EP3234073A2 - Methods and apparatuses for co-processing pyrolysis oil - Google Patents
Methods and apparatuses for co-processing pyrolysis oilInfo
- Publication number
- EP3234073A2 EP3234073A2 EP15870701.8A EP15870701A EP3234073A2 EP 3234073 A2 EP3234073 A2 EP 3234073A2 EP 15870701 A EP15870701 A EP 15870701A EP 3234073 A2 EP3234073 A2 EP 3234073A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- stream
- pyrolysis oil
- surfactant
- emulsion
- mixing
- 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.)
- Withdrawn
Links
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 130
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000004094 surface-active agent Substances 0.000 claims abstract description 82
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 71
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 71
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 70
- 238000002156 mixing Methods 0.000 claims abstract description 58
- 239000000839 emulsion Substances 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000004231 fluid catalytic cracking Methods 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000000446 fuel Substances 0.000 claims abstract description 11
- 239000003921 oil Substances 0.000 claims description 126
- 150000002632 lipids Chemical class 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 34
- 150000002148 esters Chemical class 0.000 claims description 25
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 21
- 239000000194 fatty acid Substances 0.000 claims description 21
- 229930195729 fatty acid Natural products 0.000 claims description 21
- 150000004665 fatty acids Chemical class 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 claims description 10
- 150000001298 alcohols Chemical class 0.000 claims description 10
- 239000002736 nonionic surfactant Substances 0.000 claims description 9
- 229940114072 12-hydroxystearic acid Drugs 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- -1 polyoxyethylene units Polymers 0.000 claims description 8
- 239000012530 fluid Substances 0.000 claims description 7
- 238000004891 communication Methods 0.000 claims description 6
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 claims description 4
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 150000001261 hydroxy acids Chemical class 0.000 claims description 4
- 229920001281 polyalkylene Polymers 0.000 claims description 4
- 229920001522 polyglycol ester Polymers 0.000 claims description 4
- 229940014800 succinic anhydride Drugs 0.000 claims description 4
- 235000019198 oils Nutrition 0.000 description 108
- 239000000047 product Substances 0.000 description 20
- 239000007789 gas Substances 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002029 lignocellulosic biomass Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 description 3
- 239000008158 vegetable oil Substances 0.000 description 3
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 235000014698 Brassica juncea var multisecta Nutrition 0.000 description 1
- 240000002791 Brassica napus Species 0.000 description 1
- 235000006008 Brassica napus var napus Nutrition 0.000 description 1
- 235000006618 Brassica rapa subsp oleifera Nutrition 0.000 description 1
- 244000188595 Brassica sinapistrum Species 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012075 bio-oil Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000008162 cooking oil Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940013317 fish oils Drugs 0.000 description 1
- 238000002304 fractionated pyrolysis Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
-
- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
-
- 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
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
- C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
-
- 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
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
- C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Definitions
- the technical field generally relates to methods and apparatuses for coprocessing pyrolysis oil. More particularly, the technical field relates to methods and apparatuses for co-processing pyrolysis oil with another feedstock stream in a Fluid Catalyst Cracking (FCC) unit to form an FCC product stream containing renewable components.
- FCC Fluid Catalyst Cracking
- Bio- derived sources include biomass, such as plant oils including corn, rapeseed, canola, soybean and algal oils; animal fats such as tallow, fish oils and various waste streams such as yellow and brown greases; and sewage sludge.
- Bio- derived sources also include carbon-based products formed by engineered organisms, such as engineered algae cells.
- Lignocellulosic biomass is particularly suited for processing into pyrolysis oil.
- Such biomass may be converted to pyrolysis oil by rapid thermal processing or by pyrolysis technologies such as a bubble-column, auger or intermediate pyrolysis systems.
- pyrolysis oil is less expensive.
