EP0066018B1 - Verfahren zum Vermindern der Koksablagerung in einem katalytischen Krackverfahren von schweren Kohlenwasserstoffen - Google Patents
Verfahren zum Vermindern der Koksablagerung in einem katalytischen Krackverfahren von schweren Kohlenwasserstoffen Download PDFInfo
- Publication number
- EP0066018B1 EP0066018B1 EP19810302405 EP81302405A EP0066018B1 EP 0066018 B1 EP0066018 B1 EP 0066018B1 EP 19810302405 EP19810302405 EP 19810302405 EP 81302405 A EP81302405 A EP 81302405A EP 0066018 B1 EP0066018 B1 EP 0066018B1
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- EP
- European Patent Office
- Prior art keywords
- catalyst
- zone
- metal
- hydrogen
- hydrocarbon feedstock
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- 239000000571 coke Substances 0.000 title claims description 43
- 238000000034 method Methods 0.000 title claims description 31
- 229930195733 hydrocarbon Natural products 0.000 title claims description 30
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 30
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 25
- 238000004523 catalytic cracking Methods 0.000 title description 10
- 230000015572 biosynthetic process Effects 0.000 title description 7
- 239000003054 catalyst Substances 0.000 claims description 147
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 62
- 229910052751 metal Inorganic materials 0.000 claims description 56
- 239000002184 metal Substances 0.000 claims description 56
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 44
- 230000008929 regeneration Effects 0.000 claims description 43
- 238000011069 regeneration method Methods 0.000 claims description 43
- 239000000356 contaminant Substances 0.000 claims description 41
- 229910052739 hydrogen Inorganic materials 0.000 claims description 41
- 239000001257 hydrogen Substances 0.000 claims description 41
- 230000009467 reduction Effects 0.000 claims description 38
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 37
- 239000000463 material Substances 0.000 claims description 33
- 229910052759 nickel Inorganic materials 0.000 claims description 31
- 239000007789 gas Substances 0.000 claims description 29
- 229910052720 vanadium Inorganic materials 0.000 claims description 28
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- 238000005336 cracking Methods 0.000 claims description 27
- 238000002161 passivation Methods 0.000 claims description 25
- 239000000852 hydrogen donor Substances 0.000 claims description 24
- 229910052742 iron Inorganic materials 0.000 claims description 22
- 150000002739 metals Chemical class 0.000 claims description 16
- 238000009835 boiling Methods 0.000 claims description 14
- 229910052787 antimony Inorganic materials 0.000 claims description 8
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- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
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- 239000011572 manganese Substances 0.000 claims description 2
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- 238000005984 hydrogenation reaction Methods 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 13
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
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- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
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- 238000012545 processing Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
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- 229910045601 alloy Inorganic materials 0.000 description 2
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 2
- 150000001463 antimony compounds Chemical class 0.000 description 2
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- 150000002751 molybdenum Chemical class 0.000 description 2
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- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000003134 recirculating effect Effects 0.000 description 2
- -1 C3 hydrocarbons Chemical class 0.000 description 1
- 241000288030 Coturnix coturnix Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
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- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003251 chemically resistant material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
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- 230000001627 detrimental effect Effects 0.000 description 1
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- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000000386 donor Substances 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
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- 150000004763 sulfides Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/32—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions in the presence of hydrogen-generating compounds
- C10G47/34—Organic compounds, e.g. hydrogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
-
- 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
Definitions
- This invention relates to a method for decreasing the catalytic activity of metal contaminants on cracking catalysts and for decreasing the hydrogen and coke formation on cracking catalysts. More specifically, this invention is directed to a method for reducing the coke and hydrogen formation caused by metal contaminants, such as nickel, vanadium and/or iron, which have become deposited upon cracking catalysts from feedstock containing same.
- vanadium, nickel and/or iron present in the feedstock becomes deposited on the cracking catalyst promoting excessive hydrogen and coke makes.
- metal contaminants are not removed during conventional catalyst regeneration operations during which coke deposits on the catalyst are converted to CO and C0 2 .
- passivation is defined as a method for decreasing the detrimental catalytic effects of metal contaminants such as nickel, vanadium and iron which become deposited on catalyst.
- U.S. Patent Nos. 3,711,422; 4,025,545; 4,031,002; 4,111,845; 4,141,858; 4,148,712; 4,148,714 and 4,166,806 all are directed to the contacting of the cracking catalyst with antimony compounds to passivate the catalytic activity of the iron, nickel and vanadium contaminants deposited on the catalyst.
- antimony compounds alone, may not passivate the metal contaminants to sufficiently low levels particularly where the metal contaminant concentration on the catalyst is relatively high.
