CA2173295A1 - In situ catalyst formation in fluidized bed syn gas operations - Google Patents
In situ catalyst formation in fluidized bed syn gas operationsInfo
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- CA2173295A1 CA2173295A1 CA002173295A CA2173295A CA2173295A1 CA 2173295 A1 CA2173295 A1 CA 2173295A1 CA 002173295 A CA002173295 A CA 002173295A CA 2173295 A CA2173295 A CA 2173295A CA 2173295 A1 CA2173295 A1 CA 2173295A1
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- catalyst
- catalytic
- metal
- nickel
- fluidized bed
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Catalysts useful in FBSG and partial oxidation reactions can be formed in situ within an FBSG reactor, at FBSG reaction conditions and employed in situ or ex situ with respect to the reactor in which the catalyst is prepared. In the formation of such catalysts, a decomposable compound of a catalytic metal, or catalytic metallic metal, is added to the bed of an FBSG reactor, at FBSG reaction conditions, to disperse the catalytic metal upon the particulate solids of the fluidized bed to form a catalyst, or upon a catalyst, or mixture of the catalyst and diluent solids, of the fluidized bed to increase the catalytic activity of the bed, or stabilize and maintain the catalytic activity of the bed, during the reaction.
Description
21 73~95 ,, 1. FIELD OF THE INVENTION
This invention relates to a process for the in situ formation of catalysts useful in FBSG and partial oxidaton processes; catalysts which can be employed in situ or ex situ relative to the reactor in which they are pl~ed.
This invention relates to a process for the in situ formation of catalysts useful in FBSG and partial oxidaton processes; catalysts which can be employed in situ or ex situ relative to the reactor in which they are pl~ed.
2. BACKGROUND
Fluidized bed processes are known to provide superior heat and mass transfer characteristics as contrasted with fixed bed processes.
They permit subst~nti~lly isothermal reactor conditions in conducting both exothermic and endothermic reactions.
For example, in the production of synthesis gas (hydrogen and carbon monoxide) via a known Fluidized Bed Syn Gas, FBSG, process, low molecular weight hydrocarbons e.g., natural gas (primarily CH4), are fed into the bottom of a reactor containing a mixture of catalyst, e.g., a nickel-on-aluminacatalyst, and a solids ~ ent, e.g., ~hlmin~, to form a fluidized bed of the catalyst and solids diluent. Steam is introduced into the reactor. Oxygen is fed into the fluidized bed through nozzles separate from those through which the natural gas is fed. The oxygen reacts with a portion of the natural gas in a zone near the oxygen inlet according to the following partial oxi-1~tion reaction:
(1) CH4 + 2 = CO + H2 + H20 (Partial Oxidation) 2l 73295 This is a strongly exothermic reaction and produces loc~li7ed hot spots and burning near the 2 nozzle, or no771es the high te~ e area around the 2 nozzle con~ ing a b~l",ing zone. The natural gas that does not react directly with the 2 ~ n~l~ through the reactor where it undergoes a steam lerollning reaction to produce hydrogen and carbon monoxide according to the following reaction:
(2) CH4 + H20 = CO + 3H2 (Steam Reforming) The steam reforming is highly endothermic, but by having good solids circulation in the fluidized bed, the overall bed te-l-pe~ture becomes quite uniform. The net. or overall reaction (the sum of reactions (1) and (2), supra), described as follows, is slightly exothermic.
Fluidized bed processes are known to provide superior heat and mass transfer characteristics as contrasted with fixed bed processes.
They permit subst~nti~lly isothermal reactor conditions in conducting both exothermic and endothermic reactions.
For example, in the production of synthesis gas (hydrogen and carbon monoxide) via a known Fluidized Bed Syn Gas, FBSG, process, low molecular weight hydrocarbons e.g., natural gas (primarily CH4), are fed into the bottom of a reactor containing a mixture of catalyst, e.g., a nickel-on-aluminacatalyst, and a solids ~ ent, e.g., ~hlmin~, to form a fluidized bed of the catalyst and solids diluent. Steam is introduced into the reactor. Oxygen is fed into the fluidized bed through nozzles separate from those through which the natural gas is fed. The oxygen reacts with a portion of the natural gas in a zone near the oxygen inlet according to the following partial oxi-1~tion reaction:
(1) CH4 + 2 = CO + H2 + H20 (Partial Oxidation) 2l 73295 This is a strongly exothermic reaction and produces loc~li7ed hot spots and burning near the 2 nozzle, or no771es the high te~ e area around the 2 nozzle con~ ing a b~l",ing zone. The natural gas that does not react directly with the 2 ~ n~l~ through the reactor where it undergoes a steam lerollning reaction to produce hydrogen and carbon monoxide according to the following reaction:
(2) CH4 + H20 = CO + 3H2 (Steam Reforming) The steam reforming is highly endothermic, but by having good solids circulation in the fluidized bed, the overall bed te-l-pe~ture becomes quite uniform. The net. or overall reaction (the sum of reactions (1) and (2), supra), described as follows, is slightly exothermic.