- pyrolysis oil has a much higher oxygen content (45%) compared to vegetable oil feedstocks (1 1 %). Further, it may contain up to 35% water and also contain acidic
- the high water content and acidic content of pyrolysis oil makes processing in FCC units challenging. Specifically, the high volume of water in a pyrolysis stream introduced to an FCC unit negatively impacts the heat balance of the FCC unit. Further, the acid content of the pyrolysis stream can potentially harm FCC catalysts, such as through accelerated coke formation, and reduce the FCC unit product yield.
- a method for co-processing a pyrolysis oil stream and a hydrocarbon stream includes mixing the pyrolysis oil stream and the hydrocarbon stream with a surfactant to form an emulsion.
- the method introduces the emulsion to a reaction zone in an fluid catalytic cracking (FCC) unit.
- FCC fluid catalytic cracking
- the method includes contacting the emulsion with a catalyst in the reaction zone to form an FCC product stream.
- a method for co-processing a pyrolysis oil stream and a lipid stream includes mixing the pyrolysis oil stream and the lipid stream with a surfactant to form a mixture.
- the method introduces the mixture to a reaction zone in an fluid catalytic cracking (FCC) unit. Further, the method includes contacting the mixture with a catalyst in the reaction zone to form an FCC product stream.
- FCC fluid catalytic cracking
- a fuel processing apparatus in another embodiment, includes a pyrolysis oil source and a mixing unit in fluid communication with the pyrolysis oil source and configured to mix pyrolysis oil, a hydrocarbon feedstock, and a surfactant to form an emulsion.
- the fuel processing apparatus includes a pyrolysis oil source and a mixing unit in fluid communication with the pyrolysis oil source and configured to mix pyrolysis oil, a hydrocarbon feedstock, and a surfactant to form an emulsion.
- processing apparatus also includes a fluid catalytic cracking (FCC) unit in fluid communication with the mixing unit and including a reaction chamber suitable for contacting components of the emulsion with a catalyst to form an FCC product stream.
- FCC fluid catalytic cracking
- FIGURE is a schematic diagram of an apparatus and a method for co-processing a pyrolysis oil stream in accordance with an exemplary
- embodiments contemplated herein relate to methods and apparatuses for co-processing pyrolysis oil.
- embodiments herein provide for co-processing pyrolysis oil in an FCC reactor with another stream, such as a hydrocarbon stream and/or a lipid stream.
- An exemplary process uses a surfactant to form an emulsion from the pyrolysis oil, the hydrocarbon stream, and the surfactant.
- the emulsion is fed directly into the FCC reactor through conventional means, i.e., no special injection equipment is needed.
- the FCC reactor converts the emulsion into an FCC product stream including upgraded fuel products.
- the FCC product stream may be distilled into various streams including naphtha, light coker oil, and decant oil.
- the FIGURE illustrates an exemplary apparatus 10 utilizing an exemplary method for co-processing a pyrolysis oil stream 12 with a hydrocarbon stream 14 and/or a lipid stream 16 to form an FCC product stream 18.
- the pyrolysis oil stream 12 is provided by a pyrolysis oil source 15.
- the pyrolysis oil source 15 may be a pyrolysis reactor for converting biomass into pyrolysis oil.
- Pyrolysis is the thermal decomposition of a substance into its elemental components and/or smaller molecules. Pyrolysis typically requires temperatures of 325°C or higher to sufficiently decompose the feedstock to produce pyrolysis products. Pyrolysis of a biomass feedstock typically produces water, pyrolysis oil or bio-oil, char, and gases such as hydrogen, carbon monoxide, carbon dioxide, methane and other light hydrocarbons that do not condense under typical conditions,
- Pyrolysis of lignocellulosic biomass typically produces organic compounds such as lignin fragments, aldehydes, carboxylic acids, phenols, furfurals, alcohols, and ketones, as well as water.
- the exemplary pyrolysis oil stream 12 is provided to apparatus 10 as a full, non-fractionated pyrolysis reaction product.