- 4,176,084 is directed to the passivation of metals contaminated catalyst in a regeneration zone operated for incomplete combustion of the coke to C0 2 by periodically increasing the oxygen concentration above that required for complete combustion of the coke and by maintaining the temperature above 1300°F (704°C).
- This patent does not disclose a method for passivating metals-contaminated catalyst in a system where the regeneration zone is routinely operated for complete combustion of the coke.
- U.S. Patent No. 4,162,213 is directed at decreasing the catalytic activity of metal contaminants present in cracking catalyst by regenerating the catalyst at temperatures of 1300-1400°F (704 to 760°C) in such a manner as to leave less than 0.10 wt.% residual carbon on the catalyst.
- U.S. Patent No. 3,718,553 is directed at the use of a cracking catalyst impregnated with 100-1000 parts per million by weight (WPPM) of iron, nickel or vanadium or a combination of these metals to increase the octane number of the cracked hydrocarbon products.
- WPPM parts per million by weight
- U.S. Patent Nos. 3,479,279 and 4,035,285 disclose hydrotreating of catalytic cracker product cuts and recirculating this product to the catalytic cracker.
- Related U.S. Patent Nos. 3,413,212 and 3,533,936 disclose 'the use of hydrogen donor materials for decreasing the rate of coke formation on cracking catalyst.
- These patents each disclose in Table V that hydrotreating a fraction from a catalytic cracking zone and returning the hydrotreated material with the cat cracker feed decreases the coke make in the catalytic cracking zone.
- the hydrotreated material preferably is a hydrogen donor material which releases hydrogen to unsaturated olefinic hydrocarbons in a cracking zone without dehydrogenative action.
- Suitable materials disclosed are hydroaromatic, naphthene aromatic and naphthenic compounds.
- Preferred materials are compounds having at least one and preferably 2, 3 or 4 aromatic nuclei, partially hydrogenated and containing olefinic bonds.
- the hydrogen donor material was hydrogenated by contacting the donor material with hydrogen over a suitable hydrogenation catalyst at hydrogenation conditions.
- US-A-4268416 describes a method of reducing the rate of coke production from a hydrocarbon feedstock which is cracked to lower molecular weight products by contact with a cracking catalyst, wherein the feedstock contains at least one metal selected from nickel, vanadium and irori which deposits on,-and contaminates, the catalyst, which method comprises passivation of the catalyst after regeneration treatment and before contact with further quantities of hydrocarbon feedstock at a temperature between 593 and 732°C (1100 to 1350°F), the passivation being effected by treatment of the catalyst with a reducing gas which is preferably hydrogen or less preferably carbon monoxide at a temperature in the range of from 1100 to 1350°F (593 to 732.2°C).
- a reducing gas which is preferably hydrogen or less preferably carbon monoxide at a temperature in the range of from 1100 to 1350°F (593 to 732.2°C).
- the present invention provides a method of reducing the rate of coke production from a hydrocarbon feedstock which is cracked to lower molecular weight products by contact with a cracking catalyst wherein the feedstock contains at least one metal selected from nickel, vanadium and iron and at least some of the said metal becomes deposited on the catalyst as contaminant, and wherein the catalyst is periodically subjected to a regeneration treatment in the absence of hydrocarbon feedstock, and wherein after the regeneration treatment and before contact with hydrocarbon feedstock, the metal contaminant on the catalyst is at least partially passivated by being subjected to a reduction treatment with a reducing gas at a temperature above 600°C, characterised by the steps of:
- the invention is directed at the addition of hydrogen donor material to a catalytic cracking zone in which the metals contaminated cracking catalyst has been passivated by passing the catalyst through a reduction zone maintained at an elevated temperature.
- the addition of hydrogen donor material and passivation of the cracking catalyst operate to decrease the coke makes on the. cracking catalyst.
- This invention is directed at a method for reducing the rate of coke production from a hydrocarbon feedstock cracked to lower molecular weight products in a reaction zone containing cracking catalyst where the feedstock contains at least two metals selected from the class consisting of nickel, vanadium and iron and where at least some of the metal contaminants become deposited on the catalyst.
- the method comprises passing the catalyst after regeneration from the reaction zone through a reduction zone maintained at an elevated temperature for a time sufficient to at least partially passivate the metal contaminants on the catalyst, a reducing environment being maintained in the reduction zone by the addition to the reduction zone of a material selected from the class consisting of hydrogen, carbon monoxide and mixtures thereof, said passivated catalyst thereafter passing to the reaction zone without further.processing.
