WO2014071041A1 - Process for reducing the viscosity of heavy residual crude oil during refining - Google Patents
Process for reducing the viscosity of heavy residual crude oil during refining Download PDFInfo
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- WO2014071041A1 WO2014071041A1 PCT/US2013/067813 US2013067813W WO2014071041A1 WO 2014071041 A1 WO2014071041 A1 WO 2014071041A1 US 2013067813 W US2013067813 W US 2013067813W WO 2014071041 A1 WO2014071041 A1 WO 2014071041A1
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- WIPO (PCT)
- Prior art keywords
- amine
- group
- esters
- viscosity
- combinations
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 46
- 238000007670 refining Methods 0.000 title description 12
- 239000010779 crude oil Substances 0.000 title description 11
- 239000000654 additive Substances 0.000 claims abstract description 33
- 150000002148 esters Chemical class 0.000 claims abstract description 30
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 30
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 30
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 150000001408 amides Chemical class 0.000 claims abstract description 23
- 150000001412 amines Chemical class 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 229920000768 polyamine Polymers 0.000 claims abstract description 11
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 10
- 150000002462 imidazolines Chemical class 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 3
- 230000000996 additive effect Effects 0.000 claims description 21
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- 150000002924 oxiranes Chemical class 0.000 claims description 7
- KSSJBGNOJJETTC-UHFFFAOYSA-N COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC Chemical compound COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC KSSJBGNOJJETTC-UHFFFAOYSA-N 0.000 claims description 6
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 4
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- 239000003784 tall oil Substances 0.000 claims description 4
- WBRBLKRDTHYRRV-MDWZMJQESA-N 3-[(e)-4,6,8-trimethylnon-2-en-2-yl]oxolane-2,5-dione Chemical compound CC(C)CC(C)CC(C)\C=C(/C)C1CC(=O)OC1=O WBRBLKRDTHYRRV-MDWZMJQESA-N 0.000 claims description 3
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 125000005907 alkyl ester group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 3
- 150000003580 thiophosphoric acid esters Chemical class 0.000 claims description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 229930003836 cresol Natural products 0.000 claims description 2
- 125000002636 imidazolinyl group Chemical group 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 239000012968 metallocene catalyst Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 150000001451 organic peroxides Chemical class 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000009472 formulation Methods 0.000 abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000009835 boiling Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000013031 physical testing Methods 0.000 description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- -1 ethylene diamine, tetraethyl Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
-
- 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
- C10G75/04—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of antifouling agents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/1955—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by an alcohol, ether, aldehyde, ketonic, ketal, acetal radical
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
-
- 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
- C10G2300/1077—Vacuum residues
Definitions
- This invention relates to refining crude oil. This invention particularly relates to improving processing of heavy residual crude oil during refining.
- the crude oil and resultant process streams may be subjected to distillation, thermal cracking, catalytic conversion, and various other treatments.
- Cracking is the process whereby complex organic molecules such as kerogens or heavy hydrocarbons are broken down into simpler molecules (e.g. light hydrocarbons) by the breaking of carbon-carbon bonds in the precursors.
- the invention is a process for modifying heavy residual hydrocarbons to reduce viscosity comprising admixing the heavy residual hydrocarbons with an additive comprising a first component selected from the group consisting of (alkoxylated)-(di or tri)-alkyl phenol - aldehyde (amine) resins; a-olefin - maleic anhydride co-polymers and grafted polymers including half ester/amide and full ester/amide derivatives; and combinations thereof; and a second component which is a synergist and selected from the group consisting of polyamines, amidoamines, imidazolines, and combinations thereof.
- an additive comprising a first component selected from the group consisting of (alkoxylated)-(di or tri)-alkyl phenol - aldehyde (amine) resins; a-olefin - maleic anhydride co-polymers and grafted polymers including half ester/amide and full ester/amide derivatives;
- the invention is a process for modifying heavy residual hydrocarbons to reduce viscosity comprising admixing the heavy residual hydrocarbons with an additive comprising a first component selected from the group consisting of (alkoxylated)-(di or tri)-alkyl phenol - aldehyde (amine) resins; a-olefin - maleic anhydride co-polymers and grafted polymers including half ester/amide and full ester/amide derivatives; and combinations thereof.