(3) 2CH4 + 2 = 2CO + 4H2 (Overall) The overall reactions occur in a net reducing atmosphere.
The water gas shift reaction also occurs in the bed; a very rapid reaction which produces only minor heat effects.
The water gas shift reaction also occurs in the bed; a very rapid reaction which produces only minor heat effects.
(4) CO + H20 = CO2 + H2 (Water Gas Shift) The exothermic heat of reaction produced by the oxygen ~auses burning and severe loc~li7~ heat near the oxygen inlet zone; and despite the good heat transfer in the fluid bed, the high tel"~l~ture produces net agglomeration of the catalyst, or catalyst and other solids.
The high localized flame tel,l~.dlule produced by the oxygen in the burning zone of the bed can exceed the mPlting point of the alumina, or at least produce le~l~pf ~n~les which cause the surface of the ~ min~
particles to melt, stick and fuse together as tne particles ~pe~ rely collide or recycle through the burning zone of the bed. The amount of agglomeration increases with time which adversely affects the flllidi7~tion char~cteristics of the bed, and the activity of the catalyst de~lines. The active catalytic sites become in~ccescihle to the react~nts due to the agglomeration of the particles; or active surface area lost due to metals agglomeration.
3. DESCRIPTION OF THE INVENTION
The present invention relates to the formation in an FBSG
operation of catalysts useful (a) in an FBSG process, or process for producing a syn gas, or mixture of hydrogen and carbon monoxide, from a low molecular weight hydrocarbon, steam and oxygen and (b) in a partial oxidation process for producing hydrogen and carbon monoxide from a low molecular weight hydrocarbon and oxygen. The catalysts are formed in a reaction zone at FBSG reaction conditions from a flui-li7e~
bed of (i) particulate refractory inorganic oxide solids, or (ii) a flui~li7ed bed of a deactivated, or deactivating, catalyst composite, or (iii) mixture of a deactivated, or deactivating, catalyst composite and particulate refractory inorganic oxide solids, by adding, intel..,il(ently or continuously to the reaction zone a decomposable compound of a catalytic-metal, or catalyLic m~t~llic me~ o disperse the metal, which at FBSG reaction conditions, will move from particle to particle to form catalytically active mPt~llic cryst~llites upon the solids panicles of the flui~ ed bed sllffi~ient, (i) whe;c the bed is col-~tituted of particulate inol~dnic oxide solids, to produce a catalyst in situ, (ii) where the bed is a deacliv~ted, or deactivating, catalyst co"lposile or (iii) a Il~L~lure of a deactivated, or deactivating, catalyst composite and particulate inorganic oxide solids, disperse the metal upon the particulate solids of the bed to increase the catalytic activity of the bed, or stabilize and m~int~in the catalytic activity of the bed.
