物和它们的组合。
有利地,该方法可以在现场生产设施处进行以避免与酸性原油的运输相关的腐蚀问题。
在本发明的另一实施方案中,将该酸性原油泵抽至等于或超过水临界压力的压力以产生加压的酸性原油,该加压的酸性原油保持在不超过150℃的温度。独立获得供水,并将水泵抽至等于或超过水临界压力的压力。也将水加热至等于或高于水临界温度的温度以制造加压水。随后混合该加热加压水和酸性原油物流以形成加压的原油/水混合物。这种加压的原油/水混合物在加热区中预热至大约150℃至大约400℃或优选150℃至350℃以形成预热混合物。使该预热混合物在反应区中与金属氧化物催化剂接触并在保持至少等于或高于大约22.1MPa的压力的同时加热至大约374°至大约600℃,持续可操作为产生与酸性原油的TAN相比具有显著降低的TAN的处理过的原油的反应期。该方法可有利地在不外部供应氢的情况下进行。
附图简述
为了获得和详细理解本发明的上述特征、方面和优点以及可看出的其它特征、方面和优点,可以参照构成本说明书的一部分的附图中所示的其实施方案作出上文概述的本发明的更特定描述。但是,要指出的是,附图仅显示本发明的优选实施方案,因此不应被视为限制本发明的范围,因为本发明可以有其它同样有效的实施方案。
图1显示本发明的一个优选实施方案。
图2显示本发明的另一优选实施方案。
图3显示本发明的另一实施方案。
图4显示本发明的另一实施方案。
示例性实施方案详述
本发明在现场生产设施中在不外部供应氢的情况下在金属氧化物催化剂存在下利用超临界水来降低由石油储层产生的酸性原油的酸度。本发明更特别涉及高酸原油的脱酸法,特别是通过脱羧基作用,以便在运输、储存和通过传统精炼法加工的过程中具有低得多的金属表面腐蚀趋势。也在不形成显著量焦的情况下同时实现粘度降低、密度降低(被认为是减粘裂化)、除硫、除氮和除金属。
一个实施方案包括使用整个酸性原油而非仅使用酸性原油的馏分。全原油含有多种不合意的组分。本发明不只处理酸性官能团。因此,通过处理全原油,除脱酸外,还实现与酸性原油的改质以及其它杂质、硫化合物和金属的脱除相关的显著的附加优点。
包括馏分脱酸的方法往往留下“难以处理的”组分,如沥青质(高百分比的复杂环状和芳族化合物)、含重金属的化合物和高分子量化合物,它们容易形成焦。将本发明的方法用于全原油在不造成额外成本的情况下在处理这些“难以处理的”化合物方面提供显著益处。
本发明提供使用超临界水和金属氧化物催化剂将高酸原油脱酸的有效方法。造成原油的高酸度和强腐蚀性的具有羧酸官能团的环烷酸化合物被分解,从而将羧酸基团转化成二氧化碳。
本发明可以在不存在化学中和剂的情况下进行,因此避免与牺牲化学品来降低原油的TAN相关的花费。此外,可使用环保水作为反应介质,以使该方法避免使用有毒或有害的极性有机或无机溶剂。
该方法有利地不需要氢设施,因此由于其高处理量和不要求外部供应氢而可以在高酸原油的产地使用。本发明包括高酸原油-水混合阶段、预热阶段、主反应器阶段、冷却和分离阶段。另外,来自分离阶段的回收的水中所含的有机化合物可以在氧存在下用超临界水充分氧化以获得用于再循环的清洁水和由氧化反应释放的热能。
本发明提供将高酸原油转化成具有低得多的腐蚀性并适合目前可用的工艺,包括在不腐蚀的情况下通过传统管路、油轮和精炼工艺传输的更有价值的烃原料的方法。此外,通过本发明获得的原料具有用于传统精炼工艺的良好品质以制造具有低杂质含量的石油产品,如汽油和柴油。另外,通过烃的裂化,也降低该酸性原油的粘度,以致更容易转移和加工。
在本发明中,超临界水通过促进高质量扩散、高热传递、分子内或分子间氢转移、稳定用于抑制成焦的自由基化合物和除去杂质,如含硫、氮和金属的分子来提供稳定的反应介质以供酸性原油中的有机酸性组分分解达到低得多的酸性。
利用本发明,通过使用超临界水的反应,除脱酸外,还降低粘度,降低密度,且至少部分除去该进料原油中所含的杂质,如硫、氮和金属。本发明中公开的方法可以简单地在高酸原油的产地使用。可以通过热交换和氧化回收能量以优化该方法的能量输入。
总酸值(TAN)高于0.3的的原油通常被视为“酸性原油”并具有强腐蚀趋势。通常用KOH滴定以测试TAN值。在本发明的一个实施方案中,使用处理过的油的KOH滴定来测定催化剂功能和进料通量的优化。TAN的小变化可用于调校该方法的运行条件。在大致稳态下运行的同时TAN的大变化能够表明该催化剂正要到达其有效运行期的终点。
图1显示进料入储水罐[10]的水进料[2],其中来自水进料[2]的水随后经由高压计量水泵[20]泵抽至等于或高于22.1MPa,优选23至25MPa的水进料压力。在一个实施方案中,可以将该水进料加热至等于或高于374℃,更优选400-450℃的温度。可以类似地将酸性原油[4]进料入酸性原油储罐[11],在此酸性原油[4]随后经由高压计量酸性原油泵[21]泵抽至等于或高于22.1MPa,优选23至25MPa的酸性原油压力。酸性原油[4]可以在预热器[25]中加热至基于该酸性原油的特性促进流动但不超过150℃的酸性原油温度。令人惊讶地,通过使酸性原油在高压下保持低于150℃,可以尽量降低或消除焦化。在高于大约150℃,酸性原油能够开始在预热管道中形成高粘石油淤渣,其也能够在主反应器中转化成固体物质。固体物质可堵塞排出管和造成该工艺的意外停工。本发明通过酸性原油的温度控制克服该问题。避免成焦的进一步有利的要素包括反应区的取向。通过混合区[30]将现在处于超临界态的水进料[2]与酸性原油[4]混合。混合区[30]可以简单地是管路中允许混合的三通接头,或本领域中已知的其它混合装置。水进料[2]和酸性原油[4]在混合区[30]合并形成原油/水混合物[32]。在图1中,原油/水混合物[32]是加压的原油/水混合物物流。随后将该原油/水混合物[32]进料入加热区[40]以便预热,其中将该温度提高至在150至400℃的范围内,或更优选150至350℃的范围内的温度以形成预热混合物[42]。
随后将该预热混合物[42]进料入反应区,其包括具有内部部分的主反应器[50],以使该预热混合物[42]接触金属氧化物催化剂。可以在该反应区中提供进一步加热以使温度和压力接近或超过水的超临界点,并实现至少一定程度的化学转化以转化该酸性官能团以产生与酸性原油的TAN相比具有显著降低的TAN的处理过的原油。有利地,该预热混合物[42]的至少一些烃也发生裂化以使该处理过的原油与酸性原油相比也是改质的。
有利地,独立地加热水和酸性油产生了该酸性油在进入该反应器之前仅短期承受高温的方法。由此,可以极大防止焦形成。
该酸性官能团包括环烷酸基团,如-COOH。其在反应区内在催化剂存在下转化成CO2或类似物以除去官能酸基。
使用任何可接受的冷却器[60],优选热交换器冷却该处理过的原油,以制造冷却处理过的原油混合物[62]。该冷却的处理过的混合物[62]随后使用压力调节设备[70]减压以制造减压的处理过的混合物[72]或降压处理过的混合物。该减压的处理过的混合物[72]随后进入液-气分离器[80],在此将减压的处理过的混合物[72]分离成气体部分[82]和液体部分[84]。随后将液体部分[84]进料入油-水分离设施[90]或油-水分离器以产生低酸油[92]和回收的水[94]。在图2中所示的另一实施方案中,回收的水[94]可以在该方法上游再循环至储水罐[10]之前或之后的位置和再用于补充水进料[2]。
图3显示本发明的另一实施方案,其中回收的水[94]在高压泵[100]中泵抽至等于或高于超临界水的压力。回收的水[94]在空气混合器[110]中与空气混合。空气混合器[110]可以是本领域中已知的任何类型的混合装置,包括将空气或其它氧源注入管道。使回收的水[94]和空气在氧化反应器[120]中在等于或高于超临界水的温度和压力下反应。这产生清洁的回收水物流以使该清洁的回收水物流含有明显比所述回收的水更低的烃含量。这种清洁的回收水物流可随后通过水压力调节设备[140]减压以便添加到水进料[2]中或储水罐[10]中。或者,该回收的水可以保持在高压下,由此不需要水压力调节设备[140],并再循环到该方法中的已处于压力下的位置。
图4显示另一实施方案,其中将水进料[2]和酸性原油[4]混合在一起以形成原油/水混合物[12]。在高压计量酸性原油泵[21]中将原油/水混合物[12]泵抽至至少水的临界压力,并在加热区[40]中加热至至少水的临界温度。预热混合物[42]进入反应区的主反应器[50]以使预热混合物[42]接触金属氧化物催化剂。可以在该反应区中提供进一步加热以使温度和压力接近或超过水的超临界点并实现化学转化以转化酸性官能团,从而制造与酸性原油的TAN相比具有显著降低的TAN的处理过的原油。
有利地,通过直接在进入反应器中之前和/或在反应器中提高该合并的水和酸性原油的温度,产生了该酸性原油在进入该反应器之前仅短期承受高温的方法。由此,可以极大防止焦形成。作为烃分子之间的缓冲剂的足量水的存在也有助于避免形成焦。
实施例1:
通过不限制本发明的权利要求书的下列示例性实施方案进一步验证本发明的方法。示例性实施方案数据代表预期结果。
本方法适用的高酸原油包括PETROBRAS生产的Malim油,其示例性性质列在表1中。
表1
性质 | 值 |
密度,°API | 19.2 |
硫,总重量% | 0.78 |
固体废物,重量% | 0.012 |
总酸度(mg KOH/g) | 1.26 |
沥青质,重量% | 2.6 |
氮,重量% | 0.49 |
钒,wt ppm | 25 |
镍,wt ppm | 20 |
可以通过本发明的方法加工具有表1的性质的高酸原油。将高酸原油泵抽至大约25MPa并通过用电加热器包围原油进料线路来预热至大约50℃。使水进料线路经过热交换器,随后经过电炉,并用绝热体包裹。通过合适的装置,例如T形接头或本领域技术人员已知的任何混合装置,例如叶轮,来合并原油和水物流。可以将该原油/水混合物进料入预热区以将温度升至大约250℃-400℃,更优选大约250℃至350℃。该加压的混合物能够随后在保持大约25MPa的压力和大约400℃的温度的同时引入主反应区。优选将混合物在主反应器中的停留时间调节至1分钟至30分钟。示例性催化剂包括具有23平方米/克的比表面积和12毫米的粒度的ZrO2催化剂。热优化可包括从反应区中输出以在预热区或氧化反应器中与进料混合物热交换。可随后将热交换器的输出物进料入液-气分离器以产生气体部分[82]和液体部分[84]。在此,可以使用本领域技术人员已知的任何合适的液-气分离器。可随后将来自该液-气分离器的液体部分[84]进料入油-水分离器设施[90]。位于生产井附近的GOSP设施可用于此用途。可以收集和分析由此制成的低酸油。TAN的分析能够包括用KOH或NaOH滴定以测定该低酸油的TAN。总液体收率的评估值可高于90.8重量%,且在处理过程中形成的焦和气体量为原料的3.2重量%和6.0重量%。低酸油的预期TAN为0.23,且总硫含量为0.54重量%并且完全除去进料中所含的钒。
本发明的方法优于已知方法,因为其提供适合在现场生产设施处将酸性原油脱酸的方法,从而能够将所有下游设备的腐蚀尽量降低。
在一个实施方案中,该主反应器可装有ZrO2催化剂。能够确定该催化剂的尺寸以使填充床中的压力积聚最小化,大颗粒是优选的。该主反应器能够优选是垂直的,预热进料从顶部进入。
如果需要,可以部分通过使该进料原油物流与来自主反应器的产物物流热交换来实现该方法中的温和加热。
该酸性原油的示例性加热方法包括管式加热器、追踪(tracing)、套式加热或其它方法以将进料物流的温度提高至150-350℃。如果需要,可以部分通过使进料物流与来自主反应器的产物物流热交换来实现用于此用途的加热。
反应区在一个实施方案中包括被加热器围绕的主反应器。反应区可装有具有一种或多种不同形状(如球形、三叶形或挤出体)的催化剂。大尺寸催化剂可用于产生供流体流过该催化剂的自由空间。
该预热进料物流在该主反应器中停留相对较短的时间。已经发现,大约1至60分钟的停留时间能够有效地显著改变TAN值。尽管较长时期是可行的,但在主反应器中的追加时间会降低益处。尽管在该反应器中的停留时间可持续几小时,但超过60分钟的时间预计不造成转化率的显著提高。大部分转化在进入该反应器后迅速发生。该预热进料物流优选从主反应器顶部进料,以使该物流在重力辅助下行经主反应器。
随后将来自主反应器的产物物流冷却并通过压力调节设备释放压力。
随后通过一系列合适的分离器将冷却的产物物流分离成气相和液相。制成的气体可以以传统方式除去,包括燃烧或排出到大气中。随后通过油-水分离器技术将产物物流的液体部分分离成油相和水相。