- the metal contaminants are passivated further by monitoring the concentration of each metal contaminant on the catalyst and adding predetermined amounts of selected metal contaminants to the system.
- the metal contaminants may be further passivated by the addition to the reaction zone of a hydrogen donor material which transfers hydrogen to the hydrocarbon feedstock and/or to the cracked lower molecular weight products.
- the catalyst may be still further passivated by the addition of known passivation agents to the system.
- the temperature of the reduction zone preferably is maintained above about 600°C.
- the hydrogen donor material added to the reaction zone preferably has a boiling point between about 200°C and about 500°C.
- the hydrogen donor material is obtained by fractionating the cracked molecular products from the reaction zone, passing the desired fraction through a hydrogenation zone and then recirculating the material to the reaction zone.
- the Figure is a flow diagram of a fluidized catalytic cracking unit employing the subject invention.
- Reaction or cracking zone 10 is shown containing a fluidized catalyst bed 12 having a level at 14 in which a hydrocarbon feedstock is introduced into the fluidized bed through lines 16 and 94 for catalytic cracking.
- the hydrocarbon feedstock may comprise naphthas, light gas oils, heavy gas oils, residual fractions, reduced crude oils, cycle oils derived from any of ,these, as well as suitable fractions derived from shale oil kerogen, tar sands, bitumen processing, synthetic oils, coal hydrogenation, and the like.
- Such feedstocks may be employed singly, separately in parallel reaction zones, or in any desired combination.
- these feedstocks will contain metal contaminants such as nickel, vanadium and/or iron.
- Heavy feedstocks typically contain relatively high concentrations of vanadium and/or nickel as well as coke precursors, such as Conradson carbon materials. The determination of the amount of Conradson carbon material present may be determined by ASTM test D189-65, which is incorporated herein by reference.
- Hydrocarbon gas and vapors passing through fluidized bed 12 maintain the bed in a dense turbulent fluidized condition.
- hydrogen donor material passes through line 92 for preblending with cat cracker feedstock in line 16 prior to entering fluidized catalyst bed 12 through line 94.
- the hydrogen donor material may be added directly to reaction zone 10 in close proximity to the point where the cat cracker feedstock enters reaction zone 10.
- the hydrogen donor material will comprise between about 5 and about 100 wt.% of the hydrocarbon feedstock to be cracked:
- the cracking catalyst becomes spent during contact with the hydrocarbon feedstock due to the deposition of coke thereon.
- the terms "spent” or “coke contaminated” catalyst as used herein generally refer to catalyst which has passed through a reaction zone and which contains a sufficient quantity of coke thereon to cause activity loss, thereby requiring regeneration.
- the coke content of spent catalyst can vary anywhere from about 0.5 to about 5 wt.% or more.
- spent catalyst coke contents vary from about 0.5 to about 1.5 wt.%.
- the spent catalyst Prior to actual regeneration, the spent catalyst is usually passed from reaction zone 10 into a stripping zone 18 and contacted therein with a stripping gas, which is introduced into the lower portion of zone 18 via line 20.
- the stripping gas which is usually introduced at a gauge pressure of from about 10 to about 50 psig (about 68.95 to about 344.75 kPa), serves to remove most of the volatile hydrocarbons from the spent catalyst.
- a preferred stripping gas is steam, although nitrogen, other inert gases or flue gas may be employed.
- the stripping zone is maintained at essentially the same temperature as the reaction zone, i.e. from about 450°C to about 600°C.
- Stripped spent catalyst from which most of the volatile hydrocarbons have been removed is then passed from the bottom of stripping zone 18, through U-bend 22 and into a connecting vertical riser 24 which extends into the lower portion of regeneration zone 26. Air is added to riser 24 via line 28 in an amount sufficient to reduce the density of the catalyst flowing therein, thus causing the catalyst to flow upward into regeneration zone 26 by simple hydraulic balance.
- the regeneration zone is a separate vessel (arranged at approximately the same level as reaction zone 10) containing a dense phase catalyst bed 30 having a level indicated at 32, which is undergoing regeneration to burn-off coke deposits formed in the reaction zone during the cracking reaction, above which is a dilute catalyst phase 34.
- An oxygen-containing regeneration gas enters the lower portion of regeneration zone 26 via line 36 and passes up through a grid 38 and the dense phase catalyst bed 30, maintaining said bed in a turbulent fluidized condition similar to that present in reaction zone 10.
- Oxygen-containing regeneration gases which may be employed in the process of the present invention are those gases which contain molecular oxygen in admixture with a substantial portion of an inert diluent gas. Air is a particularly suitable regeneration gas.
