CN1531583A - Extension of catalyst cycle length in residuum desulfurization processes - Google Patents
Extension of catalyst cycle length in residuum desulfurization processes Download PDFInfo
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- CN1531583A CN1531583A CNA018153259A CN01815325A CN1531583A CN 1531583 A CN1531583 A CN 1531583A CN A018153259 A CNA018153259 A CN A018153259A CN 01815325 A CN01815325 A CN 01815325A CN 1531583 A CN1531583 A CN 1531583A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims description 28
- 230000008569 process Effects 0.000 title claims description 14
- 238000006477 desulfuration reaction Methods 0.000 title claims description 6
- 230000023556 desulfurization Effects 0.000 title claims description 6
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 17
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 8
- 238000002347 injection Methods 0.000 claims abstract description 4
- 239000007924 injection Substances 0.000 claims abstract description 4
- 238000007600 charging Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000003921 oil Substances 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000010779 crude oil Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 239000003079 shale oil Substances 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims 2
- 230000008929 regeneration Effects 0.000 claims 2
- 238000011069 regeneration method Methods 0.000 claims 2
- 239000004519 grease Substances 0.000 claims 1
- 239000003027 oil sand Substances 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 16
- 230000008021 deposition Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 4
- 239000000571 coke Substances 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010606 normalization Methods 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 208000034809 Product contamination Diseases 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Images
Classifications
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- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
Solvent injection in amounts no greater than 2 wt% can favorably alter the way heavy metals, such as vanadium, are normally deposited in catalyst particles. Heavy metals may be stored on the catalyst in a more compact form, saving catalyst pore volume. Consequently catalyst cycle length is improved, since capacity for deposition is increased. The instant invention has also been demonstrated to control the rate of catalyst fouling by deposition of coke, or microcarbon residue (MCR). In the past, attempts to increase catalyst activity led to increased rates of catalyst fouling and shorter catalyst life. In the instant invention the rate of deposition of microcarbon residue is decreased, resulting in slower fouling of pores and increased cycle length.
Description
The application requires to enjoy the right of priority of the U.S. Provisional Application sequence number of submitting on September 7th, 2,000 60/230,646.
Invention field
The present invention relates to a kind of catalyst recirculation time method that prolongs when being used for residuum hydrodesulfurization.
Background of invention
In the hydrogenating desulfurization of residual oil and heavy oil, poisoning of catalyst is a long-standing problem.These raw materials usually contain organometallic compound, for example nickel and vanadium.These metallic impurity often are deposited in the surface and hole of Hydrobon catalyst.Known catalysts is poisoned and is made catalyst activity reduction, particularly under situation about existing greater than 10-20ppm dissolved metal (for example nickel and vanadium).
U.S.Pat.No.5,215,955 (Threlkel) attempt have the catalyzer of minimized number macropore to solve stained problem by use.The pore volume less than 2% catalyzer of Threlkel has the diameter greater than 1000 dusts.This catalyzer contains VIB and VIII family metal containing on the carrier of aluminum oxide.At least 80% pore volume contains the hole that straight warp is the 110-190 dust.Except improving activity, known this catalyzer also has long life-span and high metals capacity.But this terms of settlement is limited to the use special catalyst with residual oil processing really.
In the past few years used the other approach to improve the efficient of catalyzer in hydrogenating desulfurization, " solvent injection " wherein arranged.Though " solvent injection " is not new to the design of residual hydrocracking device, and in fact in many devices commercial applications many year, people for it to the influence of catalyst performance in fact solve seldom.The most frequently used solvent is water always.But if a large amount of the use, solvent injects and may produce various bad side effects so.
U.S.Pat.No.4,013,637 (Eberly Jr.) discloses a kind of hydrodesulfurization that makes water.The efficient of this method improves by the gas phase that the water with 1-32% (volume) injects conversion zone.But charging is substantially free of metal.When the charging that contains heavy metal was desulfurized, the purpose of this invention was that water increases catalyst life.
GB 1468160 and GB 1505886 are common all, disclose the oil product that is used for containing vanadium and nickel in the presence of water vapor and do not having the method for the catalytic desulfurhydrogenation under the condition of catalyst make-up.These inventions have special requirement to steam partial pressure with to the mean pore size of used catalyzer and catalyst composition and the ratio between the mean particle size.Another common all patent GB1525508 also discloses the catalytic desulfurization that makes water or other solvents (for example lower alcohol or other water precursors).
