CA2004390A1 - Process for the conversion of a hydrocarbonaceous feedstock - Google Patents
Process for the conversion of a hydrocarbonaceous feedstockInfo
- Publication number
- CA2004390A1 CA2004390A1 CA 2004390 CA2004390A CA2004390A1 CA 2004390 A1 CA2004390 A1 CA 2004390A1 CA 2004390 CA2004390 CA 2004390 CA 2004390 A CA2004390 A CA 2004390A CA 2004390 A1 CA2004390 A1 CA 2004390A1
- Authority
- CA
- Canada
- Prior art keywords
- feedstock
- process according
- catalyst
- zeolite
- conversion
- 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.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 239000010457 zeolite Substances 0.000 claims abstract description 23
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 15
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011148 porous material Substances 0.000 claims abstract description 8
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052675 erionite Inorganic materials 0.000 claims description 3
- 229910001657 ferrierite group Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 229910052914 metal silicate Inorganic materials 0.000 claims description 2
- 239000000047 product Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- -1 gallium silicates Chemical class 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000000571 coke Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 101100452593 Caenorhabditis elegans ina-1 gene Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 101100133466 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) nit-4 gene Proteins 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 241000283984 Rodentia Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BALXUFOVQVENIU-KXNXZCPBSA-N pseudoephedrine hydrochloride Chemical compound [H+].[Cl-].CN[C@@H](C)[C@@H](O)C1=CC=CC=C1 BALXUFOVQVENIU-KXNXZCPBSA-N 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- VLPFTAMPNXLGLX-UHFFFAOYSA-N trioctanoin Chemical compound CCCCCCCC(=O)OCC(OC(=O)CCCCCCC)COC(=O)CCCCCCC VLPFTAMPNXLGLX-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 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
- 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
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen
Landscapes
- 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)
- Crystallography & Structural Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
A B S T R A C T
PROCESS FOR THE CONVERSION OF A HYDROCARBONACEOUS FEEDSTOCK
A process for the conversion of a hydrotreated and/or hydrocracked hydrocarbonaceous feedstock, such as a heavy flashed distillate or deasphalted oil, comprises contacting the feedstock with a zeolitic catalyst which comprises a zeolite with a pore diameter of 0.4 to 0.7 nm at a temperature above 480 °C and a pressure of up to 10 bar for less than 10 seconds.
PROCESS FOR THE CONVERSION OF A HYDROCARBONACEOUS FEEDSTOCK
A process for the conversion of a hydrotreated and/or hydrocracked hydrocarbonaceous feedstock, such as a heavy flashed distillate or deasphalted oil, comprises contacting the feedstock with a zeolitic catalyst which comprises a zeolite with a pore diameter of 0.4 to 0.7 nm at a temperature above 480 °C and a pressure of up to 10 bar for less than 10 seconds.
Description
3~
PROCESS ~OR THE ~ONVERSION OF A HYDROCARBONACEO~S FEEDSTOCK
Th~ present inv~ntion r~laeQs to a proce;~ for the conv~rsion of a hydrocarbonacao~s aedstock and is particul~rly concsrnet wlth the upgrading o~ cartain feedstocks.
US 4,171,257 tescribes a process for upgrading a hydro-carbonacaous e~dstock by contacting tha feedstock wi~h a ZSM-5 crystalline alu~inosilicae~ caealyst at a pressure belo~ 14 bar, a temperature of 260 to 427 ~C and a space v810city of 0. 1 to 15 l/l.h. The feedseock, axemplifLed as gas oil having a boiling poine range of 230 to 437 C, must con~ain less than 5 ppmw of nitrogen-cnntainin~ co~pounds, calculated as nitrogen. The upgraded product incl~des olafinic hydrocarbons, such as propena ~nd butenes.
The production of olafins is d~sirabl~ as their resctivity renders eham suitabl~ or conv~rsion to further products, in contrast to th~ low value lower paraffins. Ho~aver, the above described process has the drawback thae ehe Initial feed~tock ~ust have been severely denitrifiad in order to avoid rapid catalyst deactivation.
I~ has surprisingly been found that a comparaei~ely hi~h yield of olefins can be obtained, under less stringent csnditions as ra~ards ni~rogen content, using certain z~olit~c catalys~s, at high te~peratur~ with a short fe~dstock r~ idenc~ Ci~Q. Furtharmor~
has be~n ~urpris~ngly found that th~ convarsion is ~u~t~bl3 for haavy hydrocarbon feedstocks and an upgsaded product rich in lower ol~fins can be-obtain~d therefro~.
Accordingly, th~ pr~sent invention provid~s a proc~ss or the conv2rsion ~f a hydrotreated and~or hydrocrack~d h~avy hytro-carbonaceous feedstock, whlch process comprises contaceing the feedstock with a zeolitic catalyst co~pri3ing a z~olitc with a por3 3~3~
diameter of 0.4 to 0.7 nm a~ a temperature of greater than 480 C
and a pressure of up to 10 bar during less than 10 seconds.
