US3761391A - Process for the production of gasoline and low molecular weight hydrocarbons - Google Patents
Process for the production of gasoline and low molecular weight hydrocarbons Download PDFInfo
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- US3761391A US3761391A US00166048A US3761391DA US3761391A US 3761391 A US3761391 A US 3761391A US 00166048 A US00166048 A US 00166048A US 3761391D A US3761391D A US 3761391DA US 3761391 A US3761391 A US 3761391A
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- gasoline
- catalyst
- recycle
- riser
- cracking
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- 239000003502 gasoline Substances 0.000 title abstract description 93
- 229930195733 hydrocarbon Natural products 0.000 title abstract description 34
- 150000002430 hydrocarbons Chemical class 0.000 title abstract description 34
- 238000000034 method Methods 0.000 title abstract description 31
- 238000004519 manufacturing process Methods 0.000 title abstract description 17
- 239000003054 catalyst Substances 0.000 abstract description 113
- 238000006243 chemical reaction Methods 0.000 abstract description 70
- 238000005336 cracking Methods 0.000 abstract description 48
- 239000000463 material Substances 0.000 abstract description 17
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 9
- 238000004064 recycling Methods 0.000 abstract description 4
- 239000000446 fuel Substances 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 74
- 239000007789 gas Substances 0.000 description 52
- 229910052799 carbon Inorganic materials 0.000 description 31
- 238000000926 separation method Methods 0.000 description 23
- 150000001336 alkenes Chemical class 0.000 description 15
- 230000008929 regeneration Effects 0.000 description 13
- 238000011069 regeneration method Methods 0.000 description 13
- 238000004523 catalytic cracking Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000003915 liquefied petroleum gas Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 6
- 239000000571 coke Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- -1 alkyl aromatic hydrocarbons Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006204 deethylation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical group 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
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
- 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
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S208/00—Mineral oils: processes and products
- Y10S208/02—Molecular sieve
Definitions
- the gas oil is cracked by contacting a freshly regenerated cracking catalyst.
- the process of recycling gasoline allows a higher production of olefinic C and C hydrocarbons which can be converted to high octane components and the increased production of C and C saturates which may be valuable in the production of LPG fuel.
- This invention relates to a process for production of gasoline and low molecular weight hydrocarbons by catalyst cracking of fresh gas oil feed and recycle gasoline stocks. More specifically, this invention relates to a riser type cracking of gas oil feed stocks and the cracking of a recycle gasoline in either a riser or a dense bed reaction zone which contains partially deactivated cracking catalysts.
- the problem associated with cracking recycle gasoline in a reaction zone Where fresh feed is present is that hydrogen transfer from the fresh feed to the olefins which are derived from the recycle gasoline causes the olefins to be saturated. Processing the recycle gasoline in a separate reaction zone over partially deactivated catalyst eliminates most hydrogen transfer from the fresh feed and allows more olefins to be produced. Hydrogen transfer occurs by the transfer of hydrogen from the fresh feed stock or higher molecular weight cracked components to the particular olefin which is being produced.
- Another advantage of using a separate reaction zone to crack recycle gasoline is that less coke is made per unit ice conversion of the recycled gasoline when partially deactivated catalyst is used.
- the use of partially deactivated catalyst in the second reaction zone prevents extensive degradation of light olefins products via polymerization which is enhanced by active acidic fresh catalysts.
- the partially deactivated catalysts are not as acidic as freshly regenerated catalysts and therefore reduce polymerization side reactions.
- the Chen patent relates to a fixed bed process using an extremely low catalyst to oil ratio-namely, 0.1.
- the average temperatures are high while the liquid hourly space velocity increases with the average temperature of the cracking reaction.
- the invention can be summarized as a process for the catalytic cracking of a gas oil feed stock in a riser reaction zone and the cracking of a recycle gasoline stream by partially deactivated catalyst in a separate reaction zone.
- the cracking of the gas oil feed stock and the recycle gasoline take place at relatively high temperatures.
- the attached drawing shows one particular mode of operation for the production of gasoline and relatively large yields of light gaseous hydrocarbons.