在一个实施方案中,来自油-水分离器的回收的水相通过氧化反应器在超临界条件下用氧处理以除去水相中所含的油性杂质。用于此用途的氧可以由液化氧气、过氧化氢、有机过氧化物和空气供应。来自氧化反应器的产物具有由氧化反应释放的高热能。因此,其可以与初始加热热交换至10℃至150℃,和/或与主反应器的进料物流和/或进入氧化反应器的水热交换。从油-水分离器回收的处理过的原油产物含有低得多的量的有机酸性化合物。该处理过的原油产物含有比高酸原油更低量硫、氮和金属化合物。因此,该处理过的原油产物由于其极低腐蚀性而适合通过传统的传输和精炼法加工。
通过使用作为反应介质的超临界水和金属氧化物催化剂(其促进羧基分解成二氧化碳),本发明非常有效地实现脱酸。来自本发明中公开的方法的产物含有降低的TAN以及较低量的杂质。另外,充分改进了该处理过的原油产物的流动性质以便经由传统管路和油轮转移。
尽管上文已经描述了本发明,本领域技术人员容易看出技术、程序、材料和设备的各种修改。尽管已经显示和描述了各种实施方案,但可以对其作出各种修改和替代。因此,要理解的是,已经举例而非限制性地描述了本发明。在所附权利要求的范围内旨在包含在本发明的范围和精神内的所有这样的变动。
Claims (24)
1.降低酸性原油的酸度的方法,包括下列步骤:
获得酸性原油的石油储层供应源,其中该石油储层具有现场生产设施;
将该酸性原油与水以10∶1至1∶50的重量比混合以形成原油/水混合物,此类混合在该现场生产设施处进行;
将该原油/水混合物加热至10℃至150℃的原油/水温度以形成可泵送原油/水混合物;
将该可泵送原油/水混合物泵抽至至少22.1MPa的压力以形成加压的原油/水混合物;
将该加压的原油/水混合物预热至150℃至350℃的加压温度;
使该加压的原油/水混合物在反应区中与金属氧化物催化剂接触,其中该反应区包含具有内部部分的主反应器;
在保持等于或高于至少22.1MPa的压力的同时将该加压的原油/水混合物加热至374°至600℃的反应温度范围,持续产生与该酸性原油的TAN相比具有降低的TAN的处理过的原油的反应期;
使用压力调节设备降低该处理过的原油的压力以产生减压的处理过的混合物;
将该减压的处理过的混合物分离成气体部分和液体部分;
将该液体部分分离成回收的水和低酸油;和
收集该低酸油,其中该低酸油是与该酸性原油相比具有降低量的含沥青质、硫、氮或金属的物质的改质原油。
2.权利要求1的方法,其中该酸性原油具有至少0.3的TAN。
3.权利要求1的方法,其中该主反应器大致垂直取向,以使该加压的原油/水混合物向下流经该垂直取向的反应器,以使该加压的原油水混合物向下流经该反应区。
4.权利要求1的方法,其中将该液体部分分离成回收的水和低酸油的步骤进一步包括将该减压的处理过的混合物进料入油-水分离设施以便将低酸油与水分离的步骤。
5.权利要求1的方法,其中将该酸性原油与水混合的步骤以10∶1至1∶10的重量比进行以形成原油/水混合物。
6.权利要求1的方法,其中该压力调节设备包含至少一个压力调节设备。
7.权利要求1的方法,其中在不外部供应氢的情况下进行该方法。
8.权利要求1的方法,其中该金属氧化物催化剂包含ZrO2。
9.权利要求1的方法,其中该酸性原油的石油储层供应源含有初始密度和粘度以及初始浓度的硫和重金属;
其中该低酸油具有比酸性原油的密度和粘度更低的密度和粘度;且
其中该低酸油中硫和重金属的浓度低于该酸性原油中硫和重金属的浓度。
10.权利要求1的方法,进一步包括下列步骤:
通过将至少一部分回收的水与用于形成原油/水混合物的水合并,使该回收的水再循环。
11..权利要求10的方法,进一步包括下列步骤:
将该回收的水泵抽和加热至等于或高于超临界条件;
向该回收的水中加入氧,
在氧化反应器中在等于或高于超临界条件下用氧处理该回收的水以产生清洁的回收水物流,以使该清洁的回收水物流含有比所述回收的水更低的烃含量。
12.权利要求11的方法,
其中在氧化反应器中用氧处理该回收的水的步骤产生由氧化反应释放的热能;且
进一步包括在所述降低酸性原油的酸度的方法中的上游经由热交换来传递由氧化反应释放的至少一部分热能的步骤。
13.权利要求10的方法,其中由选自空气、液化氧、过氧化氢、有机过氧化物和它们的组合的氧源供应氧。
14.在现场生产设施处降低酸性原油的酸度的方法,包括下列步骤:
将该酸性原油泵抽至等于或超过水临界压力的压力以产生加压的酸性原油,该加压的酸性原油保持在不超过150℃的温度;
获得供水并将该水泵抽至等于或超过水临界压力的压力和将该水加热至等于或高于水临界温度的温度以产生加压水;
在该现场生产设施处,混合该加压的酸性原油和该加压水以形成加压的原油/水混合物;
将该加压的原油/水混合物预热到150℃至350℃以形成预热混合物;
使该预热混合物在反应区中与金属氧化物催化剂接触,并在保持至少等于或高于22.1MPa的压力的同时将该预热混合物加热到374°至600℃,持续产生与酸性原油的TAN相比具有降低的TAN的处理过的原油的反应期;
在冷却器中冷却该处理过的原油;
使用压力调节设备降低该处理过的原油的压力以产生减压的处理过的混合物;
将该减压的处理过的混合物分离成气体部分和液体部分;
将该液体部分分离成回收的水和低酸油;和
收集该低酸油,其中该低酸油是与酸性原油相比具有降低量的含沥青质、硫、氮或金属的物质的改质原油。
15.权利要求14的方法,其中该酸性原油和水以10∶1至1∶10的重量比混合。
16.权利要求14的方法,其中该反应区包含主反应器,且该主反应器大致垂直取向,以使该加压的原油/水混合物向下流经该垂直取向的反应器,以使该加压的原油水混合物向下流经该反应区。
17.权利要求14的方法,其中将该液体部分分离成回收的水和低酸油的步骤进一步包括将该减压的处理过的混合物进料入油-水分离设施以便将低酸油与水分离的步骤。
18.权利要求14的方法,其中该压力调节设备包含至少一个压力调节设备。
19.权利要求14的方法,其中在不外部供应氢的情况下进行该方法。
20.权利要求14的方法,其中该金属氧化物催化剂包含ZrO2。
21.权利要求14的方法,其中酸性原油具有的一个石油储层供应源含有初始密度和粘度以及初始浓度的硫和重金属;
其中该低酸油具有比酸性原油的密度和粘度更低的密度和粘度;且
其中该低酸油中硫和重金属的浓度低于该酸性原油中硫和重金属的浓度。
22.权利要求14的方法,进一步包括下列步骤:
通过将至少一部分回收的水与用于形成原油/水混合物的水合并,使该回收的水再循环。
23.权利要求22的方法,进一步包括下列步骤
将该回收的水泵抽和加热至等于或高于超临界条件;
向该回收的水中加入氧,
在氧化反应器中在等于或高于超临界条件下用氧处理该回收的水以产生清洁的回收水物流,以使该清洁的回收水物流含有比该回收的水更低的烃含量。
24.权利要求22的方法,
其中在氧化反应器中用氧处理该回收的水的步骤产生由氧化反应释放的热能;且
进一步包括在所述降低酸性原油的酸度的方法中的上游经由热交换传递由氧化反应释放的至少一部分热能的步骤。
Applications Claiming Priority (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US99066207P | 2007-11-28 | 2007-11-28 | |
US99065807P | 2007-11-28 | 2007-11-28 | |
US99064107P | 2007-11-28 | 2007-11-28 | |
US99064807P | 2007-11-28 | 2007-11-28 | |
US99067007P | 2007-11-28 | 2007-11-28 | |
US60/990658 | 2007-11-28 | ||
US60/990641 | 2007-11-28 | ||
US60/990662 | 2007-11-28 | ||
US60/990648 | 2007-11-28 | ||
US60/990670 | 2007-11-28 | ||
PCT/US2008/084530 WO2009073442A2 (en) | 2007-11-28 | 2008-11-24 | Process to reduce acidity of crude oil |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101983227A CN101983227A (zh) | 2011-03-02 |
CN101983227B true CN101983227B (zh) | 2013-08-14 |
Family
ID=40674560
Family Applications (5)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN200880125755.7A Expired - Fee Related CN101970610B (zh) | 2007-11-28 | 2008-11-24 | 无需供应氢的重质和高蜡原油改质法 |
CN200880125762.7A Expired - Fee Related CN101970609B (zh) | 2007-11-28 | 2008-11-24 | 通过增压热水改质高蜡原油的方法 |
CN2008801257542A Expired - Fee Related CN101983227B (zh) | 2007-11-28 | 2008-11-24 | 降低原油酸度的方法 |
CN200880125761.2A Expired - Fee Related CN101970611B (zh) | 2007-11-28 | 2008-11-24 | 通过热加压水和超声波发生预混器将重油改质的方法 |
CN200880125753.8A Expired - Fee Related CN102159675B (zh) | 2007-11-28 | 2008-11-25 | 通过热加压水和采收流体将全原油改质的方法 |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN200880125755.7A Expired - Fee Related CN101970610B (zh) | 2007-11-28 | 2008-11-24 | 无需供应氢的重质和高蜡原油改质法 |
CN200880125762.7A Expired - Fee Related CN101970609B (zh) | 2007-11-28 | 2008-11-24 | 通过增压热水改质高蜡原油的方法 |
Family Applications After (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN200880125761.2A Expired - Fee Related CN101970611B (zh) | 2007-11-28 | 2008-11-24 | 通过热加压水和超声波发生预混器将重油改质的方法 |
CN200880125753.8A Expired - Fee Related CN102159675B (zh) | 2007-11-28 | 2008-11-25 | 通过热加压水和采收流体将全原油改质的方法 |
Country Status (10)
Country | Link |
---|---|
US (7) | US8025790B2 (zh) |
EP (5) | EP2231823A2 (zh) |
JP (5) | JP5346036B2 (zh) |
KR (6) | KR101606680B1 (zh) |
CN (5) | CN101970610B (zh) |
BR (5) | BRPI0819687A2 (zh) |
DK (1) | DK2240556T3 (zh) |
ES (1) | ES2582392T3 (zh) |
MX (5) | MX2010005854A (zh) |
WO (5) | WO2009073442A2 (zh) |
Families Citing this family (107)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10310199B4 (de) * | 2003-03-06 | 2007-09-20 | Kronotec Ag | Holzfaserplatte und Verfahren zu deren Herstellung |
US7943036B2 (en) | 2009-07-21 | 2011-05-17 | Chevron U.S.A. Inc. | Systems and methods for producing a crude product |