The feedstock is contacted with the ~eolitic catalyst for less than 10 seconds. Suitably, the minimum contact time is 0.1 second.
Very good results are obtainable with a process in which ths feedseock is contacted with the zeolitic catalyst during 1 to 6 seconds.
The temperature during the reaction is relatively high.
However, the combination of high temperature and short residence time allows a high conversion to olefins. A preferrçd temperature range is 480 to 900 C, more preferably 500 to 750 C.
The æeolitic catalyst comprises a zeolite with a pore diame~er of from 0.4 ~o 0.7 nm. The catalys~ suitably further comprises a refractory oxide that serves as binder material. Suitable rafractory oxides include alumina, silica, silica-alumina, magnesia, titania, zirconia and mixtures thereof. Alu~ina is espacially preferred. The weight ratio of refractory oxide and zeolite suitably ranges from 10:90 to 90:10, preferably from 50:50 to 85:}S. The catalyst may comprise further zeolites with a pore diameter above 0.7 nm. Suitable examples of such zeolites include the fau~asite-type zeolites, zeolite beta, 7eolite omega and in particular zeolite X and Y. The zeolit$c catalyst preferably comprises as æeolite substantially only zeolites with a pore diameter of from 0.4 to 0.7 nm.
The term zeolite in this specification is not to be regarded as comprising only crystalline aluminium silicates. The term slso includes crystalline silica (silicalite), silicoaluminophosphates ~SAP0), chromosilicates, gallium silicates, iron silica~es, aluminlum phosphates (ALP0), titaniu~ al~minosilicate~ (TAS0), boron silicates, titanium aluminophosphates (TAP0) and iron aluminosilicates.
Examples of zeolites that may be used in the process o~ the invention and that ha~e a pore diameter of 0.4 to 0.7 nm, include SAP0-4 and SAP0-11, which are described in US-A-4,440,871, ALP0-11, described in US-A-4,310,440, TAP0-11, described in US-A-4,500,651, 3~0 TAS0-45, described in EP-A-229,295, boron silicates, described in e.g. US-A-4,254,297, aluminium silicates like erionite, ferrierite theta and the ZSM-type zeolites such as ZC.M-5, ZSM-ll, ZSM-12, ZSM-35, ZSM-23, and ZSM-38. Preferably the æeolite ls selected from the group consisting of crystalline me~al silicates having a ZSM-5 structure, ferrierite, erionite and mixtures theraof. Sultable examples of crystalline metal silicates with ZSM-5 structure are aluminium, galli~, iron, scand1um, rhodium and/or scandlum silicatas as described in e.g. GB-B-2,110,559.
During the preparation of the zeolites usually a significant amount of alkali metal oxide is present in the prepared zeolite.
Preferably the amount of alkali metal is removed by methods known in the art, such as ion xchange, optionally followed by calcination, to yield the zeolite in its hydrogen form. Preferably the zeolite used in the present process is substantially in its hydrogen form.
Olefin production is facilitated by the absence of hydrogen or a hydrogen donor. Hence, the present process is advantageously carried out in ~he absence of added hytrogen and/or ~taam. It i9, of course, possible that during the reaction some small molecules, such as hydrogen molecules are formed. However, this ~mount is usually negligible and will be less than 0.5 ~wt of the product.
The pressure in the present process can be varied within wide ranges. It is, however, preferred that the pressure is such that at the prevailing temperature th~ feedstock is substantially in its gaseous phase. Then it is easier to achieve the short contact times envisagsd. Hence, the pressure is preferably relatively low. This is the ~ore advantageous qince no expansive compressors and high-pressure vessels and other equipment are necessary. Pressures up to 10 bar can be employed. Subatmospheric pressures are possible, but not preferred. The ~ini~um pressure is suitably 1 bar. It is economically advantsgeous to operate at atmospheric pressure.
3~
The catalyst/feedscock weight ratio ~ay vary widely, for example up eo 200 kg of catalyst per kg of faetstock. Prefasably, the caealyst/fesdscock ~eighe ratio is fro~ 2 to 200.
The process according to the pres~nt ~nvention may bo carried out in a fixed bed. However, this would i~ply ehae extramely high space veLocities be required eo attain ~he short contac~ times envisa~ed. Therefore, ~h2 pres~nt process 1~ preferably carrisd out in a moving bed. The bed of catalyse may ~ove upwards or downwards.
When the bed moves upwards a process similar to a fluidized catalytic cracking process i5 vbtained. Prefarably, the process ls carr$ed out in a downwardly ~oving bed.
During the process some coke for~s on the catalyst. Thercfore, it i9 advantageous to regen~rato the catalyst. Preferably the catalyst is regenerated by sub~ecting i~, ~ftar having bean contacted with the faedstock, to a traa~m~nt with an oxidizing gas, such as air. A continuous regeneraeion, si~ilar to the regene~ation carried out in a fluidized ca~alytic cracking proceis, is ~specially prefsrred.