- the vessels shown in the attached drawing are labeled as follows: Gas oil risen reaction zone 1; cyclone separation zone 2; recycle reaction zone 3; regeneration zone 4; and separation means 5.
- Fresh feed is passed into the process via line 7 at a given rate, and when required at preheated temperatures, into line 6 which enters the gas oil riser reaction zone 1 at its lower portion.
- Line 6 and riser reaction zone 1 may be a single long vessel generally having a large length over diameter ratio and in many cases are identical in size.
- Freshly regenerated catalyst from regeneration zone 4 which has had substantially all of the carbon present on it burned off in regeneration zone 4, leaves that zone via line 8 and contacts the fresh feed at the intersection of line 6, 7 and 8.
- the point at which lines 6, 7 and 8 meet is designed in such a manner that the regenerated catalyst vaporizes hydrocarbons which contact it.
- the vapors carry the catalyst up through line 6 into, through, and out of riser reaction zone 1 directly into a cyclone separation means 2.
- Cyclone separation zone 2 may be located within a vessel in which the recycle reaction zone 3 is located or, as indicated by the drawing, a separate vessel from the recycle reaction zone. Cyclone separation means 2 may consist of any number of cyclones in parallel or series arrangement in order to effectively separate partially deactivated catalyst and oil from the efiluent leaving the riser reaction zone 1.
- the hydrogen efiiuent which is separated from the partially deactivated catalyst flows through line 18 into separation zone 5.
- the partially deactivated catalyst passes from cyclone separation zone 2 via line 19 into the recycle reaction zone 3.
- the recycle reaction zone 3 has a recycle stream passing to it which comes from separation zone 5 via line 12 through valve 11-
- the recycle gasoline stream contacts a partially deactivated catalyst at conditions to effect partial cracking of gasoline to lighter weight olefins and/or paraffins which are subsequently removed from that zone via line 20.
- a cyclone separation means which is generally required to separate the hydrocarbon efliuent and catalyst which are withdrawn from the recycle reaction zone.
- the cyclone separation means may be located within the recycle reaction zone or externally to it.
- the catalyst which leaves the recycle reaction zone passes into the regenerator via line 21.
- the recycle reaction zone may be utilized in the form of a riser reaction zone.
- the partially deactivated catalyst leaving the cyclone separator 2 passes into the lower portion of the recycle reaction zone riser.
- the catalyst contacts recycle gasoline causing it to vaporize and carry catalyst up through the riser while cracking of the gasoline occurs.
- the catalyst and hydrocarbon leaving this riser then pass into a cyclone separation zone and are separated with the cracked gasoline passing via line 20 to separation zone 5 or another separation zone.
- the spent catalyst can then be stripped and passed into the regenerator 4.
- Separation zone 5 is generally a fractionator of known design familiar to those associated with the refinery arts. It generally has outlet points as illustrated for removing various products from this zone which are passed into it via line 18, and line 20.
- Line 13 has a dry gas stream flowing through it which generally comprises hydrogen, and C and C gaseous materials.
- Line 14 generally has a light hydrocarbon gas stream (LPG) flowing through it which contains C and C olefinic and saturated hydrocarbons.
- Line 12 carries recycle gasoline back to be recontacted with a partially deactivated cracking catalyst via line 12.
- Line 12 should contain a preheating means to supply heat to the stream passing into zone 3 to help zone 3 maintain high enough temperatures for cracking to occur. Some of the recycled gasoline may alternately pass through valve into the riser reaction zone.
- Gasoline may be withdrawn from the process via line 22 past valve 23 at any suitable rate depending on the amount of gasoline material required for recycle operations.
- the heavy and light cycle oils are removed from the process at line 15 of the fractionation zone 5.
- the material passing through line 16 from separation zone 5 contains a slurry oil which contains the heaviest materials passed into separation zone 5 and any catalyst which is carried over from the cracking section.