- a first component selected from the group consisting of (alkoxylated)-(di or tri)-alkyl phenol - aldehyde (amine) resins; a-olefin - maleic anhydride co-polymers and grafted polymers including half ester/amide and full ester/amide derivatives; and combinations thereof.
- the invention is a process for modifying heavy residual hydrocarbons comprising admixing the heavy residual hydrocarbons with an additive.
- the additive is prepared from a formulation including: a first component selected from the group consisting of (alkoxylated)-(di or tri)-alkyl phenol - aldehyde (amine) resins; a-Olefin - maleic anhydride co-polymers and grafted polymers including half ester/amide and full ester/amide derivatives; and combinations thereof.
- the formulation also includes a second component which is a synergist and selected from the group consisting of polyamines, amidoamines, imidazolines, and combinations thereof.
- the term “heavy residual hydrocarbon” means a hydrocarbon having carbon chain length of from about C 2 o to about C 70 . When derived during refining, this material is often referred to as a “resid.” Also, for the purposes of this application, the term “heavy residual hydrocarbon” can include hydrocarbons having the same chain length but derived from processes other than normal refining.
- the additive is prepared from a formulation comprising: a first component selected from the group consisting of (alkoxylated)-(di or tri)-alkyl phenol - aldehyde (amine) resins; a-olefin - maleic anhydride co-polymers and grafted polymers including half ester/amide and full ester/amide derivatives; and combinations thereof; and a second component which is a synergist and selected from the group consisting of polyamines, amidoamines, imidazolines, and combinations thereof.
- a first component selected from the group consisting of (alkoxylated)-(di or tri)-alkyl phenol - aldehyde (amine) resins
- a-olefin - maleic anhydride co-polymers and grafted polymers including half ester/amide and full ester/amide derivatives and combinations thereof
- a second component which is a synergist and selected from the group consisting of polyamines, amid
- Alkylphenol-formaldehyde resins are typically prepared by the acid or base catalyzed condensation of an alkylphenol with formaldehyde. Alkyl groups are straight or branched and contain about 3 to about 18, preferably about 4 to about 12 carbon atoms.
- Representative acid catalysts include dodecylbenzenesulfonic acid (DDBSA), toluene sulfonic acid, boron trifluoride, oxalic acid, and the like.
- Representative base catalysts include potassium hydroxide, sodium methoxide, sodium hydroxide, and the like.
- the alkylphenol-formaldehyde resins have a molecular weight (Mn) of about 1 ,000 to about 50,000. In another embodiment, the alkylphenol-formaldehyde resins have a molecular weight of about 1 ,000 to about 10,000.
- Alkylphenol-formaldehyde resins may be oxyalkylated by contacting the alkylphenol-formaldehyde resins with an epoxide such as ethylene oxide in the presence of a basic catalyst.
- an epoxide such as ethylene oxide
- such resins may be prepared using sodium hydroxide or potassium hydroxide.
- the molar ratio of epoxide to OH group on the resin may be from about 1 to about 50. In some embodiments, the molar ratio is from about 2 to about 8. In still other embodiments, the molar ratio is from about 3 to about 7.
- the alkylphenol formaldehyde resins and oxyalkylated alkylphenol formaldehyde resins may be prepared using any method known to be useful to those of ordinary skill in the art of preparing such resins.
- the resins may be prepared with ethylene oxide and/or propylene oxide.
- the alkyl groups may have from about 1 to about 30 carbons.
- Phenols that are useful include, but are not limited to phenol, cresol, and resorcinol.
- Aldehydes include but are not limited to formaldehyde, acetaldehyde, propylaldehyde, and butyraldehyde and mixtures thereof.
- Amines, useful for Mannich resins may be selected from the any amine, but in some embodiments they may be selected from the group consisting of ethylene diamine, triethylene tetra-amine, tributyl tetra-amine, tetraethyl penta-amine, pentaethyl hexa-amine, hexaethyl hepta-amine, heptaethyl octa-amine, bis-hexamethytriamine, and mixtures thereof.
- the additive when the additive includes an a-olefin - maleic anhydride co-polymer and/or grafted polymer including half ester/amide and full ester/amide derivatives, they may be prepared admixing the monomers and using a catalyst or even heat to polymerize the monomers.
- Catalysts useful with the method of the application include, but are not limited to free radical initiator, organic peroxides, chromium catalysts, Ziegler-Natta catalysts and metallocene catalysts.