U.S.Pat.No.4,052,295 (Pronk) disclose a kind of method that is used to contain the catalytic desulfurhydrogenation of vanadium heavy-hydrocarbon oil.The heavy-hydrocarbon oil that contains vanadium contacts with catalyzer with hydrogen down with boosting in intensification.Catalyzer for example is loaded with the molybdenum and/or the tungsten of nickel and/or cobalt and about 2.5-60 weight part on the aluminum oxide at the porous carrier.Do not add water vapor, until the average vanadium content of catalyzer increases at least 5 weight parts/100 weight parts in contact process.
Pronk points out, when temperature rises to the highest permission level and operation under normal circumstances is essential when stopping, the application of water vapor may be effective to desulfurization operations latter stage of operating under the situation that does not add water vapor.
Pronk has pointed out to contain the problem that the use of water vapor in the hydrogenating desulfurization of heavy oil of vanadium or other heavy metals produces in its invention.According to the view of Pronk, the use of water vapor needs the extra energy essential water yield of vaporizing, and makes the expense increase relevant with desulfurization.In addition, Pronk also finds, carries out under the constant stagnation pressure in order to ensure this method, if desulfurization is carried out in the presence of water vapor, the hydrogen dividing potential drop must be reduced.The decline of hydrogen dividing potential drop makes activity of such catalysts descend usually.Owing to these reasons, a certain stage of water in method added, but be not to add the most at the beginning.In this invention, in order to make the deposition maximum of metal, it is preferred adding entry at the initial stage of operation cycle.If water begins deposition in early days, metal constantly deposits in full cycle so.
U.S.Pat.No.3,501,396 (Gatsis) disclose a kind of method that is used for the petroleum crude oil desulfurization, and it comprises mixes crude oil with hydrogen and 2-30 weight % water, contact the mixture reaction that makes generation then under desulfurization condition with catalyst composition.This patent points out that these utilizations of comparing excessive water it seems the hydrogen rate of diffusion of passing through liquid phase on the catalyzer is improved that raising is because liquid phase viscosity and the surface tension characteristics that descends.Provide the difficulty of hydrogen to descend greatly and the catalyst stability raising to catalyst active sites.At U.S.Pat.No.3, the prolongation of not mentioned catalyst life in 501,396.In addition, this invention obtains its benefit with the water that is not more than 2 weight %.
U.S.Pat.No.3,753,894 (Shoemaker etc.) disclose a kind of hydrodesulfurizationprocess process of processing the sulfur-bearing resid feed, wherein between the several catalytic agent bed of many bed reactors, inject water, so that make the reaction product chilling, slow down the inactivation of catalyzer simultaneously, particularly the inactivation that occurs at the operation initial stage.Water can add up to the concentration of 50 weight %.
As the explanation of these reference, it is helpful slightly to it has been generally acknowledged that solvent is infused in the catalyst activity aspect, particularly relates to sulphur or heavy metal is removed, and less degree is removed little carbon residue.But, condition, charging and the catalyzer that is applicable to these inventions had the restriction of special pearl.Usually use for example water of a large amount of solvents.The needs that searching can use the method for optimum solvent amount can the minimizing method to change are simplified downstream processing, the loss that reduces process cost and reduce the hydrogen dividing potential drop.
Summary of the invention
In the residuum hydrodesulfurization procedure or just before this, the heavy metal for example fouling of catalyst that causes of vanadium can suppress by injecting effective quantity solvent.Water be injected with the temperature rise requirement that helps control whole process.The injection of water makes for example vanadium uniform deposition more in catalyst pellet of metal, thereby has postponed the beginning that the aperture is stopped up.
Most preferred solvent is a water.Found that method of the present invention can operate with various chargings and catalyzer under various conditions effectively.