- This material withdrawn from process may be recycled to riser 1 or can be used as a torch oil to maintain heat in the regeneration zone or for other refinery processes requiring such byproduct oil. Additional lines may be required where it is desired that light cycle oil or the heavy cycle oils be separately recycled to the riser reaction zone.
- this ma terial may be recontacted with the cracking catalyst and is preferably recycled as a combined feed stream with the fresh feed in line 7. This allows the heavy cycle oil to contact the relatively active freshly regenerated cata lyst in the riser type reaction allowing a more complete conversion of the heavy cycle oil to gasoline or light gaseous products. In a similar manner light cycle oil may be recycled to the riser.
- the light cycle oil or heavy cycle oil or both may be hydrogenated prior to passage into riser 1 to partially saturate rings in the polycyclic aromatics which can then be broken via cracking.
- This allows increased production of alkyl aromatic hydrocarbons such as toluene or xylene which are high octane components substantially boosting the octane rating for the gasoline produced.
- a riser reaction zone is an elongated cylindrical vessel having a large length to diameter ratio having a feed and catalyst inlet at a bottom portion thereof and a catalyst and oil efliuent outlet at the top.
- dilute phase riser operating conditions are defined as those conditions in which a feed stock and catalyst are concurrently passed through a riser type reaction zone with the catalyst density in the riser maintained somewhere between 1 up to about 20 pounds per cubic foot.
- the gas oil riser reaction zone refers to a riser reactor in which gas oil feed is cracked with freshly regenerated catalyst.
- dense phase catalytic cracking operations include a fluidized bed of catalyst located within a vessel with feed stock passing into the vessel vaporizing and bubbling through the fluidized bed of catalyst causing a reaction to occur.
- the feed stocks pass upward through the bed while catalyst particles remain in the fluidized bed.
- a catalyst draw off is utilized at the lower portion of the bed.
- the recycle reaction zone can include both a dilute phase riser operation or a dense phase cracking operation.
- Fresh catalyst generally is catalyst passing out of the regeneration zone which has not had the opportunity to contact a hydrocarbon stream before contacting the gas oil feed stock in the process.
- Partially deactivated catalyst is cracking catalyst which has contacted gas oil feed in the first riser reaction zone and has deposited thereon a quantity of coke or carbon. In most instances, it is required that the partially deactivated catalyst contain enough activity to at least cause substantial reaction of the recycle gasoline which contacts it in the recycle reaction zone.
- the catalyst which leaves the recycle reaction zone can also be termed partially deactivated catalyst, since this catalyst contains a greater quantity of coke or carbon on it than a catalyst which leaves the regeneration zone.
- the gas oil feed stocks which can be used in the process of this invention can comprise any hydrocarbon material capable of producing gasoline boiling range hydrocarbons on being subjected to normal catalytic cracking conditions.
- the feed gas oils may be obtained from various crude sources. They have boiling ranges anywhere from about 400 F. up to and including 1200 F. by ASTM method D-1160. Particularly suitable feed stocks include distillates from gulf coast and mid-continental crudes which have Conradson carbon residuals below about 1.5 wt. percent. -In many instances the feed stocks passing into the first riser reaction zone can contain heavy cycle oil or light cycle oil or quantities of both which are recycled to the process as is typically done in catalytic cracking operations.
- gasoline or recycle gasoline shall refer to cracked products which have boiling ranges of from about F. up to and including 450 to 500 F.
- gasolines include hydrocarbons of the aromatic and alkylaromatic variety along with isoand normal olefins and parafiins and in some instances cyclo-paraifins.
- the gasoline recycled to the recycle reactor may be a heart cut of the gasoline withdrawn from the main column.
- dry gases shall include hydrogen and the C and C hydrocarbons.
- the dry gases contain components which are not valuable in refinery operations and hence in this process are desired to be minimized. They are generally the product of demethylation or deethylation of aromatics or the products of thermal or free radical cracking.
- LPG refers to liquid petroleum gases and is generally synonymously used with the term light gases in a refinery art.
- the liquefied petroleum gases generally include propane or isoor normal butane or combinations thereof.