- An additional gas which may be employed is air enriched with oxygen. Additionally, if desired, steam may be added to the dense phase bed along with the regeneration gas or separately therefrom to provide additional inert diluents and/or fluidization gas.
- the specific vapor velocity of the regeneration gas will be in the range of from about 0.8 to about 6.0 feet/sec. (24.38 to 182.88 cm/s), preferably from about 1.5 to about 4 feet/sec (45.72 to 121.92 cm/s).
- Regenerated catalyst from the dense phase catalyst bed 30 in the regeneration zone 26 flows downward through standpipe 42 and passes through U-bend 44, and line 80 into reduction zone 70 maintained at a temperature above 500°C preferably above about 600°C having a reducing agent such as hydrogen or carbon monoxide, entering through line 72 to maintain a reducing environment in the reduction zone to passivate the contaminants as described in more detail hereinafter.
- the regenerated and passivated catalyst then passes from reduction zone 70 through line 82 and U-bend 84 into the reaction zone 10 by way of transfer line 46 which joins U-bend 84 near the level of the oil injection line 16 and hydrogen donor line 92.
- regenerated catalyst catalyst leaving the regeneration zone which has contacted an oxygen-containing gas causing at least a portion, preferably a substantial portion, of the coke present on the catalyst to be removed. More specifically, the carbon content of the regenerated catalyst can vary anywhere from about 0.01 to about 0.2 wt.%, but preferably is from about 0.01 to about 0.1 wt.%. Predetermined quantities of selected metals or conventional passivation promoters may be added to the hydrocarbon feedstock through lines 16 and/or 94, if desired, as described more fully hereinafter.
- the hydrocarbon feedstock forthe cracking process containing minor amounts of iron, nickel and/or vanadium contaminants is injected into line 46 through line 94 to form an oil and catalyst mixture which is passed into fluid bed 12 within reaction zone 10.
- the metal contaminants and the passivation promoter, if any, become deposited on the cracking catalyst.
- Product vapors containing entrained catalyst particles pass overhead from fluid bed 12 into a gas-solid separation means 48 wherein the entrained catalyst particles are separated therefrom and returned through diplegs 50 leading back into fluid bed 12.
- the product vapors are then conveyed through line 52 and condenser 102 into fractionation zone 100, wherein the product stream is separated into two or more fractions.
- Fractionation zone 100 may comprise any means for separating the product into fractions having different boiling ranges.
- zone 100 may comprise a plate or packed column of conventional design.
- the product is separated into an overhead stream exiting through line 104, comprising light boiling materials, i.e. compounds boiling below about 200°C, a middle cut boiling in the range of about 200 to 370°C exiting through line 106 and a bottoms stream boiling above about 370°C exiting through line 108.
- At least a fraction of the product in line 106, preferably a major fraction passes into hydrogenation zone 110 maintained under hydrogenating conditions where the product contacts hydrogen entering zone 110 through line 112.
- a gaseous stream may pass from zone 110 through line 114 for removal of any undesired by-products.
- Zone 110 typically will contain a conventional hydrogenating catalyst as, for example, a molybdenum salt such as molybdenum oxide'or molybdenum sulfide, and a nickel or cobalt salt, such as nickel or cobalt oxides and/or sulfides. These salts typically are deposited on a support material such as alumina and/or silica stabilized alumina. Hydrogenation catalysts which are particularly suitable are described in U.S. Patent No. 3,509,044, the disclosure of which is incorporated herein by reference. Zone 110 will be maintained at a temperature ranging between about 350 and 400°C and a pressure ranging between about 600 and 3000 psi (4137 and 20685 kPa). A vapor stream exits zone 110 for recycling and a further processing (not shown). The at least partially hydrogenated stream exiting zone 110, also referred to as the hydrogen donor material, is recycled to the reaction zone through line 92.
- a conventional hydrogenating catalyst as, for example, a molybden
- flue gases formed during regeneration of the spent catalyst pass from the dense phase catalyst bed 30 into the dilute catalyst phase 34 along with entrained catalyst particles.
- the catalyst particles are separated from the flue gas by a suitable gas-solid separation means 54 and returned to the dense phase catalyst bed 30 via diplegs 56.
- the substantially catalyst-free flue gas then passes into a plenum chamber 58 prior to discharge from the regeneration zone 26 through line 60.
- the flue gas typically will contain less than about 0.2, preferably less than 0.1 and more preferably less than 0.05 volume% carbon monoxide.
- the oxygen content usually will vary from about 0.4 to about 7 vol.%, preferably from about 0.8 to about 5 vol.%, more preferably from about 1 to about 3 vol.%, most preferably from about 1.0 to about 2 vol.%.