KR101606680B1 (ko) | 2007-11-28 | 2016-03-25 | 사우디 아라비안 오일 컴퍼니 | 고도로 밀납을 함유하는 원유의 유동점 및 파라핀 함량을 낮추기 위한 연속 공정 |
US20090159498A1 (en) * | 2007-12-20 | 2009-06-25 | Chevron U.S.A. Inc. | Intergrated process for in-field upgrading of hydrocarbons |
US8236169B2 (en) * | 2009-07-21 | 2012-08-07 | Chevron U.S.A. Inc | Systems and methods for producing a crude product |
US7931797B2 (en) | 2009-07-21 | 2011-04-26 | Chevron U.S.A. Inc. | Systems and methods for producing a crude product |
US8759242B2 (en) | 2009-07-21 | 2014-06-24 | Chevron U.S.A. Inc. | Hydroprocessing catalysts and methods for making thereof |
US9068132B2 (en) | 2009-07-21 | 2015-06-30 | Chevron U.S.A. Inc. | Hydroprocessing catalysts and methods for making thereof |
US8927448B2 (en) | 2009-07-21 | 2015-01-06 | Chevron U.S.A. Inc. | Hydroprocessing catalysts and methods for making thereof |
US8551323B2 (en) * | 2009-08-31 | 2013-10-08 | Chevron U.S.A. Inc. | Systems and methods for hydroprocessing a heavy oil feedstock |
US8394260B2 (en) | 2009-12-21 | 2013-03-12 | Saudi Arabian Oil Company | Petroleum upgrading process |
US8197670B2 (en) * | 2010-02-23 | 2012-06-12 | Chevron U.S.A. Inc. | Process for upgrading hydrocarbons and device for use therein |
US8444843B2 (en) | 2010-04-15 | 2013-05-21 | Saudi Arabian Oil Company | Electrocatalytic dissociation of water for hydrodesulfurization of hydrocarbon feedstock |
US9005432B2 (en) * | 2010-06-29 | 2015-04-14 | Saudi Arabian Oil Company | Removal of sulfur compounds from petroleum stream |
US9382485B2 (en) * | 2010-09-14 | 2016-07-05 | Saudi Arabian Oil Company | Petroleum upgrading process |
US9039889B2 (en) * | 2010-09-14 | 2015-05-26 | Saudi Arabian Oil Company | Upgrading of hydrocarbons by hydrothermal process |
CN102453513B (zh) * | 2010-10-22 | 2014-03-05 | 中国石油化工股份有限公司 | 降低催化裂化烟气中硫氧化物含量的方法 |
CN102453514B (zh) * | 2010-10-22 | 2014-03-05 | 中国石油化工股份有限公司 | 减少催化裂化烟气中二氧化碳排放量的方法 |
CA2815882C (en) * | 2010-10-27 | 2020-10-27 | 1555771 Alberta Ltd. | Non-aqueous hydrocarbon recovery |
US8894846B2 (en) * | 2010-12-23 | 2014-11-25 | Stephen Lee Yarbro | Using supercritical fluids to refine hydrocarbons |
WO2012091382A2 (ko) * | 2010-12-28 | 2012-07-05 | 에스케이이노베이션 주식회사 | 초임계 용매를 이용한 중질 탄화수소 유분의 수소화 분해 공정 |
KR101759351B1 (ko) | 2010-12-28 | 2017-07-21 | 에스케이이노베이션 주식회사 | 초임계 용매를 이용한 중질 탄화수소 유분의 수소화 분해 공정 |
US9018124B2 (en) | 2010-12-30 | 2015-04-28 | Chevron U.S.A. Inc. | Hydroprocessing catalysts and methods for making thereof |
US8535518B2 (en) * | 2011-01-19 | 2013-09-17 | Saudi Arabian Oil Company | Petroleum upgrading and desulfurizing process |
WO2012143972A1 (ja) * | 2011-04-19 | 2012-10-26 | 日揮株式会社 | 改質油の製造方法、及び改質油製造装置 |
EP2702121B1 (en) * | 2011-04-27 | 2019-04-10 | Saudi Arabian Oil Company | Sulfone cracking using supercritical water |
CN104039434B (zh) * | 2011-10-31 | 2015-11-25 | 沙特阿拉伯石油公司 | 用于改质石油的超临界水工艺 |
CA2757962C (en) | 2011-11-08 | 2013-10-15 | Imperial Oil Resources Limited | Processing a hydrocarbon stream using supercritical water |
KR101515690B1 (ko) | 2011-12-30 | 2015-05-06 | 연세대학교 산학협력단 | 중질 탄화수소 유분 및 목질계 바이오매스의 개질 방법 |
CN103320160B (zh) * | 2012-03-22 | 2016-01-13 | 中国石油化工股份有限公司 | 一种含酸原油的加工方法 |
AU2013280585A1 (en) * | 2012-06-27 | 2014-12-18 | Shell Internationale Research Maatschappij B.V. | Petroleum recovery process and system |
JP2014074111A (ja) * | 2012-10-03 | 2014-04-24 | Jgc Corp | 炭化水素油の処理方法及び炭化水素油の処理装置 |
KR101938171B1 (ko) | 2012-10-31 | 2019-01-14 | 대우조선해양 주식회사 | 백업 기능을 가지는 브라인 및 베이스오일 공급 시스템과 브라인 및 베이스오일의 백업 공급 방법 |
US9687823B2 (en) | 2012-12-14 | 2017-06-27 | Chevron U.S.A. Inc. | Hydroprocessing co-catalyst compositions and methods of introduction thereof into hydroprocessing units |
US9321037B2 (en) | 2012-12-14 | 2016-04-26 | Chevron U.S.A., Inc. | Hydroprocessing co-catalyst compositions and methods of introduction thereof into hydroprocessing units |
KR101898734B1 (ko) * | 2012-12-20 | 2018-09-13 | 에스케이에너지 주식회사 | 원유 탈염 시스템 |
KR101422483B1 (ko) * | 2012-12-21 | 2014-07-23 | 삼성중공업 주식회사 | 고점도의 원유 채굴방법 |
US8715488B1 (en) | 2013-01-07 | 2014-05-06 | Clean Global Energy, Inc. | Method and apparatus for making hybrid crude oils and fuels |
US10907455B2 (en) * | 2013-02-08 | 2021-02-02 | Chevron U.S.A. Inc. | System and process for recovering hydrocarbons using a supercritical fluid |
US11242735B2 (en) * | 2013-02-08 | 2022-02-08 | Chevron U.S.A. Inc. | System and process for recovering hydrocarbons using a supercritical fluid |
CA2843041C (en) | 2013-02-22 | 2017-06-13 | Anschutz Exploration Corporation | Method and system for removing hydrogen sulfide from sour oil and sour water |
US11440815B2 (en) | 2013-02-22 | 2022-09-13 | Anschutz Exploration Corporation | Method and system for removing hydrogen sulfide from sour oil and sour water |
US9708196B2 (en) | 2013-02-22 | 2017-07-18 | Anschutz Exploration Corporation | Method and system for removing hydrogen sulfide from sour oil and sour water |
US9364773B2 (en) | 2013-02-22 | 2016-06-14 | Anschutz Exploration Corporation | Method and system for removing hydrogen sulfide from sour oil and sour water |
US10215399B2 (en) | 2013-03-14 | 2019-02-26 | The Babcock & Wilcox Company | Small supercritical once-thru steam generator |
JP6248253B2 (ja) * | 2013-08-29 | 2017-12-20 | 国立大学法人秋田大学 | 溶液中の重質油回収方法及び回収システム |
CN105518101A (zh) * | 2013-09-13 | 2016-04-20 | 通用电气公司 | 处理用于产生超临界密相流体的采出水和注入地质层用于烃生产 |