- these components are relatively valuable in refinery processing as they are easily used in the fuel market.
- Included within the LPG components are the C and C olefins and the C and C parafiins.
- the light gases produced by this process are very valuable in producing high octane components in the form of alkylate gasolines.
- the C and C olefins are readily alkylatable with isobutane which is produced in high yield in this process.
- the C paraffin is typically not alkylated.
- catalysts suitable for use in catalytic cracking such as silica-alumina, silica-magnesia, silica-zirconia, acid activated clay, crystalline catalysts including faujasites dispersed in a silica containing inorganic oxide matrix, mordenite containing catalyst either dispersed in a silica containing matrix or an alumina containing matrix or used in pure form, the type X and type Y structured zeolites having certain cations including the rare earths exchanged thereon and used as a catalytic cracking catalyst in admixture with an amorphous catalyst, crystalline catalysts of the type X or type Y variety in a silica or alumina matrix.
- Specially active catalysts which find much use presently in the catalytic cracking operation are those amorphous silica-alumina catalysts having concentrations of about to 40 wt. of alumina and 90 to 60 wts. of silica or those containing 2 to of a type X, Y or faujasite structured material dispersed in a silica or in a silica-alumina matrix.
- Other suitable catalysts include the decationized form of the type X or Y structured zeolites.
- gas oil cracking conditions including temperatures of from about 800 F. to about 1275 F., pressures of from about atmospheric up to 50 p.s.i.g., catalyst to oil weight ratios of from about 1 to about 20 and combined feed ratios (fresh feed plus recycle material divided by fresh feed) of from about 1 to about 3.0.
- the fresh feed may be mixed with recycle heavy oil or light cycle oil or a slurry oil.
- Gasoline cracking conditions include the contacting of recycle gasoline and, in some instances, a gasoline material either from another processing unit, with a partially deactivated catalyst at conditions to produce light gases and gasoline. Partially deactivated catalyst should be the sole catalyst effecting gasoline cracking operations. A portion or all of the partially deactivated catalyst leaving the gas oil riser can pass into the recycle reaction zone.
- Specific gasoline cracking conditions include pressures of from about atmospheric up to about 50 p.s.i.g., temperatures of from about 950 F. up to about 1300 F. and combined feed ratios of from about 1 to 2.
- the combined feed ratio described can be utilized when part of the efiluent from the gasoline cracking zone is recycled back to that zone.
- WHSV weight hourly space velocity
- C/O catalyst to oil ratio
- the WHSV can vary from about /2 up to about 20 or higher.
- the gas oil may be cracked at gas oil cracking con ditions including a WHSV of from about 20 to about 100 or higher based on fresh feed. Again the optimum catalyst and oil contact times based on fresh feed should be around 4 seconds.
- the gas oil cracking conditions should be limited to those operations in which a dilute phase riser-type reaction zone is utilized. It is preferable that the gas oil cracking conditions include the use of a riser-type cracking zone which is connected directly to a cyclone separation unit in order to quickly and efficiently separate cracked gas oil feed stocks from partially deactivated catalyst in order to prevent gas oil feed stocks from passing through a relatively dense bed of partially deactivated catalysts.
- the gasoline cracking conditions can include both the use of a dilute phase riser or a dense phase cracking operation.
- the freshly regenerated catalysts and gas oil feed stocks are passed into a riser reaction zone at its lower end at conditions in which fresh feed and any recycle material are vaporized and carry all of the catalysts up through the riser with the conversion of at least a portion of the feed stock into gasoline lighter and heavier weight hydrocarbons.
- a riser reaction zone typically at the uppermost portion of the riser-type reaction zone there is a cyclone separation zone of one or more cyclones in series or in parallel.
- the separation zone effects the immediate separation of a partially deactivated catalyst and reaction products from the gas oil riser.
- the reaction products pass into a fractionation zone wherein they are separated into dry gas, light gases, gasoline and cycle oil. A part or all of the partially deactivated catalyst passes into the recycle reaction zone.
- the regeneration zone causes the coke deposited on the catalyst to be burned oif so it can be reused as freshly regenerated catalyst.