The coke formation does not occur at a very high raee. ~ance, it would be posslbla to arranga or a proc~ss in which the - residence ti~ of the catalyse part$cles in a reaction zone, e.g.
moving bed, is longer than the r~sidence time of the feedstock in th~ reaceion zone. Of cours~ the contact ti~e between eedstock ant catalys~ should be less than L0 second~. The contact time generally corrasponds with the residence time of ths feedstock. Suitably the rasidenca time of the cstalyst is from 1 to 20 times t~ residenco time of the feedstoc~.
She feedstock which i3 to ba convsrted i~ the present process comprises hydrotreated and/or hydrocracked hydrocarbons, preferably, though not n~ces~arily, hea~y feedstocXs.
Suitable feedstock~ arR obtainad by hydrotrQaeing and/or hydro-cracking he~vy flashed d~tillat~ iraceio~ fro~ long r~sidu~ or d~sphaltad oLls o'otainet irom short rosL~u~. Th~ fe~d~tock i~
suitably fraceLonated to ~amove lower boiling fractions aft~r 2g~ 0 hydrotreating and/or hydrocracking and prior to contacting with the zeolitic catalyst in accordance with the invention.
The product obtained by the process of the invention is op~ionally fractionated to yield an olefin-rich gas fraction, a gasoline fraction and a bottom fraction, all or part of which is optionally recycled to the feedstock upstream of the hydrotreating snd/or hydrocracking unit. In this way, high conversion of the heavy deasphalted oil or heavy flashed distillate feedstock to more valuable olefin-rich gas is obtained.
Therefore, in accordance with a fureher aspect of the in~ention, there is provided a process for ehe con~ersion of a hydrocarbonaceous feedstock comprising hydrotreating and/or hydrocracking said feedstock in the presence of a suitable catalyst, contacting at least a part of the hydrotreated and/or hydrocracked product with a zeolitic catalyst comprising a zsolite with a pore diameter of 0.4 to 0.7 nm at a temperature of greater than 480 C and a pressure of up to 10 bar during less than 10 seconds, fractionating the resulting converted material and recycling a heavier fraction to said hydrotreating and/or hydrocracking step.
The said hydrotreating step is known in the art and may be carried out at known conditions. Suitable conditions includs a temperature of 150 to 400 C, a hydrogen (partial) prsssure of 30 to 150 bar, a space velocity of n . s to 4.0 kg/l.h and a hydrogen/feedstock ratio of 100 to 2000 Nl/kg. Suitable hydro-treating catalysts comprise nickel, cobalt, tungsten, molybdenum, platinu~, palladium or mixtures thereof on a carrier, such as alu~ina, silica-alumina, silica, zirconia, zeolites and the like.
The catalyst may further comprise fluorine, phosphorus and/or boron. The temperature, gas rate and space velocity can be selected by the person skilled in the are, suitably from the range given above.
Hydrocracking is also known in the art and may be carried out under known conditions, such as over a hydrocracking catalyst at a temperature of 300 to 450 C, a hydrogen (partial) pressure of 50 3~
to 200 bar, a space velocity of 0.5 to 2.0 kg/l.catalyst.h and a H2/mineral oil fraction ratio of 500 to 2000 Nl/kg. The hydro-cracking catalyst can be selected from any hydrocracking catalyst known in the art. Suitably the hydrocracking catalyst co~prises a carrier and at least one hydrogenating metal or a co~pound thereof, which carrier has been selected from the group con.sisting of silica, alumina, silica-alumina and the faujasite-type 2eolites.
The most preferred faujasiee-type zeolite is zeolite Y. The most preferred hydrogenating metals are nickel, cobalt, tungsten and molybdenum and mixtures thereof, but platinum and/or palladium may also be used. The catalyst may further comprise fluorine and/or phosphorus and/or boron. When nickel, cobalt, molybdenum and/or tungsten are used as hydrogenating me~al, they are pref~rably present in the form of their sulphides.
One of the advantages of the present invention over the process according to US 4,171,257 re~ des in the fact that a feedstock with a nitrogen content graater than 5 ppmw may be used with substantially no effect on the caealyst activity. Suitable Peedstocks may have a nitrogen content oi more than 10 ppmw, calculated as nitrogen. The feedstoc'~ may a~en have a nitrogen content of 1000 ppmw or more, calculacad as nitrogen.
The invention will now be furtnar dsscribed with reference to the following examples and the accom?anying drawing:
The ieedstock in ehis exa~ple was a hydrotreated Arabian light deasphalted oil having the following properties:
IBP, C 453 50 ~wt 591 67 ~wt 620 density 70/4 0.B532 kgjl sulphur232 ppmw nitrogen12 ppmw The DAO feedstock was upgraded in a downflow reactor by passing it downwards co-currently with a flow of catalyse particles. The catalyst comprised ZSM-5 in an alumina ~atrix 9~
~weight ratio ZS~ 5/alu~ina 1:3). The experiment was carriad out at atmospheric pressure. Further process conditions and the results of the experiment are given in Table 1 below.