In the past, as the reference in background of invention explanation, in order to improve catalyst activity, add quite a large amount of water.Recent discovery shows that in fact the most significant aspect that the solvent of specific quantity injects is not its few relatively influence to catalyst activity, but it is to the obvious influence of catalyst recirculation time.The solvent that is no more than 2 weight % injects the controlled temperature cause by reactor to be increased, and can advantageously change for example vanadium sedimentary mode in granules of catalyst usually of heavy metal.Heavy metal may be stored on the catalyzer with form more closely, has saved catalyst pore volume.Because sedimentary capacity increases, so the increase of catalyst recirculation time.
The accompanying drawing summary
Fig. 1 explanation was compared with the operational cycle of not water filling, and 2 weight % water were added in the operational cycle influence that the temperature rise to the whole time requires in 200 hours.Located in about aborning 800 hours, about 730 normalization method temperature is evened up.The normalization method temperature remains on the temperature that needs under the 0.55 weight % for the concentration with sulphur.Do not having under the condition of temperature rise, the sulphur concentration of product all keeps constant under 0.55 weight % when the operational cycle finishes.
Fig. 2 explanation same operation cycle as shown in Figure 1.Under lower service temperature, under the situation that 2 weight % water inject, the concentration of vanadium is lower in the product, and in the cycle that does not add water, the vanadium concentration in the product is higher.This just proves and stays more vanadium that when EO they penetrate catalyzer better on catalyzer.
Detailed Description Of The Invention
Zheng describe such as the present invention, solvent Zhu enters to be applicable to that vanadium obviously causes the big of catalyst ageing Most residual hydrogenation processed and applied. Very high, harsh the adding of the common Zai operation of a little benefits of Zhe vanadium Zai amount Worker's condition and those use the application scenario Zhong of the catalyst that hangs down S/V the most obvious. Zhe To be included in Yun Zhuan process Zhong catalyst make-up (OCR) method and other big extruded catalyst Zhong uses Catalyst.
The catalyst of low S/V stops up more responsive usually to the aperture, because reach catalysis Agent piller inside (Zheng catalyst volume and the surperficial overwhelming majority) is more restricted. OCR uses Make the operating condition of big catalyst pellet, harshness and the application combination that high vanadium Zai measures. Solvent (solvent of You choosing is water, although oxygen containing compound for example alcohol, the ether of short chain in the design that Zhu enters (either) or other water precursors also can use) be specially adapted to OCR technology. To cause You Required minimal amount of water (being not more than 2 Chong amount % during Zai the is of the present invention) Zhu of sharp chemical reaction enters OCR Reactor. For the big change of Chong of avoiding method, simplify Downstream processing, reduce operating cost, Reduce the loss of hydrogen dividing potential drop and make the gas flow rate of keeping the good flow condition the littlest, make Zhu The excessive solvent that enters OCR (or Zhu enters the reactor of any hydro desulfurization Zhong) reduces to the littlest Chong of being Want. OCR method Zai U.S.Pat.No.5,076,908 (Stangeland etc.) Zhong more fully Open, it incorporates this paper Zuo into is reference. Zheng such as embodiment Zhong explanation below the Zai, when the solvent example Add fashionablely such as the water Zai operation cycle Zao phase, obtain efficient result. But Zai operation cycle Zhong Zai appoints When solvent is added, but to add when beginning be the You choosing Zai Zhou phase. Embodiment illustrates water Zai Added in front 200 hours of operation cycle.
The charging that is adapted at Zhong use of the present invention comprises " Chong " hydrocarbon liquids stream, particularly Yuan You, petroleum residual oil, You sand pitch prill, shale oil or liquefaction coal or reclaimed oil. Petroleum residual oil can be You at the bottom of the crude oil atmospheric distillation tower (topped crude or atmospheric tower Zha You), You (subtracts at the bottom of the vacuum (distilling) column Press Zha You).
These incoming flows contain the product contamination thing usually, and for example sulphur and/or nitrogen, metal comprise for example vanadium and may be at the organometallic compound in porphyrin or the chelating type works of heavy metal.Residual oil contains the metal greater than 10ppm usually.These pollutents often under the hydrogenation processing conditions with the contact process of incoming flow and hydrogen in make the granules of catalyst inactivation.The present invention is for resid feed, and for example the Mayan residual oil (Maya residuum) that uses in the following embodiments is effective especially.