- the gas oil riser can vary anywhere from a few feet to as many as a 100 or more feet in length and have diameters ranging from a few inches up to 5 or more feet in diameter.
- the recycle reaction zone is a riser type reactor it can be of the same design as the gas oil riser except it will probably be smaller in overall dimensions than the gas oil reactor.
- reaction vessel In instances where the recycle reaction zone contains a dense bed of fluidized catalyst a reaction vessel is necessary to hold the catalyst. Typically, this vessel has a large diameter and generally has a low ratio of its length to diameter in order to allow the partially deactivated catalyst to build up within the lower portion of the vessel. Gasoline is allowed to pass into the vessel at a lower portion thereof to contact the bed of partially deactivated catalyst.
- the equipment used in this example consisted of an 85-foot long riser which was made up from a inch diameter schedule stainless steel pipe.
- the riser was connected to a cyclone separator which separated all catalysts from hydrocarbons which were leaving the riser.
- the cyclone dipleg was connected to the recycle reactor which was a small vessel which contained a fluidized bed of the partially deactivated catalyst which had passed through the cyclone dipleg.
- the recycle reactor had a catalyst outlet line located at its lowermost portion.
- a gasoline recycle inlet stream passed into the reactor through its side near the bottom of the vessel.
- At the top of the pot was a hydrocarbon outlet which itself was contacted with a cyclone separator which in turn was connected to the hydrocarbon outlet of the gas oil riser cyclone.
- the hydrocarbon effluent leaving both the gas oil riser and the recycle reactor passed to a knock-out pot before passing into a pilot scale main column.
- the catalyst leaving the recycle reactor passed through a catalyst stripping zone in which steam contacted the catalyst in a countercurrent fashion to strip any hydrocarbons from the spent catalyst which was then passed into the regeneration zone.
- the regeneration zone was operated at conditions to elfect the removal of the majority of coke deposit on the catalyst passed into the regeneration zone.
- Freshly regenerated catalyst passed out of the regeneration zone and directly into the bottom portion of the 85-foot long riser where it contacted the fresh feed stock, which passed into the plant.
- the catalyst used for the experiments was the same for both the once-through operation and the gasoline recycle operations. It was a rare earth exchanged type Y crystalline aluminosilicate catalyst which had been equilibrated through process use.
- the catalyst and oil were passed into a cyclone where they were separated.
- the hydrocarbon efiluent was passed to the main column where the various components of the efiluent were separated and analyzed in order to determine a once through yield structure.
- the gas oil feed stock for both the once through and recycle operations was the same and was made up of a blend of gas oils having the properties as shown in Table I below.
- the operating conditions for both the once-through and gasoline recycle operations were essentially the same with fresh feed riser average temperatures being about the same.
- the catalyst to oil (C/O) ratios in the risers were almost identical as were the weight hourly space velocities (WHSV) which were based on the fresh feed.
- the combined feed ratios (CPR) for the recycle operations was 1.5 and is defined as the ratio of the fresh feed plus recycled gasoline all divided by the fresh feed rate.
- CPR combined feed ratios
- the gasoline recycle operation allows an increased amount of LPG based on feed stock with the resulting increase in octane number of the remaining C to 430 gasoline.
- the operations in which no recycle gasoline was utilized produced a significantly lower amount of LPG products and a gasoline having a lower octane rating than that obtained by using the gasoline recycle operations. It must be pointed out, however, that the total gasoline yield from the once-through operations was higher as would be expected when compared to the operations in which gasoline was recycled to the reactor part.
- An additional advantage of using gasoline recycle operations is that the gasoline remaining after the recycle gasoline has been cracked is of a higher octane than the gasoline produced on normal cracking operations in which gasoline is not recycled.
- a process for the production of gasoline and low molecular weight hydrocarbons which process comprises the steps of:
- Claim 1 further characterized in that said recycle 3.
- Claim 1 further characterized in that said recycle reaction zone is a riser type reaction zone.