US9771527B2 (en) | 2013-12-18 | 2017-09-26 | Saudi Arabian Oil Company | Production of upgraded petroleum by supercritical water |
DK3097165T3 (da) * | 2014-01-20 | 2022-09-12 | Applied Res Associates Inc | Højeffektiv flydepunktsnedsættende fremgangsmåde |
US20170003264A1 (en) * | 2014-01-24 | 2017-01-05 | The University Of Wyoming Research Corporation D/B/A Western Research Institute | Volatile Hydrocarbon Separation and Analysis Apparatus and Methods |
FR3018274B1 (fr) * | 2014-03-10 | 2016-04-08 | Innoveox | Procede de traitement de dechets organiques par oxydation hydrothermale |
US9505678B2 (en) | 2014-05-12 | 2016-11-29 | Saudi Arabian Oil Company | Process to produce aromatics from crude oil |
CN105368487A (zh) * | 2014-08-12 | 2016-03-02 | 罗杰·K·洛特 | 用于加工烃类的超声波处理 |
KR101568615B1 (ko) * | 2014-11-28 | 2015-11-11 | 연세대학교 산학협력단 | 중질 탄화수소 유분의 연속적 처리 방법 |
CN104492412B (zh) * | 2015-01-07 | 2016-08-24 | 苏珂 | 一种石油脱酸催化剂的制备方法 |
JP6556243B2 (ja) * | 2015-01-28 | 2019-08-07 | アプライド リサーチ アソシエーツ, インコーポレイテッド | 水熱浄化プロセス |
US9802176B2 (en) * | 2015-03-24 | 2017-10-31 | Saudi Arabian Oil Company | Method for mixing in a hydrocarbon conversion process |
US10012064B2 (en) | 2015-04-09 | 2018-07-03 | Highlands Natural Resources, Plc | Gas diverter for well and reservoir stimulation |
US10344204B2 (en) | 2015-04-09 | 2019-07-09 | Diversion Technologies, LLC | Gas diverter for well and reservoir stimulation |
US9452434B1 (en) | 2015-04-17 | 2016-09-27 | LLT International (Ireland) Ltd. | Providing wear resistance in a reactor configured to facilitate chemical reactions and/or comminution of solid feed materials using shockwaves created in a supersonic gaseous vortex |
US10427129B2 (en) * | 2015-04-17 | 2019-10-01 | LLT International (Ireland) Ltd. | Systems and methods for facilitating reactions in gases using shockwaves produced in a supersonic gaseous vortex |
US10434488B2 (en) | 2015-08-11 | 2019-10-08 | LLT International (Ireland) Ltd. | Systems and methods for facilitating dissociation of methane utilizing a reactor designed to generate shockwaves in a supersonic gaseous vortex |
KR102250734B1 (ko) * | 2015-09-25 | 2021-05-11 | 에스케이이노베이션 주식회사 | 원유 내의 유기산 및 금속의 제거 방법 |
US9926497B2 (en) * | 2015-10-16 | 2018-03-27 | Saudi Arabian Oil Company | Method to remove metals from petroleum |
CN105403347B (zh) * | 2015-11-27 | 2019-09-06 | 中国石油化工股份有限公司 | Co2驱最小混相压力测定方法及专用装置 |
US10066172B2 (en) * | 2015-12-15 | 2018-09-04 | Saudi Arabian Oil Company | Supercritical water upgrading process to produce paraffinic stream from heavy oil |
EP3370858B1 (en) | 2015-12-15 | 2022-01-26 | Saudi Arabian Oil Company | Supercritical reactor systems and processes for petroleum upgrading |
US10066176B2 (en) | 2015-12-15 | 2018-09-04 | Saudi Arabian Oil Company | Supercritical water upgrading process to produce high grade coke |
US10011790B2 (en) | 2015-12-15 | 2018-07-03 | Saudi Arabian Oil Company | Supercritical water processes for upgrading a petroleum-based composition while decreasing plugging |
KR101696376B1 (ko) | 2016-03-25 | 2017-01-12 | 서울시립대학교 산학협력단 | 촉매를 이용한 바이오 오일의 안정화 방법 |
US10982520B2 (en) | 2016-04-27 | 2021-04-20 | Highland Natural Resources, PLC | Gas diverter for well and reservoir stimulation |
JP6886480B2 (ja) * | 2016-07-08 | 2021-06-16 | アプライド リサーチ アソシエーツ, インコーポレイテッド | 超臨界水分離プロセス |
CN106350101B (zh) * | 2016-09-19 | 2018-01-23 | 华东理工大学 | 基于亚/超临界水中重芳烃自组装效应的重质油预处理的方法及应用 |
US10106748B2 (en) | 2017-01-03 | 2018-10-23 | Saudi Arabian Oil Company | Method to remove sulfur and metals from petroleum |
US10577546B2 (en) | 2017-01-04 | 2020-03-03 | Saudi Arabian Oil Company | Systems and processes for deasphalting oil |
US10815434B2 (en) | 2017-01-04 | 2020-10-27 | Saudi Arabian Oil Company | Systems and processes for power generation |
CN106701161B (zh) * | 2017-02-24 | 2018-05-08 | 哈尔滨工业大学 | 声空化协同供氢剂的重油改质系统与方法 |
US10752847B2 (en) | 2017-03-08 | 2020-08-25 | Saudi Arabian Oil Company | Integrated hydrothermal process to upgrade heavy oil |
US10703999B2 (en) | 2017-03-14 | 2020-07-07 | Saudi Arabian Oil Company | Integrated supercritical water and steam cracking process |
US10689587B2 (en) * | 2017-04-26 | 2020-06-23 | Saudi Arabian Oil Company | Systems and processes for conversion of crude oil |
KR102061960B1 (ko) * | 2017-05-11 | 2020-01-03 | 서울대학교산학협력단 | 초임계 유체를 이용한 아스팔텐 저감 방법 |
RU2655394C1 (ru) * | 2017-05-25 | 2018-05-28 | Государственное унитарное предприятие "Институт нефтехимпереработки Республики Башкортостан" (ГУП "ИНХП РБ") | Способ подготовки высоковязкой нефти |
KR101928204B1 (ko) | 2017-07-19 | 2018-12-11 | 성균관대학교산학협력단 | 중질유분 개질 방법 |
CN108452842B (zh) * | 2017-10-27 | 2020-11-06 | 中国石油天然气股份有限公司 | 催化裂化油浆糠醛抽出油加氢催化剂及其制备方法与应用 |
DE102017127417B4 (de) | 2017-11-21 | 2021-01-21 | Egm-Holding-International Gmbh | Reaktionskammer |
KR102180627B1 (ko) * | 2017-12-04 | 2020-11-18 | 주식회사 엘지화학 | 자동화된 시료 열분해 장치 |
JP2021054873A (ja) * | 2018-01-12 | 2021-04-08 | 独立行政法人石油天然ガス・金属鉱物資源機構 | 高粘度重質油からの炭化水素の生産方法、及び生産システム |
CN108251093A (zh) * | 2018-01-31 | 2018-07-06 | 南京工业大学 | 一种用于稠油热采的超临界流体的制备系统和方法 |
US11286434B2 (en) * | 2018-02-26 | 2022-03-29 | Saudi Arabian Oil Company | Conversion process using supercritical water |
US11021659B2 (en) * | 2018-02-26 | 2021-06-01 | Saudi Arabia Oil Company | Additives for supercritical water process to upgrade heavy oil |
US10927313B2 (en) * | 2018-04-11 | 2021-02-23 | Saudi Arabian Oil Company | Supercritical water process integrated with visbreaker |