The hyperergy of Mayan/Arabic heavy long residuum concoction combines with the high temperature of operation and promotes a large amount of vanadium in the catalyst pellet outside deposition usually.Such deposition usually clogging raw oil enters the passage of the inside catalytic activity part of catalyzer.In the present invention, in the inner deposition of finding a large amount of vanadium of catalyst themselves.Because the hole is not stopped up rapidly, thereby catalyst life extends greatly.
As at U.S.Pat.No.5, further disclosed in 215,955, the typical operation conditions of hydrodesulfurization comprises 600-900 conversion zone temperature, 200-3, the pressure of 000psig and 500-15, the hydrogen feeding rate of 000SCF/ bucket oil charging.Usually, such hydrogenating desulfurization is for example to carry out in the presence of the catalyzer of platinum, molybdenum, tungsten, nickel, cobalt etc. or the catalyst composition containing VI or VIII family metal.These metals can be loaded on the refractory support, for example aluminum oxide, silicon-dioxide, magnesium oxide etc.For the catalyzer that uses among the present invention, high S/V is preferred.
Aluminum oxide is preferred catalyst support material, though aluminum oxide can combine with silicon-dioxide or magnesium oxide.Solid support material can be obtained by various commercial source, and perhaps they can be by disclosed such preparation among the Tamm ' 661.The Preparation of catalysts that is suitable for residual hydrogenation processing is at U.S.Pat.No.5, and is further open in 620,592, U.S.Pat.No.5,215,955 and U.S.Pat.No.5,177,047.Merit attention, disclosed catalyzer preferably has macropore seldom in these patents.The catalyzer of OCR method is the height macropore.Therefore, the present invention can utilize pore structure to have the catalyzer of various variations to use.
Hydrocarbon Hydrobon catalyst of the present invention contains at least a hydrogenation reagent, preferably contains two kinds of such combination of agents things.One or more catalyzer can be used for any conversion zone.The sulfide and the normally gratifying catalyzer of oxide compound of metal and/or metallic compound, particularly group vib (particularly molybdenum and tungsten) and group VIII (particularly cobalt and nickel) element.The composition of cobalt, nickel and molybdenum catalyst is preferred.What be fit to is, is benchmark with total catalyst weight, and the quantity that the group VIII metal that calculates by metal exists in catalyzer is about 0.1 to about 5 weight % scopes; With total catalyst weight is benchmark, press quantity that group vib metal that metal calculates exists at about 4 weight % to about 20 weight % scopes.Most preferred catalyzer contain have an appointment 2% to about 4% nickel and about 7% to about 9% molybdenum.The catalyzer that uses in embodiment (table 3) is representational.
The required catalytic reagent of this catalyst composition can be mixed in the carrier of roasting with any suitable method, and particularly common routine is used for the pickling process of catalyst preparation technology.Find, good especially catalyzer by using cobalt or nickel salt solution and heteropolymolybdic acid for example one step of the aluminum oxide dipping of phospho-molybdic acid prepare.
Embodiment
Example I
The dirty operated reactor system that the catalyzer that contains Al/Mo/P/Ni (seeing Table 3) that commerce is provided is packed into and is made up of three reactors in series.Reactor body ties up to by the operation down of purpose material equilbristat 57%MCR transformation efficiency.Setting up similar adiabatic temperature in each reactor distributes.Temperature rise by each reactor is set to 50-55 °F, and total top temperature is 780 °F.The stagnation pressure of reactor system is maintained 2200psig, and the hydrogen dividing potential drop is that 1800psia and hydrogen flow velocity are 5000scf/bbl.The charging (seeing Table the physical properties of 1 charging 2) that Arabic heavy oil/Mayan long residuum is formed is with 0.46hr
-1Liquid hourly space velocity (LHSV) send into.
After turning round 1,508 hour under this accelerated deterioration mode, remaining time of this operation (at 2806 hours time finish) with 3 weight % or the continuous injecting feeding of 3.2gms/hr water.The result who is obtained by this operation clearlys show that catalyst recirculation time and metal carrying capacity all have obvious improvement.Compare with the reactor system of base case, increase by 27% cycling time; Increase by 28% and compare the metal carrying capacity with the reactor system of base case.