In the m situ prep~r~tiQn~ or formation of a catalyst, a fluidized bed of particulate inorganic solids, suitably alumina, is contacted at FBSG reaction conditions with a low molecular weight hydrocarbon, steam and oxygen while a decomposable compound of the catalytic metal, or catalytic metallic metal, is added to the reaction zone to form the catalyst. The catalytic metal is deposited on the non-catalytic support solids moving from one particle to another to form cryst~llit~s which render the solids of the bed catalytically active for the production in an FBSG process of hydrogen and carbon monoxide from a low molecular weight hydrocarbon feed, steam and oxygen, or in a partial o~ tion process from a low molecular weight hydrocarbon feed and oxygen. The catalyst can then be used in ~, or ex ~, relative to the reactor in which it is prepa~ed. In the formation at FBSG reaction con~itions of a catalyst (ii) where the bed is a deactivated, or deactivating, catalyst cG,--posite, or (iii) a ~"i~ of a deactivated, or deactivating catalyst composite and particulate refr~ctory inorganic oxide solids, on ~l-liti- n of the deco",posable cGIllpound of the catalytic metal, or catalytic met~llic metal, the catalytic metal is deposited on the catalyst cG.~.pos;te of the fl~ i7Pd bed, or on both the catalyst co...po~;le and the particulate refra~tory il~o~ ic oxide solids of the flui~li7ed bed, les~;ti~ely, the metal moving from one solids particle to another to form catalytic metal cryst~llites. The metal cryst~llitP~ form reaction sites on the solids particles, whether origin~lly catalytic or non-catalytic, to increase the catalytic activity of catalytic particles, or render the non-catalytic particlescatalytic, for use in an FBSG process or partial oxidation process for the production of hydrogen and carbon monoxide. The catalyst can be used in situ or ex situ relative to the reactor in which it is pr~ared. In a preferred embodiment, the catalyst is employed in ~ relative to the reactor in which it is prepared. Pursuant to the latter, a decomposable compound of the catalytic metal, or catalytic metallic metal, is added inle~ itlently or continuously to an operating FBSG process, with the hydroc~bon, steam and oxygen at FBSG reaction conditions at a rate sufficient to increase the catalytic activity of the bed, or to stabilize and maintain the catalytic activity of the bed, during the reaction vis-a-vis a similar catalyst, or fluidized bed of the catalyst and refractory inorganic oxide solids, at similar conditions except that the decomposable compound of the catalytic metal, or catalytic mPt~llic metal, is not added to the reaction zone.
Quite surprisingly, it has thus been found that at FBSG
reaction conditions, in an FBSG process, the catalytic metal component of a decomposable compound of the catalytic metal, or the catalytic me~llic metal, added to the bed can migrate from particle to particle to disperse itself as metal crystallites which are catalytically active for the production of hydrogen and carbon monoxide. In the operation of the FBSG process, albeit cintering and agglomeration is a con~im-ing phenomenon which leads to gradual catalyst deactivation, this adverse effect can be co~ enC~ for, or overcome by ~diti~nn of a d~o~ hle cG...~ound of the catalytic metal, or catalytic m.ot~llic metal, to the fl~ i7ed bed at reaction conditions at a rate s~ffi~ient to supply fresh catalytic metal reaction sites to the solids of the bed to b~l~nre~ or exceed the rate of loss of catalytic me~al sites which occurs in the bed without such ~litions, This effect is not found in fixed bed reactors, but occurs in an FBSG reactor. It occurs, it is believed, because the metal co,..lon~-t of the deco,l,l)osable co,llpound of the catalytic metal is liberated, or the catalytic met~llic metal ~E se added to the reactor, is deposited upon the solids particles moving from one solids particle to another and dispersing. The particles cont~ining the metal crystallites are transported from one part of the bed to another, experiencing in an FBSG
process both oxidizing and reducing conditions, forming cryst~llitçs which become new, fresh catalytically active sites the net effect of which is to increase the catalytic activity of the solids of the fluidized bed on which the sites are formed. By a similar mtqch~ni.~m, a fresh catalyst can be formed by depositing a catalytic metal, or metals, upon a particulate refractory inorganic oxide support to from a catalyst ab initio.