- the pyrolysis oil stream 12 may include from 15 volume percent (vol %) water to 35 vol% water.
- the pyrolysis oil stream 12 is fed into a tank or settler 25. Further, the tank 25 receives the hydrocarbon stream 14 and/or lipid stream 16.
- An exemplary hydrocarbon stream 14 may be any appropriate petroleum- based fraction. In an embodiment the hydrocarbon stream 14 is a diesel stream or an atmospheric gas oil stream.
- the hydrocarbon stream 14 is provided by a hydrocarbon source 31 , such as a processing unit located elsewhere in the apparatus 10.
- the hydrocarbon stream 14 is fed to a tank or drum 32. As shown, drum 32 also receives a surfactant 33. In an exemplary embodiment, the surfactant is dissolved in the hydrocarbon stream 14 in drum 32.
- Drum 32 may be provided with a mixing apparatus to facilitate dissolution.
- An exemplary lipid stream 16 may be any suitable lipid stream including vegetable oils, animal fats, algal oils, used cooking oil, triglycerides, esters, fatty acids, or mixtures thereof.
- the lipid stream 16 is provided by a lipid source 36, such as a processing unit located elsewhere in the apparatus 10.
- lipid stream 16 is fed to a tank or drum 37.
- drum 37 also receives a surfactant 38.
- the surfactant 38 is dissolved in the lipid stream 16 in drum 37.
- Drum 37 may be provided with a mixing apparatus to facilitate dissolution.
- each surfactant 33 and 38 is a non-ionic surfactant.
- Surfactant 33 may be the same as or different from surfactant 38.
- the surfactant 33 and/or 38 may be or include sorbitan esters of fatty acids, polyglycol esters of fatty acids, mono-glycerides, di-glycerides, a mixture of mono-glycerides and di-glycerides, esters of monofunctional fatty acids with poly- 12-hydroxystearic acid, esters of monofunctional alcohols with poly-12- hydroxystearic acid, polymeric esters of difunctional fatty acids, polymeric esters of difunctional alcohols, esters of fatty acids with polyethylene glycol having up to five polyoxyethylene units, esters of hydroxyacids with polyethylene glycol having up to five polyoxyethylene units, succinic anhydride or succinimide-modified linear and branched polyalkylene compounds. Blends of two of more surfactants can be used. In some cases
- a stream 34 of hydrocarbon with dissolved surfactant and/or a stream 39 of lipids with dissolved surfactant is fed to the tank 25.
- An exemplary tank 25 is provided with a motor driven multi-bed agitator. As a result of the agitation, an effluent 40 is formed.
- the effluent 40 may be formed as an emulsion and a dispersed phase.
- the stream 34 and pyrolysis oil stream 12 are fed in proportion to one another to form the effluent 40 with a content of from 1 to 55 vol % pyrolysis oil stream, from 45 to 50 vol % hydrocarbon stream, and 0.5 to 5 vol % surfactant.
- the effluent 40 may be formed with a content of from 1 to 8 vol % pyrolysis oil stream, from 87 to 99 vol % hydrocarbon stream, and 0.5 to 5 vol % surfactant.
- the effluent 40 may be formed with a content of from 48 to 52 vol % pyrolysis oil stream, from 47 to 48 vol %
- hydrocarbon stream and from 2 to 3 vol % surfactant.
- the effluent 40 may be a single phase, stable mixture of the lipids and the pyrolysis oil.
- the stream 39 and pyrolysis oil stream 12 are fed in proportion to one another to form the effluent 40 with a content of from 1 to 55 vol % pyrolysis oil stream 12, from 45 to 50 vol % lipid stream 16, and 0.5 to 5 vol % surfactant 38.
- the effluent 40 may be formed with a content of from 1 to 8 vol % pyrolysis oil stream 12, from 87 to 99 vol % lipid stream 16, and 0.5 to 5 vol % surfactant 38.