Example II
Except LHSV is 0.22hr
-1Outside use charging 2, reactor system is all identical with the foregoing description I with condition.(seeing Table the physical properties of 1 charging 1).
In this embodiment, when the operation beginning, finish later on the continuous injecting feeding of water of 2.0 weight % or 2.2gms/hr with at 2380 hours.Compare with the reactor system of base case, increase by 31% cycling time, the metal carrying capacity increases by 34%.
EXAMPLE III
Reactor body is a single-stage reactor, and condition is identical with example I, and different is that charging is different chargings (seeing Table the physical properties of 1 charging 3) and only uses catalyzer 2 (seeing Table 3) in this operation.
In this embodiment, in whole 750 hour operating time, with 1.5 weight % or the continuous injecting feeding of 1.7gms/hr water.But, no matter short time length and relative low catalyst metal carrying capacity of this operation all has sign to clearly illustrate that, compare with the reactor system of base case, beginning to form catalyst metal capacity that water causes and lower catalyst aging speed.
EXAMPLE IV
Reactor body is a single-stage reactor, and condition is identical with example I, and different is that charging is different chargings (seeing Table the physical properties of 1 charging 3) and only uses catalyzer 2 (seeing Table 3) in this operation.
In this embodiment, in whole 750 hour operating time, with 1.0 weight % or the continuous injecting feeding of 1.2gms/hr water.Be again the short period of time of given this operation, to there are indications that the injection of water is beginning to improve the metal carrying capacity capacity and the rate of ageing of catalyzer.
Table 1
Charging: Arabic heavy oil/Mayan long residuum
Charging 1
Charging 2
Charging 3
Sulphur, weight % 4.660 4.620 4.551
Nitrogen, ppm 4,087 4,024 4260
MCR, weight % 18.9 704.8 284.5
API 7.5 7.4 8.9
Iron, ppm 5.6 8.2 7.3
Nickel, ppm 58.9 59.6 70.2
Vanadium, ppm 264.0 265.0 358.0
IBF(°F) 684 676 641
Table 2
Water injects weight
Operating time is improved %
The metal carrying capacity is improved %
0.75％
1.5％
2.0％ +30.8％ +34.0％
3.0％ +26.6％ +28.0％
Estimate numerical value
Table 3
Form
Catalyzer 1
Catalyzer 2
Catalyzer 3
Al
2O
3 79％ 86％ 80％
MoO
3 13％ 9％ 12％
P
2O
5 4％ 2％ 4％
NiO 4％ 3％ 4％
Claims (12)
1. one kind prolongs the catalyst recirculation time method in the hydrogenating desulfurization of the charging that contains heavy metal contaminants, described method occurs in one or more conversion zones, charging contacts with Hydrobon catalyst there, the solvent that will be not more than 2 weight % before initial conversion zone is sent in charging mixes with charging, or solvent is added in initial conversion zone or the later conversion zone subsequently.
2. according to the process of claim 1 wherein that solvent is a kind of oxygen containing compound, it is selected from water, alcohol, ether and other water precursors.
3. according to the process of claim 1 wherein that heavy metal contaminants is nickel, vanadium or both mixtures.
4. according to the process of claim 1 wherein that the solvent that will be not more than 1.5 weight % before initial conversion zone is sent in charging mixes with it, or solvent is added initial conversion zone or later conversion zone subsequently.
5. according to the method for claim 4, the solvent that wherein will be not more than 0.75 weight % before initial conversion zone is sent in charging mixes with it, or solvent is added initial conversion zone or later conversion zone subsequently.
6. according to the process of claim 1 wherein with the injections in preceding 200 hours of solvent in the operational cycle.
7. according to the process of claim 1 wherein that charging is selected from crude oil, petroleum residual oil, oil-sand pitch prill, shale oil or liquefaction coal or recovered oil.
8. according to the method for claim 7, wherein petroleum residual oil is selected from the bottom of the crude oil atmospheric distillation tower oil at the bottom of oil or the vacuum tower.
9. method according to Claim 8, extricate oneself a crude oil or atmospheric tower residual oil of grease separation at the bottom of the crude oil atmospheric distillation tower.
10. according to the process of claim 1 wherein that at least one conversion zone designs for catalyst regeneration in the operation process.