WO2019222307A1 (en) * | 2018-05-15 | 2019-11-21 | Worcester Polytechnic Institute | Water-assisted zeolite upgrading of oils |
KR102098148B1 (ko) * | 2018-06-22 | 2020-04-07 | 서울대학교산학협력단 | 아스팔텐 저감 방법 |
US10526552B1 (en) | 2018-10-12 | 2020-01-07 | Saudi Arabian Oil Company | Upgrading of heavy oil for steam cracking process |
CN109650518A (zh) * | 2019-01-30 | 2019-04-19 | 中国原子能科学研究院 | 利用超临界水氧化处理有机废液的方法 |
US11118439B2 (en) | 2019-12-06 | 2021-09-14 | Saudi Arabian Oil Company | Displacing fluid for enhanced oil recovery |
US11384299B2 (en) | 2019-12-19 | 2022-07-12 | Saudi Arabian Oil Company | Systems and processes for upgrading and converting crude oil to petrochemicals through steam cracking |
CN113123740A (zh) * | 2019-12-30 | 2021-07-16 | 四川宏华石油设备有限公司 | 一种钻井液冷却系统 |
US11459511B2 (en) | 2020-04-09 | 2022-10-04 | Saudi Arabian Oil Company | Crude stabilizer bypass |
US11345861B2 (en) | 2020-06-22 | 2022-05-31 | Saudi Arabian Oil Company | Production of linear olefins from heavy oil |
US11845902B2 (en) | 2020-06-23 | 2023-12-19 | Saudi Arabian Oil Company | Online analysis in a gas oil separation plant (GOSP) |
US11781075B2 (en) | 2020-08-11 | 2023-10-10 | Applied Research Associates, Inc. | Hydrothermal purification process |
US11548784B1 (en) | 2021-10-26 | 2023-01-10 | Saudi Arabian Oil Company | Treating sulfur dioxide containing stream by acid aqueous absorption |
US11926799B2 (en) | 2021-12-14 | 2024-03-12 | Saudi Arabian Oil Company | 2-iso-alkyl-2-(4-hydroxyphenyl)propane derivatives used as emulsion breakers for crude oil |
CN114561229A (zh) * | 2022-02-28 | 2022-05-31 | 中海油天津化工研究设计院有限公司 | 一种节能的超临界水改质油品的方法 |
US20240059984A1 (en) * | 2022-08-19 | 2024-02-22 | Uop Llc | Processes and apparatuses for heating a hydrocarbon feed stream for a reactor |
US11898107B1 (en) | 2022-12-16 | 2024-02-13 | Saudi Arabian Oil Company | Systems and methods for processing hydrocarbon feedstocks |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4543177A (en) * | 1984-06-11 | 1985-09-24 | Allied Corporation | Production of light hydrocarbons by treatment of heavy hydrocarbons with water |
US4818370A (en) * | 1986-07-23 | 1989-04-04 | Cities Service Oil And Gas Corporation | Process for converting heavy crudes, tars, and bitumens to lighter products in the presence of brine at supercritical conditions |
EP0978552A2 (de) * | 1998-08-06 | 2000-02-09 | ANDERSEN, Kjeld | Verfahren zum katalytischem Entfernen von Metallverbindungen aus Schwerölen |
EP1862527A1 (en) * | 2006-05-30 | 2007-12-05 | Environmental Consulting Catalysts & Processes for a Sustainable Development | A process for the production of light hydrocarbons from natural bitumen or heavy oils |
Family Cites Families (108)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US496779A (en) * | 1893-05-02 | Tile or brick machine | ||
US2135332A (en) | 1935-12-31 | 1938-11-01 | Gasoline Prod Co Inc | Conversion of hydrocarbon oil |
US2623596A (en) * | 1950-05-16 | 1952-12-30 | Atlantic Refining Co | Method for producing oil by means of carbon dioxide |
US3325395A (en) * | 1965-04-19 | 1967-06-13 | Mcdowell Wellman Eng Co | Travelling grate method for the recovery of oil from oil bearing minerals |
US4005005A (en) * | 1974-05-31 | 1977-01-25 | Standard Oil Company (Indiana) | Process for recovering and upgrading hydrocarbons from tar sands |
US3989618A (en) | 1974-05-31 | 1976-11-02 | Standard Oil Company (Indiana) | Process for upgrading a hydrocarbon fraction |
US3948755A (en) * | 1974-05-31 | 1976-04-06 | Standard Oil Company | Process for recovering and upgrading hydrocarbons from oil shale and tar sands |
US3960706A (en) * | 1974-05-31 | 1976-06-01 | Standard Oil Company | Process for upgrading a hydrocarbon fraction |
US3983027A (en) * | 1974-07-01 | 1976-09-28 | Standard Oil Company (Indiana) | Process for recovering upgraded products from coal |
US3948754A (en) * | 1974-05-31 | 1976-04-06 | Standard Oil Company | Process for recovering and upgrading hydrocarbons from oil shale and tar sands |
US4113446A (en) * | 1975-07-22 | 1978-09-12 | Massachusetts Institute Of Technology | Gasification process |
JPS5250306A (en) | 1975-10-22 | 1977-04-22 | Kureha Chem Ind Co Ltd | Method and apparatus for decoking |
US4118797A (en) * | 1977-10-25 | 1978-10-03 | Energy And Minerals Research Co. | Ultrasonic emulsifier and method |
US4243514A (en) * | 1979-05-14 | 1981-01-06 | Engelhard Minerals & Chemicals Corporation | Preparation of FCC charge from residual fractions |
US4543190A (en) * | 1980-05-08 | 1985-09-24 | Modar, Inc. | Processing methods for the oxidation of organics in supercritical water |
US4448251A (en) * | 1981-01-08 | 1984-05-15 | Uop Inc. | In situ conversion of hydrocarbonaceous oil |
US4550198A (en) * | 1982-11-04 | 1985-10-29 | Georgia Tech Research Institute | Purification of terephthalic acid by supercritical fluid extraction |
US4446012A (en) * | 1982-12-17 | 1984-05-01 | Allied Corporation | Process for production of light hydrocarbons by treatment of heavy hydrocarbons with water |
US4443325A (en) * | 1982-12-23 | 1984-04-17 | Mobil Oil Corporation | Conversion of residua to premium products via thermal treatment and coking |
US4483761A (en) | 1983-07-05 | 1984-11-20 | The Standard Oil Company | Upgrading heavy hydrocarbons with supercritical water and light olefins |