- the effluent 40 may be formed with a content of from 48 to 52 vol % pyrolysis oil stream 12, from 47 to 48 vol % lipid stream 16, and from 2 to 3 vol % surfactant 38.
- the pyrolysis oil stream 12 is included in amounts up to 50 vol % of the lipid stream 16, such as up to 40 vol %, up to 30 vol %, or up to 20 vol %, of the lipid stream.
- Exemplary embodiments include at least 1 vol % pyrolysis oil in the effluent 40, such as at least 3 vol %, or at least 5 vol % pyrolysis oil in the effluent 40.
- the exemplary effluent 40 includes an effective amount of non-ionic surfactant 38, which compatibilizes the lipids and the pyrolysis oil, and allows the formation of a single phase, stable mixture of the two materials.
- the selection of the non-ionic surfactant 38 can be optimized for the particular lipid feedstock being used.
- the amount of non-ionic surfactant 38 may vary depending on the particular lipid feedstock and pyrolysis oil being used, and the ratio of these two components in the effluent 40.
- An effective amount of surfactant 38 is any amount equal to or above the minimum amount that results in the formation of a single phase, stable mixture. There is no upper limit to the amount of surfactant 38 that can be used. However, above a certain level, the use of more surfactant 38 does not result in the enhancement of the stability of the mixture. Although it is possible to use more than this amount without having a negative physical effect on the composition, the cost of the composition would increase. Consequently, using more surfactant than needed to provide the stability benefit is less desirable.
- the amount of non-ionic surfactant used is typically at least 0.2% by weight of pyrolysis oil in the composition, although some surfactants may require at least 0.3%, or at least 0.4%, or at least 0.5%, or at least 0.6%.
- the maximum amount of surfactant that enhances the stability of the mixture is 1 % by weight of pyrolysis oil in the composition.
- the amount of surfactant that might be used in practice, depending on the conditions of storage, handling and desired shelf life of the composition, is typically less than 10% by weight of pyrolysis oil in the composition, or less than 5%, or less than 3%, or less than 2%, or less than 1 %.
- the effluent 40 can also include one or more lower alcohols or polyols with carbon numbers of 3 to 8, such as butanol, propylene glycol and the like, for increased stability, if desired.
- the exemplary effluent 40 is a stable, intimate mixture of the lipid stream 16 and the pyrolysis oil stream 12.
- the hydrocarbon stream 14, surfactant 33, lipid stream 16 and/or surfactant 38 may be heated. If any component is a solid or paste at ambient temperature, it is heated to a temperature at which it is a liquid. If either the lipid stream 16 or the surfactant 38 is heated before being mixed, the other should be heated to a temperature within 5 degrees of the same temperature. Similarly, if either the hydrocarbon 14 stream or the surfactant 33 is heated before being mixed, the other should be heated to a temperature within 5 degrees of the same temperature. [0030] Mixing of the surfactant 33 or 38 and the hydrocarbon stream 14 or lipid stream 16 may be performed in a series of mixing tanks.
- an appropriate amount of one or more surfactants may be fed slowly into the lipid stream 16.
- laminar flow mixing should be maintained. After all of the surfactant has been mixed in, mixing may be continued for a period of time to ensure thorough mixing of the surfactant 38 in the lipid stream 16. The additional mixing period can be 15 min to 2 hours or more.
- the pyrolysis oil stream 14 may be slowly added to the
- lipid/surfactant mixture 39 in the tank 25 while maintaining mixing and heating (if any). After the addition of the pyrolysis oil has been completed, any heating is turned off, and mixing is continued for a period of time, such as 15 min to 2 hours or more.
- the effluent 40 can be filtered to remove any coarse particles that may be present, if desired.
- the effluent 40 can then be used in processes designed for pure lipid feedstocks, or pure hydrocarbon feedstocks, without any additional upgrading of the pyrolysis oil or any significant modifications to the process equipment.
- the effluent 40 is pumped by a circulation pump 45.