- the additives useful with some embodiments of the invention may include other organic compounds and organic solvents.
- Organic compounds useful with some embodiments of the additives include, but are not limited to amines and esters.
- a method of the invention may be practiced using additives including triethyl tetra-amine, tributyl tetra-amine, ethylene diamine, tetraethyl penta-amine, ethyl acetate, propyl acetate, ethyl butyrate, and the like and combinations thereof.
- the synergists include polyamines, amidoamines, imidazolines, and combinations thereof.
- the synergist is a polyamine, in some embodiments is may be selected from polymers of ethylene diamine, triethylene tetra-amine, tributyl tetra-amine, tetraethyl penta-amine, pentaethyl hexa-amine, hexaethyl hepta-amine, heptaethyl octa-amine, bis- hexamethytriamine, and mixtures thereof.
- the synergists may also be the quaternary ammonium salts of these compounds.
- the synergist when it is an amidoamines, in some embodiments, it may be a tall oil fatty acid amide prepared using one of ethylene diamine, triethylene tetra-amine, tributyl tetra-amine, tetraethyl penta-amine, pentaethyl hexa-amine, hexaethyl hepta-amine, heptaethyl octa-amine, bis- hexamethytriamine, and mixtures thereof.
- the synergists may also be the quaternary ammonium salts of these compounds.
- the synergist when it is an imidazoline, it may be prepared using a tall oil fatty acid-amidoamine and a polyamine as detailed above. It may be further substituted by forming alkyl esters, phosphate esters, thiophosphate esters, Tetra-propenyl succinic anhydride (TPSA), dodecylsuccinic anhydride, amides/esters alkylphosphate esters, arylphosphate esters along the backbone.
- TPSA Tetra-propenyl succinic anhydride
- the synergists may also be the quaternary ammonium salts of these compounds.
- their concentration in heavy resid hydrocarbons may be from about 0.1 to about 10% by weight. In other embodiments, the concentration may be from about 0.1 to about 0.5 weight %.
- the organic solvents useful with some embodiments of the invention may include but are not limited to: ethyl benzene, xylene, toluene, and the like.
- a solvent When a solvent is present in the additive, it may be present at a concentration of from about 5 w/v percent to about 95 w/v percent. In other embodiments, the solvent if present at all is present at a concentration of from about 10 to 90 percent. In still other embodiments, the solvent may be present at a concentration of from about 15 to about 85 percent.
- the additives of the application are effective at reducing the viscosity of resids.
- the additives may reduce resid viscosity by from 20 to 70 percent (Viscosity, cP@ 50°C). In some embodiments, the reduction could be from about 35 to about 60%. In other embodiments, the reduction could be from about 40 to 60%.
- the invention is a process for modifying heavy residual hydrocarbons to reduce viscosity comprising admixing the heavy residual hydrocarbons with an additive comprising a first component selected from the group consisting of (alkoxylated)-(di or tri)-alkyl phenol - aldehyde (amine) resins; a-olefin - maleic anhydride co-polymers and grafted polymers including half ester/amide and full ester/amide derivatives; and combinations thereof. While not as effective as a blend of the resin and a synergist, the resin, by itself can lower resid viscosity.
- an additive comprising a first component selected from the group consisting of (alkoxylated)-(di or tri)-alkyl phenol - aldehyde (amine) resins; a-olefin - maleic anhydride co-polymers and grafted polymers including half ester/amide and full ester/amide derivatives; and combinations thereof
- Some of the components of the additives of the application may have boiling points or vapor pressures that would cause those components to vaporize and be wasted if heated too quickly or under conditions that would not favor incorporation of those components into the heavy resid hydrocarbon. It follows then that when the resid is to be heated to a point near or above the boiling point of the additive component, the resid and additive are to be admixed first and then gradually heated to allow all, or as much as possible, of the additive component to be incorporated into the resid.
- the additives of the application may be Incorporated into the resids being treated in any way known to be useful to those of ordinary skill in the art
- the additives of the application advantageously exhibit a synergism.
- the two components of the additive formulations coming together have a substantially greater impact on improving the physical properties of the modified resid than either component does when acting alone.
- Embodiments of the methods of the application may be employed in any application where a resid is being refined, transported, or moved and it would be desirable to avoid having to reheat the resid.