In the FBSG process, the surface of the catalyst, or surfaces of the catalyst and solids diluent, melts and becomes sticky, gr~u~lly forming agglomerates of particles which cover over and hide the nrigin~l active metal sites, or form metal agglomerates, or both, which lessens the normal activity of the catalyst. As a result, the yield of hydrogen and carbon monoxide gr~d~ ly decreases. With reduced catalytic activity, less and less of the feed hydr~c~hl,ons react to form hydr~gen and carbon monoxide (or more and more of the feed hyd,~bons "leak" from the process without reacting with the steam and oxygen). Howeva, this loss of catalyst activity or "hydr~lJon leakage"
can be offset and the activity of the bed of catalyst gradu~lly increased, or the activity of the bed of catalyst ~ ol~ d, stabilized and ~ in~inP11 throughout the cycle of operation by addition of a d~Pcol.,po~hle col.lpound of the catalytic metal, or catalytic mPpllic metal, to the fl.)ir~i7pA bed. A catalytic metal co.--pould, or compounds, which decolll~ses at process conditions, or a finely divided form of the catalytic metal, can thus be added to the flui(li7ed bed to deposit the catalytic metal upon the surface of the catalyst, or upon the surfaces of all of the particles of the bed where a mixture of catalyst and solids diluent is employed to control the heats of reaction. At operating conditions the freshly added catalytic metal, when released, will migrate from the surface of one solids particle to another and become highly dispersed as new catalytically active metal sites to produce activity. In an FBSG operation, the catalytic metal col.lpound, or compounds, or a finely divided form of the catalytic metal, is preferably added to the fluidized bed to disperse fresh catalytic metal upon the surfaces of the agglomerating particles at a rate sufficient to balance the loss of active metal sites within the bed res~ nt from the agglomerate-forming reactions. Ideally, a steady-state operation is produced wherein the original catalytically active metal sites lost by normal operation, or operation without the added catalytic metal compound, or co-l-pounds. or finely divided form of the catalytic metal, is b~l~nced by the new catalytically active metal sites formed by addition to the reaction zone of the catalytic metal compound, or co--lpo~ ds, or finely divided form of the catalytic metal.
`- 21 7329S
Preferably, the deco,l,pos~ble metal cG,npound added to the reaction zone is con~tituted of a metal, or the added catalytic metal, is similar to that of the fresh, or original catalyst. The rate of ~ tic!n of the deco~ o~hle catalytic metal colll~und, or added catalytic metal, is sPlP~ted to supply fresh catalytically active metal sites e~se t;~lly equal to those lost in the bed by catalyst deactivation.
The catalyst formed in the ~lefelled practice of this invention is constituted of a refractory inorganic oxide carrier, or support, particularly ~lumin~, and more particularly alpha alumina, composited with a metal, or metals, suitably a Group VIII metal of the Periodic Chart of the Elements (Fisher Scientific Company; Copyright 1953) e.g., nickel, platinum, ruthenium, rhodium or the like, catalytic for the production of hydrogen and carbon monoxide from low molecular weight hydrocarbons contacted with a fluidized bed of the catalyst at high temperature hydrothermal conditions. Preferably, the catalyst is a nickel-on-alumina catalyst, more preferably a nickel-on-alpha alumina catalyst;
especi~lly one cont~ining from about 0.03 percent to about 10 percent nickel, preferably from about 0.3 percent to about 1 percent nickel, composited with the alumina support, based on the total weight of the fll~idi7P~d bed. Suitably, the catalyst is stabilized with one or more of a lanthanum series metal, or metals, component, e.g., l~nth~num, cerium, praseodymium, neodymium, etc. or mixture of these one with another, or with these and other components.
In start up, as practiced in a typical FBSG oper~tion~ a catalyst is ~dmil~Pd with a solids diluent to control the heat of reaction.
g Typically, a catalyst co~ ;nin~ from about 1 per~ent to about 20 percent nickel, ~refe.dbly from about 5 percent to about 20 percent nickel, based on the weight of the catalyst, is ^~lmilred with the solids diluçnt suitably a particulate refr~tory inorganic oxide solids ~liluent~ preferably ~lumin~
and more pref~l~bly alpha ~lumin~, of particle size distributions coll~onding to that of the catalyst, to form the fluidized bed of the reaction zone. Generally, in terms of bed dyn~mics, at least about 80 percent by weight to about 95 percent by weight of the particles of the bed are of ~ meters ranging from about 20 microns to about 130 microns, preferably from about 30 microns to about 110 microns. Generally also, the bed is constituted of from about 10 percent to about 99.9 percent, preferably from about 80 percent to about 99.5 percent, of the solid diluents colllponent and from about 0.1 percent to about 90 percent, preferably from about 0.5 percent to about 20 percent, of the catalyst, based on the total weight of the particulate solids constituting the fl~ i7ed bed.
Hydrogen and carbon monoxide are formed in the FBSG
reaction zone by reaction between a low molecular weight hydrocarbon, or hydrocarbons, suitably a mixture of Cl-C4 ~lk~nes, predominantly methane, e.g., natural gas, steam, and oxygen, over the fluidized bed of nickel-on-an ~lumin~ based catalyst, or catalyst and solids diluent, at tel~lpeldtures ranging from about 1500F to about 1900F, preferably from about 1600F to about 1800F, in a net reducing atmosphere. A
deco~ ?osable nickel compound, or m-ot~llic nickel, is added inte~ y or continuously to the FBSG reaction zone at a rate suffi~ ient to increase the catalytic activity of the flui~i7~1 bed, or stabilize and m~int~in the catalytic activity of the fluldized bed, throughout the cycle of operation.