- Reduction zone 70 may be any vessel providing suitable contacting of the catalyst with a reducing environment at elevated temperatures.
- the shape of reduction zone 70 is not critical.
- reduction zone 70 comprises a treater vessel having a shape generally similar to that of regeneration zone 26, with the reducing environment maintained, and catalyst fluidized by, reducing agent entering through line 72 and exiting through line 78.
- the volume of dense phase 74 having a level at 76 is dependent on the required residence time.
- the residence time of the catalyst in reduction zone 70 is not critical as long as it is sufficient to effect the passivation.
- the residence time will range from about 5 sec. to about 30 min., typically from about 2 to 5 minutes.
- the pressure in,this zone is not critical and generally will be a function of the location of reduction zone 70 in the system and the pressure in the adjacent regeneration and reaction zones.
- the absolute pressure in zone 70 will be maintained in the range of about 5 to 50 psia (34.48 to 344.75 kPa), although the reduction zone preferably should be designed to withstand absolute pressures of 100 psia (689.5 kPa).
- the temperature in reduction zone 70 should be above about 500°C preferably above 600°C, but below the temperature at which the catalyst sinters or degrades. A preferred temperature range is about 600-850°C, with the more preferred temperature range being 650-750°C.
- the reduction zone 70 can be located either before or after regeneration zone 26, with the preferred location being after the regeneration zone, so that the heat imparted to the catalyst by the regeneration obviates or minimizes the need for additional catalyst heating.
- the reducing agent utilized in the reduction zone 70 is not critical, although hydrogen and carbon monoxide are the preferred reducing agents. Other reducing agents including light hydrocarbons, such as C3 hydrocarbons, may also be satisfactory.
- Reduction zone 70 can be constructed of any chemically resistant material sufficiently able to withstand the relatively high temperatures involved and the high attrition conditions which are inherent in systems wherein fluidized catalyst is transported. Specifically, metals are contemplated which may or may not be lined. More specifically, ceramic liners are contemplated within any and all portions of the reduction zone together with alloy use and structural designs in order to withstand the maximum contemplated operating temperatures.
- the reducing agent utilized in all but one of the following tests was high purity grade hydrogen, comprising 99.9% hydrogen.
- Table VIII a reducing agent comprising 99.3% CO was utilized.
- commercial grade hydrogen, commercial grade CO, and process gas streams containing H 2 and/or CO can be utilized. Examples include cat cracker tail gas, catalytic reformer off-gas, spent hydrogen streams from catalytic hydroprocessing, synthesis gas, and flue gases.
- the rate of consumption of the reducing agent in reducing zone 70 will, of course, be dependent on the amount of reducible material entering the reducing zone.
- a gas-solids separation means may be required for use in connection with the reduction zone. If the reducing agent exiting from zone 70 is circulated back into the reduction zone, a gas-solids separation means may not be necessary.
- Preferred separation means for zones 10, 26 and 70 will be cyclone separators, multiclones or the like whose design and construction are well known in the art. In the case of cyclone separators, a single cyclone may be used, but preferably, more than one cyclone will be used in parallel or in series flow to effect the desired degree of separation.
- regeneration zone 26 can be made with any material sufficiently able to withstand the relatively high temperatures involved when afterburning is encountered within the vessel and the high attrition conditions which are inherent in systems wherein fluidized catalyst is regenerated and transported.
- metals are contemplated which may or may not be lined.
- ceramic liners are contemplated within any and all portions of the regeneration zone together with alloy use and structural designs in order to withstand temperatures of about 760°C and, for reasonably short periods of time, temperatures which may be as high as 1000°C.
- the gauge pressure in the regeneration zone is usually maintained in a range from about atmospheric to about 50 psig (zero to 344.8 kPa), preferably from about 10 to 50 psig (68.95 to 344.8 kPa). It is preferred, however, to design the regeneration zone to withstand gauge pressures of up to about 100 psig (689.5 kPa). Operation of the regeneration zone at increased pressure has the effect of promoting the conversion of carbon monoxide to carbon dioxide and reducing the temperature level within the dense bed phase at which the substantially complete combustion of carbon monoxide can be accomplished. The higher pressure also lowers the equilibrium level of carbon on regenerated catalyst at a given regeneration temperature.
- the residence time of the spent catalyst in the regeneration zone is not critical so long as the carbon on the catalyst is reduced to an acceptable level. In general, it can vary from about 1 to 30 minutes.
- the contact time or residence time of the flue gas in the dilute catalyst phase establishes the extent to which the combustion reaction can reach equilibrium.
- the residence time of the flue gas may vary from about 10 to about 60 seconds in the regeneration zone and from about 2 to about 30 seconds in the dense bed phase.