- an additive of the invention is employed within a refinery to allow a resid that, unmodified, would be too viscous to move through a unit without the use of a cutter stock or a solvent.
- the additive is used to reduce the amount of energy necessary to pump a resid.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Lubricants (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Additives may be used to decrease the viscosity of heavy residual hydrocarbons. The additives are prepared using a formulation comprising: a first component selected from the group consisting of (alkoxylated)-(di or tri)- alkyl phenol - aldehyde (amine) resins; a-Olefin - maleic anhydride co¬ polymers and grafted polymers including half ester/amide and full ester/amide derivatives; and combinations thereof; and a second component which is a synergist and selected from the group consisting of polyamines, amidoamines, imidazolines, and combinations thereof.
Description
PROCESS FOR REDUCING THE VISCOSITY OF HEAVY RESIDUAL CRUDE OIL DURING REFINING
BACKGROUND OF THE APPLICATION
1 . FIELD OF THE INVENTION
[0001] This invention relates to refining crude oil. This invention particularly relates to improving processing of heavy residual crude oil during refining.
2. BACKGROUND OF THE PRIOR ART
[0002] Refining is the process of treating raw hydrocarbon and its conversion into lighter, higher octane number components. The development of the internal combustion engine led to the production of gasoline and diesel fuels. While simple gasoline was sufficient for automobiles, it was the airplane that created a need for high-octane aviation gasoline and then for jet fuels. In addition to fuels, refineries now produce a variety of products such as lubricants but also including many required as initial feed-stocks for the petrochemical industry.
[0003] During the course of refining crude oil, the crude oil and resultant process streams may be subjected to distillation, thermal cracking, catalytic conversion, and various other treatments. Cracking is the process whereby complex organic molecules such as kerogens or heavy hydrocarbons are broken down into simpler molecules (e.g. light hydrocarbons) by the breaking of carbon-carbon bonds in the precursors.
[0004] During distillation, the higher boiling compounds are separated from compounds often having a higher molecular weight and greater viscosity. After removal of the distillate, the resulting bottoms may be subjected to further cracking until, finally, all that is left is bitumen or coke. Even these
compounds have value in today's markets, but most often it would be desirable to produce more rather than less of the comparatively low boiling and more valuable distillates.
[0005] Unfortunately, as the viscosity of the heavy distillation bottoms increases, there is a corresponding increase in the difficulty of handling (moving and further refining) such heavy hydrocarbons. In some circumstances, the bottoms can even solidify thereby blocking fluid movement. It would be desirable in the art of refining hydrocarbons to be able to reduce the viscosity of heavy residual crude oil economically and without introducing materials which could complicate further processing.
SUMMARY OF THE INVENTION
[0006] In one aspect, the invention is a process for modifying heavy residual hydrocarbons to reduce viscosity comprising admixing the heavy residual hydrocarbons with an additive comprising a first component selected from the group consisting of (alkoxylated)-(di or tri)-alkyl phenol - aldehyde (amine) resins; a-olefin - maleic anhydride co-polymers and grafted polymers including half ester/amide and full ester/amide derivatives; and combinations thereof; and a second component which is a synergist and selected from the group consisting of polyamines, amidoamines, imidazolines, and combinations thereof.
[0007] In still another aspect, the invention is a process for modifying heavy residual hydrocarbons to reduce viscosity comprising admixing the heavy residual hydrocarbons with an additive comprising a first component selected from the group consisting of (alkoxylated)-(di or tri)-alkyl phenol - aldehyde (amine) resins; a-olefin - maleic anhydride co-polymers and grafted polymers including half ester/amide and full ester/amide derivatives; and combinations thereof.
DETAI LED DESCRI PTION OF THE INVENTION
[0008] In one aspect, the invention is a process for modifying heavy residual hydrocarbons comprising admixing the heavy residual hydrocarbons with an additive. The additive is prepared from a formulation including: a first component selected from the group consisting of (alkoxylated)-(di or tri)-alkyl phenol - aldehyde (amine) resins; a-Olefin - maleic anhydride co-polymers and grafted polymers including half ester/amide and full ester/amide derivatives; and combinations thereof. The formulation also includes a second component which is a synergist and selected from the group consisting of polyamines, amidoamines, imidazolines, and combinations thereof.