11. according to the process of claim 1 wherein that the operational condition of hydrodesulfurization comprises 600-900 conversion zone temperature, the pressure of 200-3000psig and the hydrogen feeding rate of 500-15000SCF/ bucket oil charging.
12. according to the method for claim 10, wherein at least a catalyzer in one or more conversion zones is the macroporous catalyst that is applicable to catalyst regeneration in the operation process.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US23064600P | 2000-09-07 | 2000-09-07 | |
| US60/230,646 | 2000-09-07 | ||
| US09/874,202 | 2001-06-05 | ||
| US09/874,202 US20020056664A1 (en) | 2000-09-07 | 2001-06-05 | Extension of catalyst cycle length in residuum desulfurization processes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1531583A true CN1531583A (en) | 2004-09-22 |
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| CNA018153259A Pending CN1531583A (en) | 2000-09-07 | 2001-09-05 | Extension of catalyst cycle length in residuum desulfurization processes |
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| EP (1) | EP1334168A4 (en) |
| JP (1) | JP2004508452A (en) |
| KR (1) | KR20030029941A (en) |
| CN (1) | CN1531583A (en) |
| AU (1) | AU2001288832A1 (en) |
| BR (1) | BR0113718A (en) |
| TW (1) | TWI237054B (en) |
| WO (1) | WO2002020701A1 (en) |
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|---|---|---|---|---|
| US7763160B2 (en) * | 2003-12-19 | 2010-07-27 | Shell Oil Company | Systems and methods of producing a crude product |
| US20070000808A1 (en) * | 2003-12-19 | 2007-01-04 | Bhan Opinder K | Method and catalyst for producing a crude product having selected properties |
| BRPI0405572A (en) * | 2003-12-19 | 2005-08-30 | Shell Int Research | Methods of Producing a Transportable Fuel and Crude Petroleum Product, Heating Fuel, Lubricants or Chemicals, and Crude Oil Products |
| US20050167328A1 (en) * | 2003-12-19 | 2005-08-04 | Bhan Opinder K. | Systems, methods, and catalysts for producing a crude product |
| US20060289340A1 (en) * | 2003-12-19 | 2006-12-28 | Brownscombe Thomas F | Methods for producing a total product in the presence of sulfur |
| US20070000810A1 (en) * | 2003-12-19 | 2007-01-04 | Bhan Opinder K | Method for producing a crude product with reduced tan |
| US20070012595A1 (en) * | 2003-12-19 | 2007-01-18 | Brownscombe Thomas F | Methods for producing a total product in the presence of sulfur |
| US7745369B2 (en) * | 2003-12-19 | 2010-06-29 | Shell Oil Company | Method and catalyst for producing a crude product with minimal hydrogen uptake |
| TW200602591A (en) * | 2004-07-08 | 2006-01-16 | hong-yang Chen | Gas supply device by gasifying burnable liquid |
| CN101068932B (en) * | 2004-10-27 | 2013-02-13 | 塞弗德公司 | Closed-system multi-stage nucleic acid amplification reactions |
| TWI415930B (en) * | 2005-04-06 | 2013-11-21 | Shell Int Research | A process for reducing the total acid number (tan) of a liquid hydrocarbonaceous feedstock |
| RU2007141711A (en) * | 2005-04-11 | 2009-05-20 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. (NL) | METHOD FOR PRODUCING A SEMI-PRODUCT WITH A REDUCED NITROGEN AND CATALYST CONTENT FOR ITS IMPLEMENTATION |
| EP1874897A1 (en) | 2005-04-11 | 2008-01-09 | Shell Internationale Research Maatschappij B.V. | Method and catalyst for producing a crude product having a reduced mcr content |
| CN101166811A (en) | 2005-04-11 | 2008-04-23 | 国际壳牌研究有限公司 | Method and catalyst for producing a crude product having a reduced nitrogen content |
| CA2655581A1 (en) * | 2006-06-22 | 2007-12-27 | Shell Internationale Research Maatschappij B.V. | Methods for producing a crude product from selected feed |