- the residence time of the flue gas varies from about 15 to about 20 seconds in the dense bed.
- the present invention may be applied beneficially to any type of fluid cat cracking unit without limitation as to the spatial arrangement of the reaction, stripping, and regeneration zones, with only the addition of reduction zone 70 and related elements.
- any commercial catalytic cracking catalyst * volumes at 0°C and atmospheric pressure designed for high thermal stability could be suitably employed in the present invention.
- Such catalysts include those containing silica and/or alumina.
- Catalysts containing combustion promoters such as platinum can be used.
- Other refractory metal oxides such as magnesia or zirconia may be employed and are limited only by their ability to be effectively regenerated under the selected conditions.
- preferred catalysts include the combinations of silica and alumina, containing 10 to 50 wt.%' alumina, and particualrly their admixtures with molecular sieves or crystalline aluminosilicates.
- Suitable molecular sieves include both naturally occurring and synthetic aluminosilicate materials, such as faujasite, chabazite, X-type and Y-type aluminosilicate materials and ultra stable, large pore crystalline aluminosilicate materials.
- the molecular sieve content of the fresh finished catalyst particles is suitably within the range from 5-35 wt.%, preferably 8-20 wt.%.
- An equilibrium molecular sieve cracking catalyst may contain as little as about 1 wt.% crystalline material. Admixtures of clay-extended aluminas may also be employed.
- Such catalysts may be prepared in any suitable method such as by impregnation, milling, co-gelling, and the like, subject only to the provision that the finished catalyst be in a physical form capable of fluidization. In the following tests a commercially available silica alumina zeolite catalyst sold under the tradename CBZ-1, manufactured by Davison Division, W. R. Grace & Company was used after steaming to simulate the approximate equilibrium activity of the catalyst.
- Fractionation zone 100 typically is maintained at a top pressure ranging between about 10 and 20 psi (68.95 and 137.9 kPa) and a bottoms temperature ranging up to about 400°C.
- the specific conditions will be a function of many variables including inlet product composition, inlet feed rates and desired compositions in the overhead, middle cut and bottoms.
- the middle cut fed to hydrogenation zone 110 preferably has a boiling range of about 200 to about 370°C and is frequently referred to as a light cat cycle oil.
- the feed to the hydrogenation zone, preferably light cat cycle oil should include compounds which will accept hydrogen in zone 110 and readily release the hydrogen in reaction zone 10 without dehydrogenative action.
- Preferred hydrogen donor compounds include two ring naphthenic compounds such as decahydronaphthalene (decalin) and two ring hydroaromatic compounds such as tetrahydronaphthalene (tetralin).
- Hydrogenation zone 110 may be of conventional design. Typical hydrogenation catalysts include molybdenum salts and nickel and/or cobalt salts deposited on a support material.
- the residence time of the middle cut from zone 100 in the hydrogenation zone may range from about 10 to about 240 minutes, depending on the hydrogen donor, hydrogenation catalyst, operating conditions and the desired degree of hydrogenation.
- the CBZ-1 antimony-free catalyst utilized was first steamed at 760°C for 16 hours after which the catalyst was contaminated .with the indicated metals by laboratory impregnation followed by calcining in air at about 540°C for four hours. The catalyst was then subjected to the indicated number of redox cycles. Each cycle consisted of a five-minute residence in a hydrogen atmosphere, a five-minute nitrogen flush and then a five-minute residence in an air atmosphere at the indicated temperatures. Following the redox cycles the catalyst was utilized in a microcatalytic cracking (MCC) unit.
- MCC microcatalytic cracking
- the MCC unit comprises a captive fluidized bed of catalyst kept at a cracking zone temperature of 500°C.
- Table II illustrates that hydrogen and coke make reductions similar to that shown in Table I also were obtained on a metals contaminated catalyst wherein the metals had been deposited by the processing of heavy metal containing feeds rather than by laboratory impregnation.
- Table III illustrates that the degree of passivation is a function of the reduction zone temperature. It can be seen that the adverse catalytic effects of the metal contaminants are only slightly reduced over that of untreated catalyst, where the temperature in reduction zone 70 is only 500°C. As the reduction zone temperature is increased, it can be seen that the degree of passivation increases. Based on this data, it is believed that the reduction step decreases the hydrogen and coke makes and that the reduction must be performed at a temperature in excess of 500°C.
- Table IV illustrates that where only one of the metal contaminants is present, the redox step at 650°C is not as effective in reducing the hydrogen and coke makes.