[0009] For the purposes of this application, the term "heavy residual hydrocarbon" means a hydrocarbon having carbon chain length of from about C2o to about C70. When derived during refining, this material is often referred to as a "resid." Also, for the purposes of this application, the term "heavy residual hydrocarbon" can include hydrocarbons having the same chain length but derived from processes other than normal refining.
[0010]As noted in the background of the application, it is often desirable to produce as much lower molecular weight hydrocarbon from crude oil as possible. One problem in doing so is that resid crude oil increases in viscosity as the resid crude oil is subject to more and more extractions of lower molecular weight hydrocarbons. If too much lower molecular weight hydrocarbons are removed from crude oil resid, then it may become too viscous at a point in the process where the process cannot further transport the resulting material for further processing. When this occurs, then expensive and time consuming efforts may have to be employed.
[0011] In some embodiments of the method of the application, the additive is prepared from a formulation comprising: a first component selected from the group consisting of (alkoxylated)-(di or tri)-alkyl phenol - aldehyde (amine) resins; a-olefin - maleic anhydride co-polymers and grafted polymers
including half ester/amide and full ester/amide derivatives; and combinations thereof; and a second component which is a synergist and selected from the group consisting of polyamines, amidoamines, imidazolines, and combinations thereof. Alkylphenol-formaldehyde resins are typically prepared by the acid or base catalyzed condensation of an alkylphenol with formaldehyde. Alkyl groups are straight or branched and contain about 3 to about 18, preferably about 4 to about 12 carbon atoms. Representative acid catalysts include dodecylbenzenesulfonic acid (DDBSA), toluene sulfonic acid, boron trifluoride, oxalic acid, and the like. Representative base catalysts include potassium hydroxide, sodium methoxide, sodium hydroxide, and the like. In an embodiment, the alkylphenol-formaldehyde resins have a molecular weight (Mn) of about 1 ,000 to about 50,000. In another embodiment, the alkylphenol-formaldehyde resins have a molecular weight of about 1 ,000 to about 10,000.
[0012] Alkylphenol-formaldehyde resins may be oxyalkylated by contacting the alkylphenol-formaldehyde resins with an epoxide such as ethylene oxide in the presence of a basic catalyst. For example, such resins may be prepared using sodium hydroxide or potassium hydroxide. The molar ratio of epoxide to OH group on the resin may be from about 1 to about 50. In some embodiments, the molar ratio is from about 2 to about 8. In still other embodiments, the molar ratio is from about 3 to about 7. The alkylphenol formaldehyde resins and oxyalkylated alkylphenol formaldehyde resins may be prepared using any method known to be useful to those of ordinary skill in the art of preparing such resins.
[0013] The resins, in some embodiments, may be prepared with ethylene oxide and/or propylene oxide. The alkyl groups may have from about 1 to about 30 carbons. Phenols that are useful include, but are not limited to phenol, cresol, and resorcinol. Aldehydes include but are not limited to formaldehyde, acetaldehyde, propylaldehyde, and butyraldehyde and mixtures thereof. Amines, useful for Mannich resins may be selected from the any amine, but in some embodiments they may be selected from the group
consisting of ethylene diamine, triethylene tetra-amine, tributyl tetra-amine, tetraethyl penta-amine, pentaethyl hexa-amine, hexaethyl hepta-amine, heptaethyl octa-amine, bis-hexamethytriamine, and mixtures thereof.
[0014] When the additive includes an a-olefin - maleic anhydride co-polymer and/or grafted polymer including half ester/amide and full ester/amide derivatives, they may be prepared admixing the monomers and using a catalyst or even heat to polymerize the monomers. Catalysts useful with the method of the application include, but are not limited to free radical initiator, organic peroxides, chromium catalysts, Ziegler-Natta catalysts and metallocene catalysts.
[0015] The additives useful with some embodiments of the invention may include other organic compounds and organic solvents. Organic compounds useful with some embodiments of the additives include, but are not limited to amines and esters. For example, a method of the invention may be practiced using additives including triethyl tetra-amine, tributyl tetra-amine, ethylene diamine, tetraethyl penta-amine, ethyl acetate, propyl acetate, ethyl butyrate, and the like and combinations thereof.