21 7~29$
In other words, the deco~ osable nickel coll,~ound, or mPt~llie nickel, is added periodically to the reaction zone while the reaction is continl)ed to raise the activity of the bed back to a given level after a decline in catalyst activity, or added continllously to ~ in a constant level of catalyst activity for the bed during the operation. Thus, fresh catalytic metal reaction sites are added to the total solids of the bed to exce~d, or b~l~nce the loss of catalytic metal sites which occurs without such additions.
Exemplary of the catalytic metal cG"lpound, or compounds useful as sources of the catalytic metal in the practice of this invention are those which contain, e.g., nickel, platinum, rhodium, ruthenium or the like, i.e., such oxides and salts as: nickel oxide, nickel acetate, nickel acetylacetonate, nickel carbonate, nickel propionate, nickel formate, nickel nitrate, platinum pentanedionate, platinum oxides, rhodium acetate, rhodium nitrate, ruthenium nitrosylnitrate, rushPnillm carbonyl and the like; or a mixture of these and other oxides and salts. Finely divided m~t~llit~. metals, e.g., nickel, ruthenium and the like, can also be employed as a source of the catalytic metal. The catalytic metal source, e.g., catalytic metal compound, or compounds, is added to the fluidized bed of the reaction zone in concentration suffi~ ient that the decomposing co~"pound that is dispersed upon the catalyst, or ~uppoll, provides sufficient activity to balance the activity lost due to the agglomerating solids, and agglomerating original- catalytic metals components of the catalyst.
The invention will be better understood by lef~ence to the following clelTon~tr~tion, and non-limiting e~ ...pl~s All parts are given in terms of weight units except as otherwise specified- ~es~ .s are ~ -11- 21 73~95 given in terms of pounds per square inch absolute, and te,llpel~lu~s are t;Apless~d in terms of degrees Fahrenheit.
The following demon~tration shows that in an FBSG
reactor, at FBSG opeld~ g co~ditions, nickel has the ability to move from one solids particle to another to disperse, and spread throughout the fluidi7ed solids bed to rorm catalytically active nickel metal sites on the particles even where the source of nickel is a fresh nickel cat~lyst.
Demonstration A catalyst characterized as a 50 cc sample of 1 wt. % Ni on tabular o~-AI203 particles (106 to l50~m) was loaded into a small FBSG
reactor, or fluidized bed reactor having a fli~eng~ging zone at the top, and an internal filter to limit the loss of solids. Gases were fed to the reactor through small refractory nozzles at the bottom of the reactor; a mixture of steam and natural gas through one set of nozzles and oxygen through a second set of nozzles. The molar ratios of the components of the feed gas were mçth~ne/steam/oxygen at about 211/1. The reactor was operated at 1800F and 360 psia. The fluidized bed was operated near equilibrium conditions.
Intel",;l~el-tly the fluidized bed reactor was shut-down, a sample of the bed uas removed for activity determination, and the removed sample was replaced with pure, uncatalyzed ~lllmin~ The activity of the bed sample removed from the FBSG reactor was dele-,l~incd in a ~;xed bed reactor operation operating at 1800F and 360 psig. The fixed bed reactor used a 1 cc sample of catalyst and employed a rapid quench to allow sampling of the product gas without back reaction. Feed to this reactor was a post partial o~ tioll~ or POX gas ~ ule and contained CH4/H2lCO/H2O in a molar ratio of 1/1/1/2.
The activities of the catalysts taken from the fl~ 7ed bed over about a 70 day period showed a drop in activity for the catalyst spe~imPn~ placed in the fixed bed reactor. However, when the activity was adjusted for nickel loading (some nickel being lost from the fluid bed and also removed and diluted because of sampling), the activity was found to remain constant. An end of run bed sample from the FBSG reactor unit was analyzed on a Sc~nning electron microscope using energy dispersive x-rays to look at nickel dispersion on the solids. It was found that nickel was evenly dispersed on all particles even though over 30% of the bed was replaced with uncatalyzed ~lllmin~. In a continuous run with a fresh catalyst in a fixed bed it was found that the catalyst activity decreased by about two orders of m~nitude over a 90 day period. This decrease is due to loss of active nickel sites because of sintering. In contrast a relatively stable activity was found in the FBSG, or fluidized bed reactor due to redispersion of the nickel.