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- 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)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US16604871A | 1971-07-26 | 1971-07-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3761391A true US3761391A (en) | 1973-09-25 |
Family
ID=22601586
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00166048A Expired - Lifetime US3761391A (en) | 1971-07-26 | 1971-07-26 | Process for the production of gasoline and low molecular weight hydrocarbons |
Country Status (2)
Country | Link |
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US (1) | US3761391A (ru) |
PL (1) | PL84617B1 (ru) |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3928172A (en) * | 1973-07-02 | 1975-12-23 | Mobil Oil Corp | Catalytic cracking of FCC gasoline and virgin naphtha |
US3954600A (en) * | 1974-02-15 | 1976-05-04 | Exxon Research & Engineering Co. | Catalytic cracking process for producing middle distillate |
US4067798A (en) * | 1976-02-26 | 1978-01-10 | Standard Oil Company (Indiana) | Catalytic cracking process |
US4172812A (en) * | 1978-04-03 | 1979-10-30 | Exxon Research & Engineering Co. | Catalytic cracking process |
EP0022883A1 (en) * | 1979-07-18 | 1981-01-28 | Exxon Research And Engineering Company | Catalytic cracking and hydrotreating process for producing gasoline from hydrocarbon feedstocks containing sulfur |
US4436613A (en) | 1982-12-03 | 1984-03-13 | Texaco Inc. | Two stage catalytic cracking process |
US5087349A (en) * | 1988-11-18 | 1992-02-11 | Stone & Webster Engineering Corporation | Process for selectively maximizing product production in fluidized catalytic cracking of hydrocarbons |
WO1999057230A1 (en) * | 1998-05-05 | 1999-11-11 | Exxon Research And Engineering Company | Two stage fluid catalytic cracking process for selectively producing c2 to c4 olefins |
US6565739B2 (en) | 2000-04-17 | 2003-05-20 | Exxonmobil Research And Engineering Company | Two stage FCC process incorporating interstage hydroprocessing |
US6569315B2 (en) | 2000-04-17 | 2003-05-27 | Exxonmobil Research And Engineering Company | Cycle oil conversion process |
US6569316B2 (en) | 2000-04-17 | 2003-05-27 | Exxonmobil Research And Engineering Company | Cycle oil conversion process incorporating shape-selective zeolite catalysts |
US20030150775A1 (en) * | 2000-04-17 | 2003-08-14 | Stuntz Gordon F. | Cycle oil conversion process |
US6803494B1 (en) * | 1998-05-05 | 2004-10-12 | Exxonmobil Chemical Patents Inc. | Process for selectively producing propylene in a fluid catalytic cracking process |
US6811682B2 (en) | 2000-04-17 | 2004-11-02 | Exxonmobil Research And Engineering Company | Cycle oil conversion process |
WO2006020547A1 (en) * | 2004-08-10 | 2006-02-23 | Shell Internationale Research Maatschappij B.V. | Method and apparatus for making a middle distillate product and lower olefins from a hydrocarbon feedstock |
US20080188702A1 (en) * | 2004-12-20 | 2008-08-07 | Shell Oil Company | Gasoline Cracking |
US20100163455A1 (en) * | 2007-04-13 | 2010-07-01 | Hadjigeorge George A | Systems and methods for making a middle distillate product and lower olefins from a hydrocarbon feedstock |
US20100200460A1 (en) * | 2007-04-30 | 2010-08-12 | Shell Oil Company | Systems and methods for making a middle distillate product and lower olefins from a hydrocarbon feedstock |
US20100324232A1 (en) * | 2007-10-10 | 2010-12-23 | Weijian Mo | Systems and methods for making a middle distillate product and lower olefins from a hydrocarbon feedstock |
-
1971
- 1971-07-26 US US00166048A patent/US3761391A/en not_active Expired - Lifetime
-
1972
- 1972-06-02 PL PL1972155768A patent/PL84617B1/pl unknown
Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3928172A (en) * | 1973-07-02 | 1975-12-23 | Mobil Oil Corp | Catalytic cracking of FCC gasoline and virgin naphtha |
US3954600A (en) * | 1974-02-15 | 1976-05-04 | Exxon Research & Engineering Co. | Catalytic cracking process for producing middle distillate |
US4067798A (en) * | 1976-02-26 | 1978-01-10 | Standard Oil Company (Indiana) | Catalytic cracking process |
US4172812A (en) * | 1978-04-03 | 1979-10-30 | Exxon Research & Engineering Co. | Catalytic cracking process |
EP0022883A1 (en) * | 1979-07-18 | 1981-01-28 | Exxon Research And Engineering Company | Catalytic cracking and hydrotreating process for producing gasoline from hydrocarbon feedstocks containing sulfur |
US4436613A (en) | 1982-12-03 | 1984-03-13 | Texaco Inc. | Two stage catalytic cracking process |
US5087349A (en) * | 1988-11-18 | 1992-02-11 | Stone & Webster Engineering Corporation | Process for selectively maximizing product production in fluidized catalytic cracking of hydrocarbons |
WO1999057230A1 (en) * | 1998-05-05 | 1999-11-11 | Exxon Research And Engineering Company | Two stage fluid catalytic cracking process for selectively producing c2 to c4 olefins |
US6106697A (en) * | 1998-05-05 | 2000-08-22 | Exxon Research And Engineering Company | Two stage fluid catalytic cracking process for selectively producing b. C.su2 to C4 olefins |
US6803494B1 (en) * | 1998-05-05 | 2004-10-12 | Exxonmobil Chemical Patents Inc. | Process for selectively producing propylene in a fluid catalytic cracking process |
US20030150775A1 (en) * | 2000-04-17 | 2003-08-14 | Stuntz Gordon F. | Cycle oil conversion process |
US6569316B2 (en) | 2000-04-17 | 2003-05-27 | Exxonmobil Research And Engineering Company | Cycle oil conversion process incorporating shape-selective zeolite catalysts |
US6569315B2 (en) | 2000-04-17 | 2003-05-27 | Exxonmobil Research And Engineering Company | Cycle oil conversion process |
US6565739B2 (en) | 2000-04-17 | 2003-05-20 | Exxonmobil Research And Engineering Company | Two stage FCC process incorporating interstage hydroprocessing |
US6811682B2 (en) | 2000-04-17 | 2004-11-02 | Exxonmobil Research And Engineering Company | Cycle oil conversion process |
US6837989B2 (en) | 2000-04-17 | 2005-01-04 | Exxonmobil Research And Engineering Company | Cycle oil conversion process |
US20060231461A1 (en) * | 2004-08-10 | 2006-10-19 | Weijian Mo | Method and apparatus for making a middle distillate product and lower olefins from a hydrocarbon feedstock |
WO2006020547A1 (en) * | 2004-08-10 | 2006-02-23 | Shell Internationale Research Maatschappij B.V. | Method and apparatus for making a middle distillate product and lower olefins from a hydrocarbon feedstock |
US20080188702A1 (en) * | 2004-12-20 | 2008-08-07 | Shell Oil Company | Gasoline Cracking |
US8076525B2 (en) * | 2004-12-20 | 2011-12-13 | Shell Oil Company | Gasoline cracking |
US20100163455A1 (en) * | 2007-04-13 | 2010-07-01 | Hadjigeorge George A | Systems and methods for making a middle distillate product and lower olefins from a hydrocarbon feedstock |
US8920630B2 (en) | 2007-04-13 | 2014-12-30 | Shell Oil Company | Systems and methods for making a middle distillate product and lower olefins from a hydrocarbon feedstock |
US20100200460A1 (en) * | 2007-04-30 | 2010-08-12 | Shell Oil Company | Systems and methods for making a middle distillate product and lower olefins from a hydrocarbon feedstock |
US20100324232A1 (en) * | 2007-10-10 | 2010-12-23 | Weijian Mo | Systems and methods for making a middle distillate product and lower olefins from a hydrocarbon feedstock |
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PL84617B1 (ru) | 1976-04-30 |
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