Process conditions:
Reactor temperature, C 531 Catalyst/oil ratio, g~g 4.3 Contact time, s 2.2 Product, ~w on feed Cl 1.0 C2 1.2 C2 4.9 C3 2.0 C3 17.9 C4 2.1 C4 16.4 CS-221 C 26.3 221-~50 C 18.2 450 ~C+ 9.1 Coka 0.8 Conversion of 450 C+ feed, ~w 91 Fro~ the above results it will be seen that a high proportion of the gaseous products was olefinically unsaturated and the product contained a comparatively high proportion of midd}e distillates.
EXA~IPLE 2 The feedstock in this example was a hydrocracked heavy flashed distillate ha~ing the following properties:
IBP, C 330 50 3wt 432 FBP, C 620 fraction boiling below 370 C, ~wt 7,7 density 70/4 0.8157 kg/l sulphur 20 ppmw nitrogen 2 pp~w 3~
Tha ~xperiment was carried out as described in E~ample 1, but using the process conditions described in Table 2 below to ~ive the results given in Table 2.
Process conditions:
Reactor temperature, C 579 Catalyst/oil ratio, g/~ 141 Contact time, s 1.7 Product, ~w on fead Cl 1.6 C2 1.0 ~2 14.7 C3 3.9 C3 37.3 C4 4.6 C4 18.8 G5-221 ~C 8.6 221-370 C 2.3 370 C~ 0.4 Coke 6.3 Conversion of 370 C~, ~w 99.6 This example employed as feedstock an Arabian heavy heavy flashed distillate which, after initial hydrocracking, typically had the proper~iec gi~en in Table 3 below.
The flashed distillate was treated in accordance with the process illustrated in Fig. 1 as follows.
Feedstock W85 introduced on line 1, af er mixing with hydrogen from line 2, to a hydrotreating/hydrocracking unit 3 operated at 90 bar hydrogen partial pressure at 400 C with a suitable ~i/Mo/alumina hytrotreating catalyst.
The hydrotreated product was fractionated in ~nit 4 into a gaseous fraction 5, a naphtha fraction 6, a kerosine fraction 7, a ~as oil fraction 8 and a bottoms fraction 9. Under conditions as described herein, bottoms fraction 9 was passed to a downflow 3~
reactor 10 as described in Example 1, containing catalyst as described in Example 1 and provided with suitable regeneration means from which coke can be removed in line 11 when necessary, while gaseous and liquid product is saparated in fractionation unit 12 lnto a gaseous product 13, a gasoline product 14 and a bottoms stream 15, which is recycled to ehe feedstock in line 1 for re-processing.
Bottoms fraction 9 which is upgraded in reactor 10 comprises about 69% by weight based on the initial feed in llne 1 when fractionated in unit 12. The co~position of the fract$on obtalned from unit 12 i5 given in Table 3 below:
Hydrocracked feedstock Refractive index, ~1.4720 W aromatics, ~ol/100 g mono25 di 4 poly 3 Initial boiling point, C 340 50 ~wt 420 Final boiling point540 Product, ~w on feed Gas (Cl 4) 31.5 H2 0.1 Cl 0.7 C2 0.8 C2 3.4 C3 1.4 C3 12.3 C4 1.5 C4 11.3 Gasoline (C5-221 C)18.5 Coke o.5 Recycle (221 C) 19 3 91`~
It will be seen from the above results that the bottoms component sepsrated from the ini~ial flashed distillate has yielded a high proportion of olefinically unsaturated gaseous products and gasoline while ehe recycling facility enables maxlmum upgrading to S more valuable products.
PROCESS ~OR THE ~ONVERSION OF A HYDROCARBONACEO~S FEEDSTOCK
Th~ present inv~ntion r~laeQs to a proce;~ for the conv~rsion of a hydrocarbonacao~s aedstock and is particul~rly concsrnet wlth the upgrading o~ cartain feedstocks.
US 4,171,257 tescribes a process for upgrading a hydro-carbonacaous e~dstock by contacting tha feedstock wi~h a ZSM-5 crystalline alu~inosilicae~ caealyst at a pressure belo~ 14 bar, a temperature of 260 to 427 ~C and a space v810city of 0. 1 to 15 l/l.h. The feedseock, axemplifLed as gas oil having a boiling poine range of 230 to 437 C, must con~ain less than 5 ppmw of nitrogen-cnntainin~ co~pounds, calculated as nitrogen. The upgraded product incl~des olafinic hydrocarbons, such as propena ~nd butenes.
The production of olafins is d~sirabl~ as their resctivity renders eham suitabl~ or conv~rsion to further products, in contrast to th~ low value lower paraffins. Ho~aver, the above described process has the drawback thae ehe Initial feed~tock ~ust have been severely denitrifiad in order to avoid rapid catalyst deactivation.
I~ has surprisingly been found that a comparaei~ely hi~h yield of olefins can be obtained, under less stringent csnditions as ra~ards ni~rogen content, using certain z~olit~c catalys~s, at high te~peratur~ with a short fe~dstock r~ idenc~ Ci~Q. Furtharmor~
has be~n ~urpris~ngly found that th~ convarsion is ~u~t~bl3 for haavy hydrocarbon feedstocks and an upgsaded product rich in lower ol~fins can be-obtain~d therefro~.