In the examples which follow, the effectiveness of various sources of catalytic nickel added to an FBSG reactor are demonstrated.
Examples Activity increases for the steam reforming of m~th~ne were observed in an FBSG reactor with the ~ ition to the reactor of nickel from various sources. The FBSG reàctor was ~e~dted at about 1750F
and 360 psia with an alpha ~lllmin~ bed m~t~ri~l Cont~ining from about 0.3 to 1% nickel; the particles of the bed having an average particle , rli~mlotrr of about 70 ,~m. The ratios of the molar gas feeds to the unit were ~etl~n~/steam/oxygen of about 2/1/1. In the oper~ti~n of this unit, various nickel col.t~inin~ m~trri~lc, i.e., NiCO3 and NiO powders and 60 ~m Ni metal particles, were added to determine their catalytic effectiveness at re~iucin~ the m~oth~ne leak (reduçing the meth~ne conc~nl.dlion in the product gas by catalyzing steam reforming). Thus, if the nickel-cont~ining co---ponent added is active, the mPth~nto concentration will decrease; and the pelrol",ance of the added component is defined by the observed decrease of m~th~ne divided by the quantity of nickel added.
The performance index, CH4 decrease . wt. added Ni, for the various nickel-containing compound additions, and metallic nickel, is shown in the last column of the Table. This performance index was 0.55 for NiC03, an average of 0.54 for NiO, and 0.12 for Ni metal particles.
An 8.6 wt. ~ nickel-on-alumina catalyst was also used as a nickel source, for purposes of comparison. These data show that the performance of these added nickel-cont~ining, or metallic nickel, m~tçri~lc are very good when compared to the performance of the fresh, supported, nickel reforming catalyst. As shown in the Table the pe,Çol--.allce index for the 8.6 wt.% Ni on ~-Al203 catalyst was 0.14. The fact that the d~i~iiLiUnS of these non-~uppolled nickel m~trri~l~ to the reactor give catalytic pelfor~ res co-,-p~dble to suppol~ed nickel catalysts is surprising and llnP-~pected 21 732q5 _ z o o o o o o o ~4 .~
x x oo o ~ ~ c o o o _ ~
~ ~ ~ e O ~
~ ~ -- C ~
,C-~ -- C
_ c a.~ ~
~ oo x x ~ ~ 8 ~ .e :~ m ~ x oo ~ ~
~ n n Z o o ~ ~ -- ~
6 s c~ ~ .~
c~ -- c . C 01~
.~ ~ X _ ~ ~ O v~ 3 B i~ o ~ ~ ~ C
O .
z ~ 3 g ,o
The high localized flame tel,l~.dlule produced by the oxygen in the burning zone of the bed can exceed the mPlting point of the alumina, or at least produce le~l~pf ~n~les which cause the surface of the ~ min~
particles to melt, stick and fuse together as tne particles ~pe~ rely collide or recycle through the burning zone of the bed. The amount of agglomeration increases with time which adversely affects the flllidi7~tion char~cteristics of the bed, and the activity of the catalyst de~lines. The active catalytic sites become in~ccescihle to the react~nts due to the agglomeration of the particles; or active surface area lost due to metals agglomeration.
3. DESCRIPTION OF THE INVENTION
The present invention relates to the formation in an FBSG
operation of catalysts useful (a) in an FBSG process, or process for producing a syn gas, or mixture of hydrogen and carbon monoxide, from a low molecular weight hydrocarbon, steam and oxygen and (b) in a partial oxidation process for producing hydrogen and carbon monoxide from a low molecular weight hydrocarbon and oxygen. The catalysts are formed in a reaction zone at FBSG reaction conditions from a flui-li7e~
bed of (i) particulate refractory inorganic oxide solids, or (ii) a flui~li7ed bed of a deactivated, or deactivating, catalyst composite, or (iii) mixture of a deactivated, or deactivating, catalyst composite and particulate refractory inorganic oxide solids, by adding, intel..,il(ently or continuously to the reaction zone a decomposable compound of a catalytic-metal, or catalyLic m~t~llic me~ o disperse the metal, which at FBSG reaction conditions, will move from particle to particle to form catalytically active mPt~llic cryst~llites upon the solids panicles of the flui~ ed bed sllffi~ient, (i) whe;c the bed is col-~tituted of particulate inol~dnic oxide solids, to produce a catalyst in situ, (ii) where the bed is a deacliv~ted, or deactivating, catalyst co"lposile or (iii) a Il~L~lure of a deactivated, or deactivating, catalyst composite and particulate inorganic oxide solids, disperse the metal upon the particulate solids of the bed to increase the catalytic activity of the bed, or stabilize and m~int~in the catalytic activity of the bed.