[0016] The synergists include polyamines, amidoamines, imidazolines, and combinations thereof. When the synergist is a polyamine, in some embodiments is may be selected from polymers of ethylene diamine, triethylene tetra-amine, tributyl tetra-amine, tetraethyl penta-amine, pentaethyl hexa-amine, hexaethyl hepta-amine, heptaethyl octa-amine, bis- hexamethytriamine, and mixtures thereof. The synergists may also be the quaternary ammonium salts of these compounds.
[0017] When the synergist is an amidoamines, in some embodiments, it may be a tall oil fatty acid amide prepared using one of ethylene diamine, triethylene tetra-amine, tributyl tetra-amine, tetraethyl penta-amine, pentaethyl hexa-amine, hexaethyl hepta-amine, heptaethyl octa-amine, bis- hexamethytriamine, and mixtures thereof. The synergists may also be the quaternary ammonium salts of these compounds.
[0018] When the synergist is an imidazoline, it may be prepared using a tall oil fatty acid-amidoamine and a polyamine as detailed above. It may be further substituted by forming alkyl esters, phosphate esters, thiophosphate esters, Tetra-propenyl succinic anhydride (TPSA), dodecylsuccinic anhydride, amides/esters alkylphosphate esters, arylphosphate esters along the backbone. The synergists may also be the quaternary ammonium salts of these compounds.
[0019] In employing the additives of the application, their concentration in heavy resid hydrocarbons may be from about 0.1 to about 10% by weight. In other embodiments, the concentration may be from about 0.1 to about 0.5 weight %.
[0020] The organic solvents useful with some embodiments of the invention may include but are not limited to: ethyl benzene, xylene, toluene, and the like. When a solvent is present in the additive, it may be present at a concentration of from about 5 w/v percent to about 95 w/v percent. In other embodiments, the solvent if present at all is present at a concentration of from about 10 to 90 percent. In still other embodiments, the solvent may be present at a concentration of from about 15 to about 85 percent.
[0021] The additives of the application are effective at reducing the viscosity of resids. When used at a concentration of 2500 ppm the additives may reduce resid viscosity by from 20 to 70 percent (Viscosity, cP@ 50°C). In some embodiments, the reduction could be from about 35 to about 60%. In other embodiments, the reduction could be from about 40 to 60%.
[0022] In one embodiment, the invention is a process for modifying heavy residual hydrocarbons to reduce viscosity comprising admixing the heavy residual hydrocarbons with an additive comprising a first component selected from the group consisting of (alkoxylated)-(di or tri)-alkyl phenol - aldehyde (amine) resins; a-olefin - maleic anhydride co-polymers and grafted polymers including half ester/amide and full ester/amide derivatives; and combinations thereof. While not as effective as a blend of the resin and a synergist, the resin, by itself can lower resid viscosity.
[0023] Some of the components of the additives of the application may have boiling points or vapor pressures that would cause those components to vaporize and be wasted if heated too quickly or under conditions that would not favor incorporation of those components into the heavy resid hydrocarbon. It follows then that when the resid is to be heated to a point near or above the boiling point of the additive component, the resid and additive are to be admixed first and then gradually heated to allow all, or as much as possible, of the additive component to be incorporated into the resid. The additives of the application may be Incorporated into the resids being treated in any way known to be useful to those of ordinary skill in the art
[0024] The additives of the application advantageously exhibit a synergism. The two components of the additive formulations coming together have a substantially greater impact on improving the physical properties of the modified resid than either component does when acting alone.
[0025] Embodiments of the methods of the application may be employed in any application where a resid is being refined, transported, or moved and it would be desirable to avoid having to reheat the resid. In another application, an additive of the invention is employed within a refinery to allow a resid that, unmodified, would be too viscous to move through a unit without the use of a cutter stock or a solvent. In still another embodiment, the additive is used to reduce the amount of energy necessary to pump a resid.
EXAMPLES
[0026] The following examples are provided to illustrate the present invention. The examples are not intended to limit the scope of the present invention and they should not be so interpreted. Amounts are in w/v parts or w/v percentages unless otherwise indicated.
Examples 1 -3 and Comparative Example A
[0027] A sample of a very heavy resid hydrocarbon (BP: 750° F to about 1300+° F) is tested for pour point according to ASTM D5950 and viscosity at
50°C using a scanning Brookfield viscometer. Results are recorded below in Table 1 as Comparative Example A. The same material is then treated with an additive which is a blend of an alkoxylated phenol resin (80%) and imidazoline (20%) at the dosages shown below in Table 1 where the results are also recorded.