US4684372A (en) * | 1983-11-02 | 1987-08-04 | Petroleum Fermentations N.V. | Combustion of viscous hydrocarbons |
US4529037A (en) * | 1984-04-16 | 1985-07-16 | Amoco Corporation | Method of forming carbon dioxide mixtures miscible with formation crude oils |
US4839326A (en) | 1985-04-22 | 1989-06-13 | Exxon Research And Engineering Company | Promoted molybdenum and tungsten sulfide catalysts, their preparation and use |
US4753666A (en) * | 1986-07-24 | 1988-06-28 | Chevron Research Company | Distillative processing of CO2 and hydrocarbons for enhanced oil recovery |
US4733724A (en) * | 1986-12-30 | 1988-03-29 | Texaco Inc. | Viscous oil recovery method |
US4840725A (en) * | 1987-06-19 | 1989-06-20 | The Standard Oil Company | Conversion of high boiling liquid organic materials to lower boiling materials |
US4813370A (en) * | 1988-04-21 | 1989-03-21 | Capamaggio Scott A | Bookmarker |
US5110443A (en) * | 1989-02-14 | 1992-05-05 | Canadian Occidental Petroleum Ltd. | Converting heavy hydrocarbons into lighter hydrocarbons using ultrasonic reactor |
US4951561A (en) * | 1989-06-06 | 1990-08-28 | Kraft General Foods, Inc. | Apparatus for fluid-solid bed processing |
US5096567A (en) | 1989-10-16 | 1992-03-17 | The Standard Oil Company | Heavy oil upgrading under dense fluid phase conditions utilizing emulsified feed stocks |
US5851381A (en) * | 1990-12-07 | 1998-12-22 | Idemitsu Kosan Co., Ltd. | Method of refining crude oil |
US5133877A (en) * | 1991-03-29 | 1992-07-28 | The United States Of America As Represented By The United States Department Of Energy | Conversion of hazardous materials using supercritical water oxidation |
EP0721360A1 (en) * | 1992-11-09 | 1996-07-17 | SIPIN, Anatole J. | Controlled fluid transfer system |
US5496464A (en) * | 1993-01-04 | 1996-03-05 | Natural Resources Canada | Hydrotreating of heavy hydrocarbon oils in supercritical fluids |
IT1263961B (it) * | 1993-02-24 | 1996-09-05 | Eniricerche Spa | Procedimento per la deasfaltazione e la demetallazione di residui petroliferi |
US5316659A (en) | 1993-04-02 | 1994-05-31 | Exxon Research & Engineering Co. | Upgrading of bitumen asphaltenes by hot water treatment |
US5389240A (en) * | 1993-08-02 | 1995-02-14 | Uop | Naphthenic acid removal as an adjunct to liquid hydrocarbon sweetening |
CA2200945C (en) * | 1994-10-27 | 2006-06-06 | Minas Robert Apelian | Wax hydroisomerization process |
US5720551A (en) * | 1994-10-28 | 1998-02-24 | Shechter; Tal | Forming emulsions |
FR2727634A1 (fr) * | 1994-12-06 | 1996-06-07 | Electrolyse L | Procede en milieu reducteur de transformation chimique de structures chimiques complexes dans un fluide supercritique |
US5674405A (en) * | 1995-07-28 | 1997-10-07 | Modar, Inc. | Method for hydrothermal oxidation |
US5725054A (en) * | 1995-08-22 | 1998-03-10 | Board Of Supervisors Of Louisiana State University And Agricultural & Mechanical College | Enhancement of residual oil recovery using a mixture of nitrogen or methane diluted with carbon dioxide in a single-well injection process |
DE69631901T2 (de) * | 1995-08-25 | 2005-02-03 | Exxonmobil Research And Engineering Co. | Verfahren zur verminderung der korrosivität und acidität von rohöl |
US5885440A (en) * | 1996-10-01 | 1999-03-23 | Uop Llc | Hydrocracking process with integrated effluent hydrotreating zone |
US5871637A (en) * | 1996-10-21 | 1999-02-16 | Exxon Research And Engineering Company | Process for upgrading heavy oil using alkaline earth metal hydroxide |
US5778977A (en) * | 1997-01-03 | 1998-07-14 | Marathon Oil Company | Gravity concentrated carbon dioxide for process |
US5904839A (en) | 1997-06-06 | 1999-05-18 | Exxon Research And Engineering Co. | Process for upgrading heavy oil using lime |
US6268447B1 (en) * | 1998-12-18 | 2001-07-31 | Univation Technologies, L.L.C. | Olefin polymerization catalyst |
US5928502A (en) * | 1997-08-29 | 1999-07-27 | Exxon Research And Engineering Co. | Process for reducing total acid number of crude oil |
US5871636A (en) * | 1997-08-29 | 1999-02-16 | Exxon Research And Engineering Company | Catalytic reduction of acidity of crude oils in the absence of hydrogen |
JP3572176B2 (ja) * | 1997-09-03 | 2004-09-29 | 三菱重工業株式会社 | コンバインド・サイクル発電方法及び発電装置 |
US6016867A (en) * | 1998-06-24 | 2000-01-25 | World Energy Systems, Incorporated | Upgrading and recovery of heavy crude oils and natural bitumens by in situ hydrovisbreaking |
JP2000100850A (ja) | 1998-09-24 | 2000-04-07 | Ebara Udylite Kk | 低融点金属バンプの形成方法 |
JP2000104311A (ja) | 1998-09-30 | 2000-04-11 | Matsushita Electric Works Ltd | 衛生洗浄装置 |
JP2000109850A (ja) | 1998-10-07 | 2000-04-18 | Mitsubishi Materials Corp | 重質油の発電設備用流体燃料への転換方法及びその装置 |
JP3489478B2 (ja) | 1999-03-31 | 2004-01-19 | 三菱マテリアル株式会社 | 超臨界水を用いた炭化水素資源の転換方法 |
US6190541B1 (en) | 1999-05-11 | 2001-02-20 | Exxon Research And Engineering Company | Process for treatment of petroleum acids (LAW824) |
JP3900764B2 (ja) * | 1999-11-11 | 2007-04-04 | 三菱マテリアル株式会社 | 重質油の軽質化方法及びその装置 |
JP2001192676A (ja) | 2000-01-11 | 2001-07-17 | Mitsubishi Materials Corp | 炭化水素資源等の高効率転換方法 |
US20010035006A1 (en) * | 2000-02-01 | 2001-11-01 | Danan Dou | Sulfur trap in NOx adsorber systems for enhanced sulfur resistance |
US20020076212A1 (en) * | 2000-04-24 | 2002-06-20 | Etuan Zhang | In situ thermal processing of a hydrocarbon containing formation producing a mixture with oxygenated hydrocarbons |