- a recycle portion 51 is redirected for mixing with the pyrolysis oil stream 12 while a product portion 52 flows into product processing.
- the recycle portion 51 passes through a flow control valve 55 for maintaining an appropriate ratio of recycle effluent 40 and fresh pyrolysis oil stream 12.
- the recycle portion 51 is then introduced to the pyrolysis oil stream 12 to form a combined stream 56.
- the combined stream 56 is mixed together.
- the combined stream 56 passes through a static mixer 60 and through a mixing valve 65 to form mixed stream 66.
- Mixed stream 66 is fed to the tank 25. In this manner, the pyrolysis oil stream 12 is introduced to the tank 25.
- the apparatus 10 may include a pressure differential indicator controller (PDIC) 70 connected to the pyrolysis oil stream 12 and the combined stream 56.
- the controller 70 is utilized to ensure a fixed pressure drop from combined stream 56 to mixed stream 66 through mixing valve 65 to ensure proper mixing of the pyrolysis oil stream 12 and the recycle portion 51 before introduction to the tank 25.
- the product portion 52 of the effluent 40 may be optionally blended with a hydrocarbon stream 71 from a hydrocarbon source 72 to form a blended stream 75.
- the hydrocarbon source 72 is a processing unit from elsewhere in apparatus 10. While any suitable and available hydrocarbon stream may be blended, an exemplary hydrocarbon stream 71 is a vacuum gas oil (VGO) stream.
- VGO vacuum gas oil
- the product portion 52 of the effluent 40 is fed to and processed by an FCC reactor 80.
- the FCC reactor 80 includes a reaction zone 82 holding catalyst 84.
- the effluent 40 or blended stream 75 is fed into the FCC reactor 80 through a main feed line.
- the effluent 40 or blended stream 75 need not be introduced into the FCC reactor 80 through special injectors or nozzles.
- the components of the pyrolysis oil stream 12, hydrocarbon stream 14, lipid stream 16, surfactant stream 33, surfactant stream 38, and/or hydrocarbon stream 70 are introduced to the FCC reactor 80 in a single stream, rather than separately.
- the various embodiments comprise upgrading a pyrolysis oil through mixing with a hydrocarbon stream and surfactant and/or with a lipid stream and surfactant. Further, the embodiments provide for FCC processing of the effluent formed by mixing the pyrolysis oil and the selected stream or streams without requiring water removal.
- a first embodiment of the invention is a method for co-processing a pyrolysis oil stream and a hydrocarbon stream, the method comprising the steps of mixing the pyrolysis oil stream and the hydrocarbon stream with a surfactant to form an emulsion; introducing the emulsion to a reaction zone in an fluid catalytic cracking (FCC) unit; and contacting the emulsion with a catalyst in the reaction zone to form an FCC product stream.