Table 1
Examples 4-9 and Comparative Examples B-D
[0028] A sample of vacuum towers bottoms from a refining process, a common form of resid (BP750° F to about 1300° F), is tested for viscosity improvements using the additive of example 1 and a cutter stock. The cutter stock is a middle distillate hydrocarbon (BP: 350° F to about 700° F). The dosages and physical testing results are shown below in Table 2.
Table 2
Example 10 and Comparative Example E
[0029] A sample of virgin uncracked residue from a first distillation from a refining process (BP: 500° F to about 1200° F), is tested for viscosity improvements using the additive of Example 1 . The dosages and physical testing results are shown below in Table 3.
Table 3
Claims
1 . A process for modifying heavy residual hydrocarbons to reduce viscosity comprising admixing the heavy residual hydrocarbons with an additive comprising:
a first component selected from the group consisting of
(alkoxylated)-(di or tri)-alkyl phenol - aldehyde (amine) resins;
a-olefin - maleic anhydride co-polymers and grafted polymers including half ester/amide and full ester/amide derivatives; and
combinations thereof; and
a second component which is a synergist and selected from the group consisting of polyamines, amidoamines, imidazolines, and combinations thereof.
2. The process of Claim 1 wherein the (alkoxylated)-(di or tri)-alkyl phenol - aldehyde (amine) resins are prepared by the acid or base catalyzed condensation of an alkylphenol with an aldehyde.
3. The process of Claim 2 wherein alkyl groups of the alkylphenol are straight or branched and contain from about 3 to about 18 carbon atoms.
4. The process of Claim 3 wherein the alkyl group have from about 4 to about 12 carbon atoms.
5. The process of Claim 2 wherein the (alkoxylated) alkylphenol- formaldehyde resins have a molecular weight (Mn) of from about 1 ,000 to about 50,000.
6. The process of Claim 5 wherein the (alkoxylated) alkylphenol- formaldehyde resins have a molecular weight (Mn) of from about 1 ,000 to about 10,000.
7. The process of Claim 2 wherein the (alkoxylated)-(di or tri)-alkyl phenol - aldehyde (amine) resins are oxyalkylated by contacting the alkylphenol- formaldehyde resins with an epoxide.
8. The process of Claim 7 wherein the epoxide is selected from the group consisting of ethylene oxide, propylene oxide and combinations thereof.
9. The process of Claim 7 wherein the molar ratio of epoxide to OH group on the resin is from about 1 to about 50.
10. The process of Claim 9 wherein the molar ratio of epoxide to OH group on the resin is from about 2 to about 8.
1 1. The process of Claim 10 wherein the molar ratio of epoxide to OH group on the resin is from about 3 to about 7.
12. The process of Claim 2 wherein the alkylphenol is prepared using components selected from the group consisting of phenol, cresol, resorcinol, and combinations thereof.
13. The process of Claim 2 wherein the aldehyde is selected from the group consisting of formaldehyde, acetaldehyde, propylaldehyde, and butyraldehyde and combinations thereof.
14. The process of Claim 1 wherein the additive includes an a-olefin - maleic anhydride co-polymer and/or grafted polymer including half ester/amide and full ester/amide derivatives which is prepared by admixing monomers and using a catalyst or heat to polymerize the monomers.
15. The process of Claim 14 wherein the catalysts are selected from the group consisting of free radical initiators, organic peroxides, chromium catalysts, Ziegler-Natta catalysts and metallocene catalysts.
16. The process of Claim 1 wherein the synergist is a polyamine selected from the group consisting of polymers of ethylene diamine, triethylene tetra- amine, tributyl tetra-amine, tetraethyl penta-amine, pentaethyl hexa-amine, hexaethyl hepta-amine, heptaethyl octa-amine, bis-hexamethytriamine, and mixtures thereof.
17. The process of Claim 16 wherein the synergist is a quaternary ammonium salts of the compounds of Claim 16.
18. The process of Claim 1 wherein the synergist is an imidazoline prepared using a tall oil fatty acid-amidoamine and a polyamine.
19. The process of Claim 18 wherein the imidazoline is further substituted by forming alkyl esters, phosphate esters, thiophosphate esters, Tetra-propenyl succinic anhydride (TPSA), dodecylsuccinic anhydride, amides/esters alkylphosphate esters, arylphosphate esters along the backbone.