FR2814967B1 (fr) * | 2000-10-10 | 2003-11-14 | Commissariat Energie Atomique | Procede et dispositif pour l'oxydation en eau supercritique de matieres |
US6547957B1 (en) | 2000-10-17 | 2003-04-15 | Texaco, Inc. | Process for upgrading a hydrocarbon oil |
US6475396B1 (en) * | 2000-11-14 | 2002-11-05 | Hydroprocessing, Llc | Apparatus and method for applying an oxidant in a hydrothermal oxidation process |
JP2002155286A (ja) * | 2000-11-20 | 2002-05-28 | Mitsubishi Materials Corp | 重質炭素資源の改質方法 |
US20020086150A1 (en) * | 2000-12-28 | 2002-07-04 | Hazlebeck David A. | System and method for hydrothermal reactions-two layer liner |
US6454936B1 (en) | 2001-03-09 | 2002-09-24 | Exxonmobil Research And Engineering Company | Removal of acids from oils |
CA2348947A1 (en) * | 2001-03-19 | 2002-09-19 | Venanzio Di Tullio | A process for the catalytic reduction of heavy oils, kerogens, plastics, bio-masses, sludges and organic waste to light hydrocarbon liquids, carbon dioxide and amines |
US20020157991A1 (en) * | 2001-03-27 | 2002-10-31 | Mason Thomas G. | Disaggregation of asphaltenes in incompatible petroleum oil mixtures |
US7081196B2 (en) * | 2001-05-10 | 2006-07-25 | Mark Cullen | Treatment of crude oil fractions, fossil fuels, and products thereof with sonic energy |
JP3791363B2 (ja) | 2001-08-07 | 2006-06-28 | 株式会社日立製作所 | 重質油の軽質化方法 |
WO2003025098A2 (en) * | 2001-09-17 | 2003-03-27 | Southwest Research Institute | Pretreatment processes for heavy oil and carbonaceous materials |
JP3724438B2 (ja) * | 2002-03-08 | 2005-12-07 | 株式会社日立製作所 | 超臨界水による重質油の処理方法と処理装置及び重質油処理装置を備えた発電システム |
JP3669340B2 (ja) | 2002-03-27 | 2005-07-06 | 株式会社日立製作所 | 石油の精製方法と精製装置および発電プラント |
JP2004000825A (ja) * | 2002-05-31 | 2004-01-08 | Kurita Water Ind Ltd | 水熱酸化反応方法 |
NO20033230D0 (no) * | 2003-07-16 | 2003-07-16 | Statoil Asa | Fremgangsmåte for utvinning og oppgradering av olje |
JP4098181B2 (ja) | 2003-08-05 | 2008-06-11 | 株式会社日立製作所 | 重質油の処理方法及び重質油類処理システム |
US7435330B2 (en) * | 2003-10-07 | 2008-10-14 | Hitachi, Ltd. | Heavy oil reforming method, an apparatus therefor, and gas turbine power generation system |
JP4942911B2 (ja) | 2003-11-28 | 2012-05-30 | 東洋エンジニアリング株式会社 | 水素化分解触媒、重質油を水素化分解する方法 |
NL1027766C2 (nl) * | 2003-12-19 | 2006-07-13 | Shell Int Research | Systemen, methoden en katalysatoren voor het produceren van een ruwe-oliehoudend product. |
BRPI0405563A (pt) * | 2003-12-19 | 2005-09-20 | Shell Int Research | Métodos de produzir um produto de petróleo bruto e combustìvel de transporte, combustìvel de aquecimento, lubrificantes ou substâncias quìmicas e produto de petróleo bruto |
US7144498B2 (en) * | 2004-01-30 | 2006-12-05 | Kellogg Brown & Root Llc | Supercritical hydrocarbon conversion process |
US20060016723A1 (en) * | 2004-07-07 | 2006-01-26 | California Institute Of Technology | Process to upgrade oil using metal oxides |
JP4555010B2 (ja) | 2004-07-15 | 2010-09-29 | 株式会社日立製作所 | 改質燃料焚きガスタービン及びその運転方法 |
US7381320B2 (en) * | 2004-08-30 | 2008-06-03 | Kellogg Brown & Root Llc | Heavy oil and bitumen upgrading |
WO2006037368A1 (en) | 2004-10-04 | 2006-04-13 | Petroleo Brasileiro S.A.-Petrobras | Process for reducing the organic acid content of hydrocarbon feedstocks |
JP2006104311A (ja) | 2004-10-05 | 2006-04-20 | Mitsubishi Materials Corp | 未利用重質油の改質方法及びその装置。 |
SE529006C2 (sv) * | 2004-11-15 | 2007-04-03 | Chematur Eng Ab | Förfarande och system för överkritisk vattenoxidation av en ström som innehåller oxiderbart material |
SE528840C2 (sv) * | 2004-11-15 | 2007-02-27 | Chematur Eng Ab | Reaktor och förfarande för överkritisk vattenoxidation |
JP2006169401A (ja) * | 2004-12-16 | 2006-06-29 | Chubu Electric Power Co Inc | 改質プラント及び方法 |
US20070045881A1 (en) * | 2005-09-01 | 2007-03-01 | Aguirre Everardo L M | Air humidifier |
US7947165B2 (en) * | 2005-09-14 | 2011-05-24 | Yeda Research And Development Co.Ltd | Method for extracting and upgrading of heavy and semi-heavy oils and bitumens |
US7938954B2 (en) * | 2005-12-16 | 2011-05-10 | Chevron U.S.A. Inc. | Systems and methods for producing a crude product |
DE102006008809B4 (de) | 2006-02-25 | 2008-04-24 | Junghans Microtec Gmbh | Mechanischer Raketenzünder |
US20070289898A1 (en) * | 2006-06-14 | 2007-12-20 | Conocophillips Company | Supercritical Water Processing of Extra Heavy Crude in a Slurry-Phase Up-Flow Reactor System |
US7730958B2 (en) * | 2006-08-31 | 2010-06-08 | David Randolph Smith | Method and apparatus to enhance hydrocarbon production from wells |
JP2008094829A (ja) * | 2006-10-12 | 2008-04-24 | Kocat Inc | Mc型均一触媒およびo2/co2混合気体を用いた有機酸またはその誘導体の製造方法 |
US20080099378A1 (en) * | 2006-10-31 | 2008-05-01 | Chevron U.S.A. Inc. | Process and reactor for upgrading heavy hydrocarbon oils |
US20080099377A1 (en) * | 2006-10-31 | 2008-05-01 | Chevron U.S.A. Inc. | Process for upgrading heavy hydrocarbon oils |
US20080099376A1 (en) * | 2006-10-31 | 2008-05-01 | Chevron U.S.A. Inc. | Upgrading heavy hydrocarbon oils |
US20080099374A1 (en) * | 2006-10-31 | 2008-05-01 | Chevron U.S.A. Inc. | Reactor and process for upgrading heavy hydrocarbon oils |
EP2099624A1 (en) | 2006-12-01 | 2009-09-16 | The Four Wheeled Motorcycle Company Limited | Suspension system |
WO2008085436A1 (en) | 2006-12-27 | 2008-07-17 | Case Western Reserve University | Situated simulation for training, education, and therapy |
US8052848B2 (en) * | 2007-06-26 | 2011-11-08 | The Penn State Research Foundation | Ultrasonic and microwave methods for enhancing the rate of a chemical reaction and apparatus for such methods |