- FCC fluid catalytic cracking
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the pyrolysis oil stream comprises from 15 vol % water to 35 vol % water.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising dissolving the surfactant in the hydrocarbon stream before mixing the pyrolysis oil stream and the hydrocarbon stream.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein mixing the pyrolysis oil stream and the hydrocarbon stream with the surfactant to form the emulsion comprises mixing the pyrolysis oil stream and the hydrocarbon stream with a non-ionic surfactant.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein mixing the pyrolysis oil stream and the hydrocarbon stream with the surfactant to form the emulsion comprises mixing the pyrolysis oil stream and the hydrocarbon stream with sorbitan esters of fatty acids, polyglycol esters of fatty acids, mono- glycerides, di-glycerides, a mixture of mono-glycerides and di-glycerides, esters of monofunctional fatty acids with poly-12-hydroxystearic acid, esters of monofunctional alcohols with poly-12-hydroxystearic acid, polymeric esters of difunctional fatty acids, polymeric esters of difunctional alcohols, esters of fatty acids with polyethylene glycol having up to five polyoxyethylene units, esters of hydroxyacids with polyethylene glycol having up to five polyoxyethylene units, succinic anhydride or succinimide-modified linear and branched polyalkylene compounds, or mixtures thereof.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein mixing the pyrolysis oil stream and the hydrocarbon stream with the surfactant to form the emulsion comprises forming the emulsion with a content of from 1 to 55 vol % pyrolysis oil stream, from 45 to 50 vol %
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein mixing the pyrolysis oil stream and the hydrocarbon stream with the surfactant to form the emulsion comprises forming the emulsion with a content of from 1 to 8 vol % pyrolysis oil stream, from 87 to 99 vol % hydrocarbon stream, and 0.5 to 5 vol % surfactant.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein mixing the pyrolysis oil stream and the hydrocarbon stream with the surfactant to form the emulsion comprises forming the emulsion with a content of from 48 to 52 vol % pyrolysis oil stream, from 47 to 48 vol % hydrocarbon stream, and 2 to 3 vol % surfactant.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the hydrocarbon stream is a diesel stream or an atmospheric gas oil stream; mixing the pyrolysis oil stream and the hydrocarbon stream with the surfactant comprises mixing the pyrolysis oil stream and the hydrocarbon stream with the surfactant to form the emulsion; the method further comprises blending the emulsion with a vacuum gas oil (VGO) stream to form a blended stream; introducing the emulsion to the reaction zone in the FCC unit comprises introducing the blended stream to the reaction zone in the FCC unit; and contacting the emulsion with the catalyst in the reaction zone comprises contacting the blended stream with the catalyst in the reaction zone to form the FCC product stream.
- VGO vacuum gas oil
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein mixing the pyrolysis oil stream and the hydrocarbon stream with the surfactant comprises mixing the pyrolysis oil stream, the hydrocarbon stream and a lipid stream with the surfactant to form the emulsion.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein mixing the pyrolysis oil stream and the hydrocarbon stream with the surfactant to form the emulsion further comprises forming a dispersed phase.
- a second embodiment of the invention is a method for co-processing a pyrolysis oil stream and a lipid stream, the method comprising the steps of mixing the pyrolysis oil stream and the lipid stream with a surfactant to form a mixture; introducing the mixture to a reaction zone in an fluid catalytic cracking (FCC) unit; and contacting the mixture with a catalyst in the reaction zone to form an FCC product stream.
- FCC fluid catalytic cracking
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the pyrolysis oil stream comprises from 15 vol % water to 35 vol % water.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph further comprising dissolving the surfactant in the lipid stream before mixing the pyrolysis oil stream and the lipid stream.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein mixing the pyrolysis oil stream and the lipid stream with the surfactant comprises mixing the pyrolysis oil stream and the lipid stream with a non-ionic surfactant.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein mixing the pyrolysis oil stream and the lipid stream with the surfactant comprises mixing the pyrolysis oil stream and the lipid stream with sorbitan esters of fatty acids, polyglycol esters of fatty acids, mono- glycerides, di-glycerides, a mixture of mono-glycerides and di-glycerides, esters of monofunctional fatty acids with poly-12-hydroxystearic acid, esters of
- monofunctional alcohols with poly-12-hydroxystearic acid polymeric esters of difunctional fatty acids, polymeric esters of difunctional alcohols, esters of fatty acids with polyethylene glycol having up to five polyoxyethylene units, esters of hydroxyacids with polyethylene glycol having up to five polyoxyethylene units, succinic anhydride or succinimide-modified linear and branched polyalkylene compounds, or mixtures thereof.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein mixing the pyrolysis oil stream and the lipid stream with the surfactant to form the mixture comprises forming the mixture with a content of from 1 to 55 vol % pyrolysis oil stream, from 45 to 50 vol % lipid stream, and 0.5 to 5 vol % surfactant.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein mixing the pyrolysis oil stream and the lipid stream with the surfactant to form the mixture comprises forming the mixture with a content of from 1 to 8 vol % pyrolysis oil stream, from 87 to 99 vol % lipid stream, and 0.5 to 5 vol % surfactant.