Accordingly, th~ pr~sent invention provid~s a proc~ss or the conv2rsion ~f a hydrotreated and~or hydrocrack~d h~avy hytro-carbonaceous feedstock, whlch process comprises contaceing the feedstock with a zeolitic catalyst co~pri3ing a z~olitc with a por3 3~3~
diameter of 0.4 to 0.7 nm a~ a temperature of greater than 480 C
and a pressure of up to 10 bar during less than 10 seconds.
The feedstock is contacted with the ~eolitic catalyst for less than 10 seconds. Suitably, the minimum contact time is 0.1 second.
Very good results are obtainable with a process in which ths feedseock is contacted with the zeolitic catalyst during 1 to 6 seconds.
The temperature during the reaction is relatively high.
However, the combination of high temperature and short residence time allows a high conversion to olefins. A preferrçd temperature range is 480 to 900 C, more preferably 500 to 750 C.
The æeolitic catalyst comprises a zeolite with a pore diame~er of from 0.4 ~o 0.7 nm. The catalys~ suitably further comprises a refractory oxide that serves as binder material. Suitable rafractory oxides include alumina, silica, silica-alumina, magnesia, titania, zirconia and mixtures thereof. Alu~ina is espacially preferred. The weight ratio of refractory oxide and zeolite suitably ranges from 10:90 to 90:10, preferably from 50:50 to 85:}S. The catalyst may comprise further zeolites with a pore diameter above 0.7 nm. Suitable examples of such zeolites include the fau~asite-type zeolites, zeolite beta, 7eolite omega and in particular zeolite X and Y. The zeolit$c catalyst preferably comprises as æeolite substantially only zeolites with a pore diameter of from 0.4 to 0.7 nm.
The term zeolite in this specification is not to be regarded as comprising only crystalline aluminium silicates. The term slso includes crystalline silica (silicalite), silicoaluminophosphates ~SAP0), chromosilicates, gallium silicates, iron silica~es, aluminlum phosphates (ALP0), titaniu~ al~minosilicate~ (TAS0), boron silicates, titanium aluminophosphates (TAP0) and iron aluminosilicates.
Examples of zeolites that may be used in the process o~ the invention and that ha~e a pore diameter of 0.4 to 0.7 nm, include SAP0-4 and SAP0-11, which are described in US-A-4,440,871, ALP0-11, described in US-A-4,310,440, TAP0-11, described in US-A-4,500,651, 3~0 TAS0-45, described in EP-A-229,295, boron silicates, described in e.g. US-A-4,254,297, aluminium silicates like erionite, ferrierite theta and the ZSM-type zeolites such as ZC.M-5, ZSM-ll, ZSM-12, ZSM-35, ZSM-23, and ZSM-38. Preferably the æeolite ls selected from the group consisting of crystalline me~al silicates having a ZSM-5 structure, ferrierite, erionite and mixtures theraof. Sultable examples of crystalline metal silicates with ZSM-5 structure are aluminium, galli~, iron, scand1um, rhodium and/or scandlum silicatas as described in e.g. GB-B-2,110,559.
During the preparation of the zeolites usually a significant amount of alkali metal oxide is present in the prepared zeolite.
Preferably the amount of alkali metal is removed by methods known in the art, such as ion xchange, optionally followed by calcination, to yield the zeolite in its hydrogen form. Preferably the zeolite used in the present process is substantially in its hydrogen form.
Olefin production is facilitated by the absence of hydrogen or a hydrogen donor. Hence, the present process is advantageously carried out in ~he absence of added hytrogen and/or ~taam. It i9, of course, possible that during the reaction some small molecules, such as hydrogen molecules are formed. However, this ~mount is usually negligible and will be less than 0.5 ~wt of the product.
The pressure in the present process can be varied within wide ranges. It is, however, preferred that the pressure is such that at the prevailing temperature th~ feedstock is substantially in its gaseous phase. Then it is easier to achieve the short contact times envisagsd. Hence, the pressure is preferably relatively low. This is the ~ore advantageous qince no expansive compressors and high-pressure vessels and other equipment are necessary. Pressures up to 10 bar can be employed. Subatmospheric pressures are possible, but not preferred. The ~ini~um pressure is suitably 1 bar. It is economically advantsgeous to operate at atmospheric pressure.
3~
The catalyst/feedscock weight ratio ~ay vary widely, for example up eo 200 kg of catalyst per kg of faetstock. Prefasably, the caealyst/fesdscock ~eighe ratio is fro~ 2 to 200.
The process according to the pres~nt ~nvention may bo carried out in a fixed bed. However, this would i~ply ehae extramely high space veLocities be required eo attain ~he short contac~ times envisa~ed. Therefore, ~h2 pres~nt process 1~ preferably carrisd out in a moving bed. The bed of catalyse may ~ove upwards or downwards.