- the metal contaminants on a catalyst where at least a major portion i.e., at least 50 wt.% of the total of the metal contaminants comprises nickel, vanadium or iron, it may be desirable to add predetermined quantities of either of the other two contaminants.
- crude oil will not contain relatively high concentrations of iron.
- Vanadium and nickel typically are found in many crudes, with the relative amounts varying with the type of crude.
- certain Venezuelan crudes have relatively high vanadium and relatively low nickel concentrations, while the converse is true for certain domestic crudes.
- certain hydrotreated residual oils and hydrotreated gas oils may have relatively high nickel and relatively low vanadium concentrations, since hydrotreating removes vanadium more effectively than nickel.
- a catalyst could have substantial iron depositions where the iron oxide scale on process equipment upstream of the catalyst breaks off and is transported through the system by the feedstock.
- the relative catalytic activity of the individual metal contaminants nickel, vanadium and iron for the formation of hydrogen and coke are approximately 10:2.5:1.
- iron preferably should be added to passivate catalyst contaminated only with nickel, or vanadium.
- Table V illustrates the passivation that is achieved by adding quantities of iron to catalyst comprising only vanadium or only nickel.
- Table VI illustrates the passivation achieved by adding varying weights of vanadium to catalyst comprising only the nickel contaminant. Attention is directed to the fact that the addition of 0.02 wt.% vanadium followed by redox partially passivated the catalyst. Combination of the nickel contaminated catalyst with 0.12 wt.% vanadium followed by redox further passivated the catalyst. However, combination of the nickel contaminated catalyst with 0.50 wt.% vanadium resulted in an increase in undesired catalytic activity over that of the catalyst containing only 0.12 wt.% nickel. Thus, there appears to be a level of addition of the second metal component, above which the effectiveness of the passivation decreases. The exact amount of nickel, vanadium or iron which should be added to a metal-contaminated catalyst has not been determined.
- Table VII illustrates passivation of a catalyst impregnated with equal weight percentages of nickel and vanadium. It should be noted that the redox at 650°C resulted in a significant decrease in hydrogen and coke makes, but that, here also, the further addition of passivating metal in the form of iron actually increased the undesired catalytic activity of the metal contaminants slightly.
- Table VIII illustrates that metals-contaminated catalyst also can be passivated by the use of carbon monoxide rather than hydrogen as the reducing agent. In one run CP * grade CO containing 99.3 % CO by volume was utilized in the previously described passivation process while reagent grade hydrogen was used in the comparative run. It can be seen that both reducing agents passivated the catalyst to about the same extent.
- the quantity of metal contaminant, or passivation promoter, if any, that should be added to the system may be determined preferably by monitoring the hydrogen and coke makes in the reaction zone or by analyzing the metal contaminant concentration either in the hydrocarbon feed or on the catalyst. Where additional iron, vanadium or nickel is to be added to the system to reduce the hydrogen and coke makes, it * Chemically Pure is believed that the additional quantities of these metals should be added to the feed, rather than impregnated onto the catalyst prior to use. Impregnation of an excess of these metals onto the catalyst prior to use in the cracking operation may lead to higher initial hydrogen and coke makes.
- passivation promoters having relatively high vapor pressures such as antimony
- some of the passivation promoter may be lost to the atmosphere if it is impregnated onto the catalyst. It has been found that the passivation efficiency of antimony is higher when the antimony is incorporated into the hydrocarbon feedstock than when it is impregnated onto the catalyst.
- Table X shows that the addition of a hydrogen donor to the reaction zone reduces the hydrogen and coke makes. When this is combined with the previously described passivation process, still lower coke makes result.
- the feed for all tests was 60% vacuum gas oil (VGO), and 40% light cat cycle oil (LCCO).
- the vacuum gas oil had a minimum boiling point of about 340°C and a maximum boiling point of about 565°C as in the previous tests.
- the light cat cycle oil had a minimum boiling point of about 200°C and a maximum boiling point of about 325°C.
- the LCCO was not hydrogenated and the metals contaminated catalyst was not passivated.
- the LCCO fraction of the feed was hydrogenated by passing the LCCO through a hydrogenation zone maintained at a temperature of about 371°C and 2000 psig, comprising a nickel-molybdenum sulfided catalyst in a carbonaceous matrix to increase the hydrogen content of the LCCO fraction from 10.51 wt.% hydrogen to 12.10 wt.% hydrogen.
- the average residence time of the LCCO in the hydrogenation zone was about 180 minutes.
- the LCCO fraction of the feed was not hydrogenated, but the catalyst was passivated by subjecting the catalyst to 4 redox cycles in a hydrogen atmosphere as previously described.