KR101606680B1 (ko) * | 2007-11-28 | 2016-03-25 | 사우디 아라비안 오일 컴퍼니 | 고도로 밀납을 함유하는 원유의 유동점 및 파라핀 함량을 낮추기 위한 연속 공정 |
US20090166261A1 (en) | 2007-12-28 | 2009-07-02 | Chevron U.S.A. Inc. | Upgrading heavy hydrocarbon oils |
US20090166262A1 (en) | 2007-12-28 | 2009-07-02 | Chevron U.S.A. Inc. | Simultaneous metal, sulfur and nitrogen removal using supercritical water |
US8394260B2 (en) * | 2009-12-21 | 2013-03-12 | Saudi Arabian Oil Company | Petroleum upgrading process |
-
2008
- 2008-11-24 KR KR1020157033396A patent/KR101606680B1/ko active IP Right Grant
- 2008-11-24 BR BRPI0819687A patent/BRPI0819687A2/pt active Search and Examination
- 2008-11-24 MX MX2010005854A patent/MX2010005854A/es unknown
- 2008-11-24 CN CN200880125755.7A patent/CN101970610B/zh not_active Expired - Fee Related
- 2008-11-24 US US12/277,270 patent/US8025790B2/en active Active
- 2008-11-24 WO PCT/US2008/084530 patent/WO2009073442A2/en active Application Filing
- 2008-11-24 CN CN200880125762.7A patent/CN101970609B/zh not_active Expired - Fee Related
- 2008-11-24 WO PCT/US2008/084526 patent/WO2009073440A2/en active Application Filing
- 2008-11-24 US US12/277,268 patent/US9295957B2/en active Active
- 2008-11-24 BR BRPI0820363-6A patent/BRPI0820363B1/pt not_active IP Right Cessation
- 2008-11-24 MX MX2010005855A patent/MX2010005855A/es unknown
- 2008-11-24 EP EP08857382A patent/EP2231823A2/en not_active Ceased
- 2008-11-24 EP EP08855883.8A patent/EP2240556B1/en not_active Not-in-force
- 2008-11-24 WO PCT/US2008/084542 patent/WO2009073446A2/en active Application Filing
- 2008-11-24 US US12/277,275 patent/US7740065B2/en active Active
- 2008-11-24 DK DK08855883.8T patent/DK2240556T3/en active
- 2008-11-24 JP JP2010536103A patent/JP5346036B2/ja not_active Expired - Fee Related
- 2008-11-24 US US12/277,263 patent/US10010839B2/en active Active
- 2008-11-24 JP JP2010536096A patent/JP5202644B2/ja active Active
- 2008-11-24 KR KR1020107014239A patent/KR101419977B1/ko active IP Right Grant
- 2008-11-24 WO PCT/US2008/084543 patent/WO2009073447A2/en active Application Filing
- 2008-11-24 CN CN2008801257542A patent/CN101983227B/zh not_active Expired - Fee Related
- 2008-11-24 KR KR1020107013449A patent/KR20100105611A/ko not_active Application Discontinuation
- 2008-11-24 KR KR1020107014333A patent/KR101504384B1/ko active IP Right Grant
- 2008-11-24 EP EP08858300.0A patent/EP2222819B1/en active Active
- 2008-11-24 CN CN200880125761.2A patent/CN101970611B/zh not_active Expired - Fee Related
- 2008-11-24 MX MX2010005852A patent/MX357637B/es active IP Right Grant
- 2008-11-24 US US12/277,255 patent/US8815081B2/en active Active
- 2008-11-24 JP JP2010536099A patent/JP5290317B2/ja not_active Expired - Fee Related
- 2008-11-24 MX MX2010005851A patent/MX2010005851A/es unknown
- 2008-11-24 KR KR1020107014331A patent/KR101577082B1/ko active IP Right Grant
- 2008-11-24 BR BRPI0820360A patent/BRPI0820360B1/pt not_active IP Right Cessation
- 2008-11-24 JP JP2010536102A patent/JP5269089B2/ja active Active
- 2008-11-24 EP EP08857144A patent/EP2245119A2/en not_active Ceased
- 2008-11-24 BR BRPI0820362 patent/BRPI0820362A2/pt not_active IP Right Cessation
- 2008-11-25 KR KR1020107014334A patent/KR101419978B1/ko active IP Right Grant
- 2008-11-25 EP EP08865032.0A patent/EP2231824B1/en not_active Not-in-force
- 2008-11-25 JP JP2010536095A patent/JP5514118B2/ja not_active Expired - Fee Related
- 2008-11-25 ES ES08865032.0T patent/ES2582392T3/es active Active
- 2008-11-25 MX MX2010005853A patent/MX2010005853A/es active IP Right Grant
- 2008-11-25 CN CN200880125753.8A patent/CN102159675B/zh not_active Expired - Fee Related
- 2008-11-25 BR BRPI0819674A patent/BRPI0819674A2/pt not_active Application Discontinuation
- 2008-11-25 WO PCT/US2008/084520 patent/WO2009082585A2/en active Application Filing
-
2011
- 2011-08-18 US US13/212,509 patent/US8216520B2/en active Active
-
2014
- 2014-07-23 US US14/338,749 patent/US9656230B2/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4543177A (en) * | 1984-06-11 | 1985-09-24 | Allied Corporation | Production of light hydrocarbons by treatment of heavy hydrocarbons with water |
US4818370A (en) * | 1986-07-23 | 1989-04-04 | Cities Service Oil And Gas Corporation | Process for converting heavy crudes, tars, and bitumens to lighter products in the presence of brine at supercritical conditions |
EP0978552A2 (de) * | 1998-08-06 | 2000-02-09 | ANDERSEN, Kjeld | Verfahren zum katalytischem Entfernen von Metallverbindungen aus Schwerölen |
EP1862527A1 (en) * | 2006-05-30 | 2007-12-05 | Environmental Consulting Catalysts & Processes for a Sustainable Development | A process for the production of light hydrocarbons from natural bitumen or heavy oils |
Also Published As
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101983227B (zh) | 降低原油酸度的方法 | |
CN102834489B (zh) | 将水、氧化剂和重油在超临界温度和压力条件下混合,并最终使混合物经受微波处理的方法 | |
EP3567089A1 (en) | Method to remove metals from petroleum | |
EP3565873B1 (en) | Processes for power generation | |
US8563792B2 (en) | Systems and methods of generating renewable diesel | |
CN105623736A (zh) | 一种高温煤焦油全馏分催化热裂解方法 | |
CN111849555A (zh) | 一种加氢处理含卤素废油的系统及方法 | |
NL2024523B1 (en) | Method for co-processing | |
JP2017214507A (ja) | 石油精製装置のナフサ脱硫装置における脱硫ナフサ中の塩酸の中和方法 | |
CN215947199U (zh) | 一种用于废矿物油再生的预处理系统装置 | |
CN115678601A (zh) | 一种重质原油的无氢化升级工艺 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130814 |