When the bed moves upwards a process similar to a fluidized catalytic cracking process i5 vbtained. Prefarably, the process ls carr$ed out in a downwardly ~oving bed.
During the process some coke for~s on the catalyst. Thercfore, it i9 advantageous to regen~rato the catalyst. Preferably the catalyst is regenerated by sub~ecting i~, ~ftar having bean contacted with the faedstock, to a traa~m~nt with an oxidizing gas, such as air. A continuous regeneraeion, si~ilar to the regene~ation carried out in a fluidized ca~alytic cracking proceis, is ~specially prefsrred.
The coke formation does not occur at a very high raee. ~ance, it would be posslbla to arranga or a proc~ss in which the - residence ti~ of the catalyse part$cles in a reaction zone, e.g.
moving bed, is longer than the r~sidence time of the feedstock in th~ reaceion zone. Of cours~ the contact ti~e between eedstock ant catalys~ should be less than L0 second~. The contact time generally corrasponds with the residence time of ths feedstock. Suitably the rasidenca time of the cstalyst is from 1 to 20 times t~ residenco time of the feedstoc~.
She feedstock which i3 to ba convsrted i~ the present process comprises hydrotreated and/or hydrocracked hydrocarbons, preferably, though not n~ces~arily, hea~y feedstocXs.
Suitable feedstock~ arR obtainad by hydrotrQaeing and/or hydro-cracking he~vy flashed d~tillat~ iraceio~ fro~ long r~sidu~ or d~sphaltad oLls o'otainet irom short rosL~u~. Th~ fe~d~tock i~
suitably fraceLonated to ~amove lower boiling fractions aft~r 2g~ 0 hydrotreating and/or hydrocracking and prior to contacting with the zeolitic catalyst in accordance with the invention.
The product obtained by the process of the invention is op~ionally fractionated to yield an olefin-rich gas fraction, a gasoline fraction and a bottom fraction, all or part of which is optionally recycled to the feedstock upstream of the hydrotreating snd/or hydrocracking unit. In this way, high conversion of the heavy deasphalted oil or heavy flashed distillate feedstock to more valuable olefin-rich gas is obtained.
Therefore, in accordance with a fureher aspect of the in~ention, there is provided a process for ehe con~ersion of a hydrocarbonaceous feedstock comprising hydrotreating and/or hydrocracking said feedstock in the presence of a suitable catalyst, contacting at least a part of the hydrotreated and/or hydrocracked product with a zeolitic catalyst comprising a zsolite with a pore diameter of 0.4 to 0.7 nm at a temperature of greater than 480 C and a pressure of up to 10 bar during less than 10 seconds, fractionating the resulting converted material and recycling a heavier fraction to said hydrotreating and/or hydrocracking step.
The said hydrotreating step is known in the art and may be carried out at known conditions. Suitable conditions includs a temperature of 150 to 400 C, a hydrogen (partial) prsssure of 30 to 150 bar, a space velocity of n . s to 4.0 kg/l.h and a hydrogen/feedstock ratio of 100 to 2000 Nl/kg. Suitable hydro-treating catalysts comprise nickel, cobalt, tungsten, molybdenum, platinu~, palladium or mixtures thereof on a carrier, such as alu~ina, silica-alumina, silica, zirconia, zeolites and the like.
The catalyst may further comprise fluorine, phosphorus and/or boron. The temperature, gas rate and space velocity can be selected by the person skilled in the are, suitably from the range given above.
Hydrocracking is also known in the art and may be carried out under known conditions, such as over a hydrocracking catalyst at a temperature of 300 to 450 C, a hydrogen (partial) pressure of 50 3~
to 200 bar, a space velocity of 0.5 to 2.0 kg/l.catalyst.h and a H2/mineral oil fraction ratio of 500 to 2000 Nl/kg. The hydro-cracking catalyst can be selected from any hydrocracking catalyst known in the art. Suitably the hydrocracking catalyst co~prises a carrier and at least one hydrogenating metal or a co~pound thereof, which carrier has been selected from the group con.sisting of silica, alumina, silica-alumina and the faujasite-type 2eolites.
The most preferred faujasiee-type zeolite is zeolite Y. The most preferred hydrogenating metals are nickel, cobalt, tungsten and molybdenum and mixtures thereof, but platinum and/or palladium may also be used. The catalyst may further comprise fluorine and/or phosphorus and/or boron. When nickel, cobalt, molybdenum and/or tungsten are used as hydrogenating me~al, they are pref~rably present in the form of their sulphides.
One of the advantages of the present invention over the process according to US 4,171,257 re~ des in the fact that a feedstock with a nitrogen content graater than 5 ppmw may be used with substantially no effect on the caealyst activity. Suitable Peedstocks may have a nitrogen content oi more than 10 ppmw, calculated as nitrogen. The feedstoc'~ may a~en have a nitrogen content of 1000 ppmw or more, calculacad as nitrogen.