- psi designates “pounds per square inch” and is converted to the equivalent pressure in kg/cm 2 by multiplying by 0.07031.
- SCF designates "standard cubic feet”, and is converted to litres by multiplying by 28.316.
- Temperatures in °F are converted to °C by subtracting 32 and then dividing by 1.8.
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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)
- Catalysts (AREA)
Claims (9)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE8181302405T DE3174040D1 (en) | 1981-06-01 | 1981-06-01 | Method of reducing coke formation in heavy hydrocarbon feed catalytic cracking |
EP19810302405 EP0066018B1 (de) | 1981-06-01 | 1981-06-01 | Verfahren zum Vermindern der Koksablagerung in einem katalytischen Krackverfahren von schweren Kohlenwasserstoffen |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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EP19810302405 EP0066018B1 (de) | 1981-06-01 | 1981-06-01 | Verfahren zum Vermindern der Koksablagerung in einem katalytischen Krackverfahren von schweren Kohlenwasserstoffen |
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EP0066018A1 EP0066018A1 (de) | 1982-12-08 |
EP0066018B1 true EP0066018B1 (de) | 1986-03-12 |
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EP19810302405 Expired EP0066018B1 (de) | 1981-06-01 | 1981-06-01 | Verfahren zum Vermindern der Koksablagerung in einem katalytischen Krackverfahren von schweren Kohlenwasserstoffen |
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DE (1) | DE3174040D1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9193913B2 (en) | 2012-09-21 | 2015-11-24 | Suncoke Technology And Development Llc | Reduced output rate coke oven operation with gas sharing providing extended process cycle |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4409093A (en) * | 1981-05-04 | 1983-10-11 | Exxon Research And Engineering Co. | Process for reducing coke formation in heavy feed catalytic cracking |
US5198098A (en) * | 1990-10-19 | 1993-03-30 | Ashland Oil, Inc. | Magnetic separation of old from new equilibrium particles by means of manganese addition |
DE102011005400B4 (de) | 2011-03-11 | 2015-05-28 | Deere & Company | Anordnung und Verfahren zur Abschätzung des Füllgrades beim Überladen landwirtschaftlichen Ernteguts von einer Erntemaschine auf ein Transportfahrzeug |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
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CA729167A (en) * | 1966-03-01 | F. Crocoll James | Conversion process | |
US2575258A (en) * | 1948-12-06 | 1951-11-13 | Standard Oil Dev Co | Regenerating an iron-contaminated cracking catalyst |
US3224961A (en) * | 1962-09-25 | 1965-12-21 | Sinclair Research Inc | Cracking with poison-resistant catalyst |
US3413212A (en) * | 1965-12-08 | 1968-11-26 | Mobil Oil Corp | Cracking of hydrocarbons with a crystalline aluminosilicate in the presence of a hydrogen donor |
US3479279A (en) * | 1966-08-22 | 1969-11-18 | Universal Oil Prod Co | Gasoline producing process |
US4013546A (en) * | 1974-07-19 | 1977-03-22 | Texaco Inc. | Removing metal contaminant from regenerated catalyst in catalytic cracking process |
US4031002A (en) * | 1975-02-18 | 1977-06-21 | Phillips Petroleum Company | Passivating metals on cracking catalysts with antimony compounds |
US3977963A (en) * | 1975-04-17 | 1976-08-31 | Gulf Research & Development Company | Method of negating the effects of metals poisoning on cracking catalysts |
US4183803A (en) * | 1976-03-29 | 1980-01-15 | Phillips Petroleum Company | Passivating metals on cracking catalysts |
US4264433A (en) * | 1978-10-06 | 1981-04-28 | Phillips Petroleum Company | Passivating metals on cracking catalysts by indium antimonide |
US4263172A (en) * | 1979-08-13 | 1981-04-21 | Phillips Petroleum Company | Cracking catalysts |
US4257919A (en) * | 1979-11-01 | 1981-03-24 | Phillips Petroleum Company | Method of transferring a passivating agent to or from a cracking catalyst |
US4244810A (en) * | 1979-12-10 | 1981-01-13 | Texaco Inc. | Fluidized catalytic cracking process for increased hydrogen production |
-
1981
- 1981-06-01 EP EP19810302405 patent/EP0066018B1/de not_active Expired
- 1981-06-01 DE DE8181302405T patent/DE3174040D1/de not_active Expired
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9193913B2 (en) | 2012-09-21 | 2015-11-24 | Suncoke Technology And Development Llc | Reduced output rate coke oven operation with gas sharing providing extended process cycle |
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EP0066018A1 (de) | 1982-12-08 |
DE3174040D1 (en) | 1986-04-17 |
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