| US20070295646A1 (en) * | 2006-06-22 | 2007-12-27 | Bhan Opinder K | Method for producing a crude product with a long-life catalyst |
| RU2009101923A (en) * | 2006-06-22 | 2010-07-27 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. (NL) | METHODS FOR PRODUCING A TOTAL PRODUCT WITH SELECTIVE PRODUCTION OF HYDROCARBONS |
| US20080085225A1 (en) * | 2006-10-06 | 2008-04-10 | Bhan Opinder K | Systems for treating a hydrocarbon feed |
| JP5168509B2 (en) * | 2009-07-14 | 2013-03-21 | コスモ石油株式会社 | Regeneration method of hydrodesulfurization catalyst |
| SG11201508586YA (en) * | 2013-04-24 | 2015-11-27 | Shell Int Research | Activation of a hydroprocessing catalyst with steam |
| WO2016099787A1 (en) | 2014-12-17 | 2016-06-23 | Exxonmobil Chemical Patents Inc. | Methods and systems for treating a hydrocarbon feed |
| US10604709B2 (en) | 2017-02-12 | 2020-03-31 | Magēmā Technology LLC | Multi-stage device and process for production of a low sulfur heavy marine fuel oil from distressed heavy fuel oil materials |
| US11788017B2 (en) | 2017-02-12 | 2023-10-17 | Magëmã Technology LLC | Multi-stage process and device for reducing environmental contaminants in heavy marine fuel oil |
| US20180230389A1 (en) | 2017-02-12 | 2018-08-16 | Magēmā Technology, LLC | Multi-Stage Process and Device for Reducing Environmental Contaminates in Heavy Marine Fuel Oil |
| US10253272B2 (en) * | 2017-06-02 | 2019-04-09 | Uop Llc | Process for hydrotreating a residue stream |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL182489C (en) * | 1975-03-24 | 1988-03-16 | Shell Int Research | PROCESS FOR DESULFULIFYING HEAVY HYDROCARBONS CONTAINING VANADIUM. |
| CA1094489A (en) * | 1976-03-29 | 1981-01-27 | Mobil Oil Corporation | Desulfurization and demetalation of heavy charge stocks |
| US4828683A (en) * | 1987-02-06 | 1989-05-09 | Phillips Petroleum Company | Hydrofining employing a support material for fixed beds |
| US4941964A (en) * | 1988-03-14 | 1990-07-17 | Texaco Inc. | Hydrotreatment process employing catalyst with specified pore size distribution |
| US4969990A (en) * | 1988-06-29 | 1990-11-13 | Union Oil Company Of California | Hydroprocessing with a catalyst having a narrow pore size distribution |
| US5164078A (en) * | 1989-12-28 | 1992-11-17 | Chevron Research And Technology Company | Process for removal of calcium from a hydrocarbon feedstock |
-
2001
- 2001-06-05 US US09/874,202 patent/US20020056664A1/en not_active Abandoned
- 2001-09-05 AU AU2001288832A patent/AU2001288832A1/en not_active Abandoned
- 2001-09-05 WO PCT/US2001/027669 patent/WO2002020701A1/en active Application Filing
- 2001-09-05 EP EP01968592A patent/EP1334168A4/en not_active Withdrawn
- 2001-09-05 JP JP2002525709A patent/JP2004508452A/en active Pending
- 2001-09-05 CN CNA018153259A patent/CN1531583A/en active Pending
- 2001-09-05 KR KR10-2003-7003372A patent/KR20030029941A/en not_active Application Discontinuation
- 2001-09-05 BR BR0113718-2A patent/BR0113718A/en not_active Application Discontinuation
- 2001-09-07 TW TW090122241A patent/TWI237054B/en not_active IP Right Cessation
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2002
- 2002-12-03 US US10/310,470 patent/US20030085155A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| US20020056664A1 (en) | 2002-05-16 |
| WO2002020701A1 (en) | 2002-03-14 |
| EP1334168A4 (en) | 2005-01-19 |
| EP1334168A1 (en) | 2003-08-13 |
| US20030085155A1 (en) | 2003-05-08 |
| KR20030029941A (en) | 2003-04-16 |
| TWI237054B (en) | 2005-08-01 |
| JP2004508452A (en) | 2004-03-18 |
| BR0113718A (en) | 2003-07-22 |
| AU2001288832A1 (en) | 2002-03-22 |
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