The invention will now be furtnar dsscribed with reference to the following examples and the accom?anying drawing:
The ieedstock in ehis exa~ple was a hydrotreated Arabian light deasphalted oil having the following properties:
IBP, C 453 50 ~wt 591 67 ~wt 620 density 70/4 0.B532 kgjl sulphur232 ppmw nitrogen12 ppmw The DAO feedstock was upgraded in a downflow reactor by passing it downwards co-currently with a flow of catalyse particles. The catalyst comprised ZSM-5 in an alumina ~atrix 9~
~weight ratio ZS~ 5/alu~ina 1:3). The experiment was carriad out at atmospheric pressure. Further process conditions and the results of the experiment are given in Table 1 below.
Process conditions:
Reactor temperature, C 531 Catalyst/oil ratio, g~g 4.3 Contact time, s 2.2 Product, ~w on feed Cl 1.0 C2 1.2 C2 4.9 C3 2.0 C3 17.9 C4 2.1 C4 16.4 CS-221 C 26.3 221-~50 C 18.2 450 ~C+ 9.1 Coka 0.8 Conversion of 450 C+ feed, ~w 91 Fro~ the above results it will be seen that a high proportion of the gaseous products was olefinically unsaturated and the product contained a comparatively high proportion of midd}e distillates.
EXA~IPLE 2 The feedstock in this example was a hydrocracked heavy flashed distillate ha~ing the following properties:
IBP, C 330 50 3wt 432 FBP, C 620 fraction boiling below 370 C, ~wt 7,7 density 70/4 0.8157 kg/l sulphur 20 ppmw nitrogen 2 pp~w 3~
Tha ~xperiment was carried out as described in E~ample 1, but using the process conditions described in Table 2 below to ~ive the results given in Table 2.
Process conditions:
Reactor temperature, C 579 Catalyst/oil ratio, g/~ 141 Contact time, s 1.7 Product, ~w on fead Cl 1.6 C2 1.0 ~2 14.7 C3 3.9 C3 37.3 C4 4.6 C4 18.8 G5-221 ~C 8.6 221-370 C 2.3 370 C~ 0.4 Coke 6.3 Conversion of 370 C~, ~w 99.6 This example employed as feedstock an Arabian heavy heavy flashed distillate which, after initial hydrocracking, typically had the proper~iec gi~en in Table 3 below.
The flashed distillate was treated in accordance with the process illustrated in Fig. 1 as follows.
Feedstock W85 introduced on line 1, af er mixing with hydrogen from line 2, to a hydrotreating/hydrocracking unit 3 operated at 90 bar hydrogen partial pressure at 400 C with a suitable ~i/Mo/alumina hytrotreating catalyst.
The hydrotreated product was fractionated in ~nit 4 into a gaseous fraction 5, a naphtha fraction 6, a kerosine fraction 7, a ~as oil fraction 8 and a bottoms fraction 9. Under conditions as described herein, bottoms fraction 9 was passed to a downflow 3~
reactor 10 as described in Example 1, containing catalyst as described in Example 1 and provided with suitable regeneration means from which coke can be removed in line 11 when necessary, while gaseous and liquid product is saparated in fractionation unit 12 lnto a gaseous product 13, a gasoline product 14 and a bottoms stream 15, which is recycled to ehe feedstock in line 1 for re-processing.
Bottoms fraction 9 which is upgraded in reactor 10 comprises about 69% by weight based on the initial feed in llne 1 when fractionated in unit 12. The co~position of the fract$on obtalned from unit 12 i5 given in Table 3 below:
Hydrocracked feedstock Refractive index, ~1.4720 W aromatics, ~ol/100 g mono25 di 4 poly 3 Initial boiling point, C 340 50 ~wt 420 Final boiling point540 Product, ~w on feed Gas (Cl 4) 31.5 H2 0.1 Cl 0.7 C2 0.8 C2 3.4 C3 1.4 C3 12.3 C4 1.5 C4 11.3 Gasoline (C5-221 C)18.5 Coke o.5 Recycle (221 C) 19 3 91`~
It will be seen from the above results that the bottoms component sepsrated from the ini~ial flashed distillate has yielded a high proportion of olefinically unsaturated gaseous products and gasoline while ehe recycling facility enables maxlmum upgrading to S more valuable products.
Claims (12)
1. A process for the conversion of a hydrotreated and/or hydrocracked hydrocarbonaceous feedstock, which process comprises contacting the feedstock with a zeolitic catalyst comprising a zeolite with a pore diameter of 0.4 to 0.7 nm at a temperature of greater than 480°C and a pressure of up to 10 bar during less than 10 seconds.
2. A process according to claim 1 wherein the feedstock is contacted with the zeolitic catalyst during 1 to 6 seconds.
3. A process according to claim 1 or 2 wherein the temperature is 480 to 900°C.
4. A process according to any one of the preceding claims wherein the zeolite is selected from crystalline metal silicates having a ZSM-5 structure, ferrierite, erionite and mixtures thereof.
5. A process according to any one of the preceding claims in which the zeolite is substantially in its hydrogen form.
6. A process according to any one of the preceding claims which is carried out in the absence of added hydrogen or steam.