- a third embodiment of the invention is a fuel processing apparatus comprising a pyrolysis oil source; a mixing unit in fluid communication with the pyrolysis oil source and configured to mix a pyrolysis oil, a hydrocarbon feedstock, and a surfactant to form an emulsion; and a fluid catalytic cracking (FCC) unit in fluid communication with the mixing unit and including a reaction chamber suitable for contacting components of the emulsion with a catalyst to form an FCC product stream.
- FCC fluid catalytic cracking
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph wherein the apparatus is configured to blend the emulsion with a gas oil stream to form a blended stream, wherein the blended stream is fed to the FCC unit.
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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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14/570,978 US20160168481A1 (en) | 2014-12-15 | 2014-12-15 | Methods and apparatuses for co-processing pyrolysis oil |
| PCT/US2015/064425 WO2016100003A2 (en) | 2014-12-15 | 2015-12-08 | Methods and apparatuses for co-processing pyrolysis oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP3234073A2 true EP3234073A2 (en) | 2017-10-25 |
| EP3234073A4 EP3234073A4 (en) | 2018-07-18 |
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| EP15870701.8A Withdrawn EP3234073A4 (en) | 2014-12-15 | 2015-12-08 | Methods and apparatuses for co-processing pyrolysis oil |
Country Status (3)
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| US (1) | US20160168481A1 (en) |
| EP (1) | EP3234073A4 (en) |
| WO (1) | WO2016100003A2 (en) |
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| DK3421572T3 (en) | 2017-06-29 | 2020-11-09 | Neste Oyj | Process for increasing gasoline and middle distillate selectivity by catalytic cracking |
| US10696906B2 (en) | 2017-09-29 | 2020-06-30 | Marathon Petroleum Company Lp | Tower bottoms coke catching device |
| US12000720B2 (en) | 2018-09-10 | 2024-06-04 | Marathon Petroleum Company Lp | Product inventory monitoring |
| US12031676B2 (en) | 2019-03-25 | 2024-07-09 | Marathon Petroleum Company Lp | Insulation securement system and associated methods |
| US11975316B2 (en) | 2019-05-09 | 2024-05-07 | Marathon Petroleum Company Lp | Methods and reforming systems for re-dispersing platinum on reforming catalyst |
| CA3212045A1 (en) | 2019-05-30 | 2020-11-30 | Marathon Petroleum Company Lp | Methods and systems for minimizing nox and co emissions in natural draft heaters |
| CA3109606C (en) | 2020-02-19 | 2022-12-06 | Marathon Petroleum Company Lp | Low sulfur fuel oil blends for paraffinic resid stability and associated methods |
| US11306253B2 (en) * | 2020-03-30 | 2022-04-19 | Chevron U.S.A. Inc. | Circular economy for plastic waste to polyethylene via refinery FCC or FCC/alkylation units |
| US12461022B2 (en) | 2021-02-25 | 2025-11-04 | Marathon Petroleum Company Lp | Methods and assemblies for determining and using standardized spectral responses for calibration of spectroscopic analyzers |
| US11702600B2 (en) | 2021-02-25 | 2023-07-18 | Marathon Petroleum Company Lp | Assemblies and methods for enhancing fluid catalytic cracking (FCC) processes during the FCC process using spectroscopic analyzers |
| US11905468B2 (en) | 2021-02-25 | 2024-02-20 | Marathon Petroleum Company Lp | Assemblies and methods for enhancing control of fluid catalytic cracking (FCC) processes using spectroscopic analyzers |