20 The process of Claim 18 wherein the synergists is a quaternary ammonium salts of an imidazoline prepared using a tall oil fatty acid- amidoamine and a polyamine.
21. The process of Claim 19 wherein the sysnergist is a quaternary ammonium salts of the imidazoline is further substituted by forming alkyl esters, phosphate esters, thiophosphate esters, Tetra-propenyl succinic anhydride (TPSA), dodecylsuccinic anhydride, amides/esters alkylphosphate esters, arylphosphate esters along the backbone.
22. The process of Claim 1 wherein the concentration of the additive in heavy resid hydrocarbons may be from about 0.1 to about 10% by weight.
23. The process of Claim 22 wherein the concentration may be from about 0.1 to about 0.5 weight %.
24. The process of Claim 1 wherein the additives are effective at reducing the viscosity of resids; when used at a concentration of 2500 ppm; reduces resid viscosity by from 20 to 70 percent (Viscosity, cP@ 50°C).
25. The process of Claim 24 wherein the reduction in viscosity is from about 35 to about 60%.
26. The process of Claim 25 wherein the reduction in viscosity is from about 40 to 60%.
27. A process for modifying heavy residual hydrocarbons to reduce viscosity comprising admixing the heavy residual hydrocarbons with an additive comprising a component selected from the group consisting of (alkoxylated)- (di or tri)-alkyl phenol - aldehyde (amine) resins; a-olefin - maleic anhydride co-polymers and grafted polymers including half ester/amide and full ester/amide derivatives; and combinations thereof.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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ES13852048T ES2777937T3 (en) | 2012-10-31 | 2013-10-31 | Process to reduce the viscosity of heavy residual crude during refining |
EP13852048.1A EP2914548B1 (en) | 2012-10-31 | 2013-10-31 | Process for reducing the viscosity of heavy residual crude oil during refining |
CA2889675A CA2889675C (en) | 2012-10-31 | 2013-10-31 | Process for reducing the viscosity of heavy residual crude oil during refining |
CN201380056607.5A CN104781194B (en) | 2012-10-31 | 2013-10-31 | Method for reducing heavy residual viscosity of crude during refining |
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US201261720806P | 2012-10-31 | 2012-10-31 | |
US61/720,806 | 2012-10-31 | ||
US14/067,429 | 2013-10-30 | ||
US14/067,429 US9212330B2 (en) | 2012-10-31 | 2013-10-30 | Process for reducing the viscosity of heavy residual crude oil during refining |
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WO2014071041A1 true WO2014071041A1 (en) | 2014-05-08 |
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PCT/US2013/067813 WO2014071041A1 (en) | 2012-10-31 | 2013-10-31 | Process for reducing the viscosity of heavy residual crude oil during refining |
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US (1) | US9212330B2 (en) |
EP (1) | EP2914548B1 (en) |
CN (1) | CN104781194B (en) |
CA (1) | CA2889675C (en) |
ES (1) | ES2777937T3 (en) |
PT (1) | PT2914548T (en) |
WO (1) | WO2014071041A1 (en) |
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WO2021018467A1 (en) | 2019-07-29 | 2021-02-04 | Clariant International Ltd | Wax inhibitors with improved flowability |
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CN113784943A (en) | 2019-04-29 | 2021-12-10 | 埃科莱布美国股份有限公司 | Oxygen-containing aminophenol compound and method for preventing polymerization of monomer |
CA3196257A1 (en) | 2020-10-21 | 2022-04-28 | Ashish Dhawan | Alkoxylated (hydroxyalkyl)aminophenol polymers and methods of use |
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Also Published As
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CN104781194A (en) | 2015-07-15 |
US9212330B2 (en) | 2015-12-15 |
US20140115953A1 (en) | 2014-05-01 |
CA2889675A1 (en) | 2014-05-08 |
EP2914548B1 (en) | 2020-01-01 |
PT2914548T (en) | 2020-03-25 |
CN104781194B (en) | 2017-11-28 |
EP2914548A4 (en) | 2016-07-20 |
ES2777937T3 (en) | 2020-08-06 |
CA2889675C (en) | 2017-04-25 |
EP2914548A1 (en) | 2015-09-09 |
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