7. A process according to any one of the preceding claims in which the catalyst/feedstock weight ratio is from 2 to 200.
8. A process according to any one of the preceding claims which is carried out in a downwardly moving bed.
9. A process according to any one of the preceding claims wherein the feedstock is a hydrotreated and/or hydrocracked deasphalted oil or heavy flashed distillate.
10. A process for the conversion of a hydrocarbonacoous feedstock comprising hydrotreating and/or hydrocracking said feedstock in the presence of a suitable catalyst, contacting at least a part of the hydrotreated and/or hydrocracked product with a zeolitic catalyst comprising a zeolite with a pore diameter of 0.4 to 0.7 nm at a temperature of greater than 480°C and a pressure of up to 10 bar during less than 10 seconds, fractionating the resulting converted material and recycling a heavier fraction to said hydrotreating and/or hydrocracking step.
11. A process according to claim 10 wherein said feedstock is a heavy flashed distillate,
12. A hydrocarbonaceous product, or a fraction thereof, when obtained by the process of any one of the preceding claims.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8828206 | 1988-12-02 | ||
| GB888828206A GB8828206D0 (en) | 1988-12-02 | 1988-12-02 | Process for conversion of hydrocarbonaceous feedstock |
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| CA2004390A1 true CA2004390A1 (en) | 1990-06-02 |
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| CA 2004390 Abandoned CA2004390A1 (en) | 1988-12-02 | 1989-12-01 | Process for the conversion of a hydrocarbonaceous feedstock |
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| EP (1) | EP0372632B1 (en) |
| JP (1) | JPH02212594A (en) |
| CN (1) | CN1025216C (en) |
| AU (1) | AU621169B2 (en) |
| BR (1) | BR8906158A (en) |
| CA (1) | CA2004390A1 (en) |
| DE (1) | DE68925574T2 (en) |
| ES (1) | ES2082769T3 (en) |
| GB (1) | GB8828206D0 (en) |
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|---|---|---|---|---|
| US3420770A (en) * | 1966-09-28 | 1969-01-07 | Mobil Oil Corp | Catalytic cracking of hydrocarbons |
| US3856659A (en) * | 1972-12-19 | 1974-12-24 | Mobil Oil Corp | Multiple reactor fcc system relying upon a dual cracking catalyst composition |
| US4171257A (en) * | 1978-10-23 | 1979-10-16 | Chevron Research Company | Petroleum distillate upgrading process |
| US4502945A (en) * | 1982-06-09 | 1985-03-05 | Chevron Research Company | Process for preparing olefins at high pressure |
| DE3479225D1 (en) * | 1983-04-18 | 1989-09-07 | Shell Int Research | A process for the production of low-asphaltenes hydrocarbon mixtures |
| NL8301352A (en) * | 1983-04-18 | 1984-11-16 | Shell Int Research | PROCESS FOR THE PREPARATION OF LOW-ASPHALTENE HYDROCARBON MIXTURES. |
| AU614626B2 (en) * | 1988-06-16 | 1991-09-05 | Shell Internationale Research Maatschappij B.V. | Process for the conversion of a hydrocarbonaceous feedstock |
-
1988
- 1988-12-02 GB GB888828206A patent/GB8828206D0/en active Pending
-
1989
- 1989-11-29 EP EP19890203038 patent/EP0372632B1/en not_active Revoked
- 1989-11-29 DE DE1989625574 patent/DE68925574T2/en not_active Revoked
- 1989-11-29 ES ES89203038T patent/ES2082769T3/en not_active Expired - Lifetime
- 1989-12-01 JP JP31084489A patent/JPH02212594A/en active Pending
- 1989-12-01 CN CN 89109758 patent/CN1025216C/en not_active Expired - Fee Related
- 1989-12-01 CA CA 2004390 patent/CA2004390A1/en not_active Abandoned
- 1989-12-01 AU AU45799/89A patent/AU621169B2/en not_active Ceased
- 1989-12-01 RU SU4742676 patent/RU2017790C1/en active
- 1989-12-04 BR BR8906158A patent/BR8906158A/en not_active Application Discontinuation
- 1989-12-08 PH PH39654A patent/PH27238A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE68925574T2 (en) | 1996-08-08 |
| EP0372632B1 (en) | 1996-01-31 |
| CN1025216C (en) | 1994-06-29 |
| AU621169B2 (en) | 1992-03-05 |
| RU2017790C1 (en) | 1994-08-15 |
| CN1043156A (en) | 1990-06-20 |
| DE68925574D1 (en) | 1996-03-14 |
| AU4579989A (en) | 1990-06-07 |
| BR8906158A (en) | 1990-07-31 |
| GB8828206D0 (en) | 1989-01-05 |
| ES2082769T3 (en) | 1996-04-01 |
| JPH02212594A (en) | 1990-08-23 |
| PH27238A (en) | 1993-05-04 |
| EP0372632A1 (en) | 1990-06-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Dead |