| US20250012744A1 (en) | 2021-02-25 | 2025-01-09 | Marathon Petroleum Company Lp | Methods and assemblies for enhancing control of refining processes using spectroscopic analyzers |
| US11898109B2 (en) | 2021-02-25 | 2024-02-13 | Marathon Petroleum Company Lp | Assemblies and methods for enhancing control of hydrotreating and fluid catalytic cracking (FCC) processes using spectroscopic analyzers |
| US12473500B2 (en) | 2021-02-25 | 2025-11-18 | Marathon Petroleum Company Lp | Assemblies and methods for enhancing control of fluid catalytic cracking (FCC) processes using spectroscopic analyzers |
| US12018216B2 (en) | 2021-10-10 | 2024-06-25 | Marathon Petroleum Company Lp | Methods and systems for enhancing processing of hydrocarbons in a fluid catalytic cracking unit using plastic |
| US12037548B2 (en) | 2021-10-10 | 2024-07-16 | Marathon Petroleum Company Lp | Methods and systems for enhancing processing of hydrocarbons in a fluid catalytic cracking unit using a renewable additive |
| US11692141B2 (en) | 2021-10-10 | 2023-07-04 | Marathon Petroleum Company Lp | Methods and systems for enhancing processing of hydrocarbons in a fluid catalytic cracking unit using a renewable additive |
| US11926793B2 (en) * | 2021-10-27 | 2024-03-12 | ExxonMobil Technology and Engineering Company | FCC co-processing of biomass oil |
| US11802257B2 (en) | 2022-01-31 | 2023-10-31 | Marathon Petroleum Company Lp | Systems and methods for reducing rendered fats pour point |
| CN119403909A (en) * | 2022-05-06 | 2025-02-07 | 可再生能源集团公司 | Lipid-assisted transformation |
| US12311305B2 (en) | 2022-12-08 | 2025-05-27 | Marathon Petroleum Company Lp | Removable flue gas strainer and associated methods |
| US12306076B2 (en) | 2023-05-12 | 2025-05-20 | Marathon Petroleum Company Lp | Systems, apparatuses, and methods for sample cylinder inspection, pressurization, and sample disposal |
| US12533615B2 (en) | 2023-06-02 | 2026-01-27 | Marathon Petroleum Company Lp | Methods and systems for reducing contaminants in a feed stream |
| US12415962B2 (en) | 2023-11-10 | 2025-09-16 | Marathon Petroleum Company Lp | Systems and methods for producing aviation fuel |
| US12599848B2 (en) | 2024-06-03 | 2026-04-14 | Marathon Petroleum Company Lp | Systems, analyzers, controllers, and associated methods to enhance fluid separation for distillation operations |
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| CN103314078B (en) * | 2010-09-14 | 2015-08-19 | Ifp新能源公司 | Method for upgrading bio-oil to transportation-grade hydrocarbon fuel |
| US8377152B2 (en) * | 2010-10-29 | 2013-02-19 | Kior, Inc. | Production of renewable bio-distillate |
| US9109177B2 (en) * | 2011-12-12 | 2015-08-18 | Ensyn Renewables, Inc. | Systems and methods for renewable fuel |
| US20130178672A1 (en) * | 2012-01-06 | 2013-07-11 | Shell Oil Company | Process for making a distillate product and/or c2-c4 olefins |
| US9944859B2 (en) * | 2013-04-19 | 2018-04-17 | Phillips 66 Company Albermarle Corporation | Deep deoxygenation of biocrudes utilizing fluidized catalytic cracking co-processing with hydrocarbon feedstocks |
-
2014
- 2014-12-15 US US14/570,978 patent/US20160168481A1/en not_active Abandoned
-
2015
- 2015-12-08 WO PCT/US2015/064425 patent/WO2016100003A2/en not_active Ceased
- 2015-12-08 EP EP15870701.8A patent/EP3234073A4/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| US20160168481A1 (en) | 2016-06-16 |
| WO2016100003A3 (en) | 2016-08-11 |
| WO2016100003A2 (en) | 2016-06-23 |
| EP3234073A4 (en) | 2018-07-18 |
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