In the m situ prep~r~tiQn~ or formation of a catalyst, a fluidized bed of particulate inorganic solids, suitably alumina, is contacted at FBSG reaction conditions with a low molecular weight hydrocarbon, steam and oxygen while a decomposable compound of the catalytic metal, or catalytic metallic metal, is added to the reaction zone to form the catalyst. The catalytic metal is deposited on the non-catalytic support solids moving from one particle to another to form cryst~llit~s which render the solids of the bed catalytically active for the production in an FBSG process of hydrogen and carbon monoxide from a low molecular weight hydrocarbon feed, steam and oxygen, or in a partial o~ tion process from a low molecular weight hydrocarbon feed and oxygen. The catalyst can then be used in ~, or ex ~, relative to the reactor in which it is prepa~ed. In the formation at FBSG reaction con~itions of a catalyst (ii) where the bed is a deactivated, or deactivating, catalyst cG,--posite, or (iii) a ~"i~ of a deactivated, or deactivating catalyst composite and particulate refr~ctory inorganic oxide solids, on ~l-liti- n of the deco",posable cGIllpound of the catalytic metal, or catalytic met~llic metal, the catalytic metal is deposited on the catalyst cG.~.pos;te of the fl~ i7Pd bed, or on both the catalyst co...po~;le and the particulate refra~tory il~o~ ic oxide solids of the flui~li7ed bed, les~;ti~ely, the metal moving from one solids particle to another to form catalytic metal cryst~llites. The metal cryst~llitP~ form reaction sites on the solids particles, whether origin~lly catalytic or non-catalytic, to increase the catalytic activity of catalytic particles, or render the non-catalytic particlescatalytic, for use in an FBSG process or partial oxidation process for the production of hydrogen and carbon monoxide. The catalyst can be used in situ or ex situ relative to the reactor in which it is pr~ared. In a preferred embodiment, the catalyst is employed in ~ relative to the reactor in which it is prepared. Pursuant to the latter, a decomposable compound of the catalytic metal, or catalytic metallic metal, is added inle~ itlently or continuously to an operating FBSG process, with the hydroc~bon, steam and oxygen at FBSG reaction conditions at a rate sufficient to increase the catalytic activity of the bed, or to stabilize and maintain the catalytic activity of the bed, during the reaction vis-a-vis a similar catalyst, or fluidized bed of the catalyst and refractory inorganic oxide solids, at similar conditions except that the decomposable compound of the catalytic metal, or catalytic mPt~llic metal, is not added to the reaction zone.
Quite surprisingly, it has thus been found that at FBSG
reaction conditions, in an FBSG process, the catalytic metal component of a decomposable compound of the catalytic metal, or the catalytic me~llic metal, added to the bed can migrate from particle to particle to disperse itself as metal crystallites which are catalytically active for the production of hydrogen and carbon monoxide. In the operation of the FBSG process, albeit cintering and agglomeration is a con~im-ing phenomenon which leads to gradual catalyst deactivation, this adverse effect can be co~ enC~ for, or overcome by ~diti~nn of a d~o~ hle cG...~ound of the catalytic metal, or catalytic m.ot~llic metal, to the fl~ i7ed bed at reaction conditions at a rate s~ffi~ient to supply fresh catalytic metal reaction sites to the solids of the bed to b~l~nre~ or exceed the rate of loss of catalytic me~al sites which occurs in the bed without such ~litions, This effect is not found in fixed bed reactors, but occurs in an FBSG reactor. It occurs, it is believed, because the metal co,..lon~-t of the deco,l,l)osable co,llpound of the catalytic metal is liberated, or the catalytic met~llic metal ~E se added to the reactor, is deposited upon the solids particles moving from one solids particle to another and dispersing. The particles cont~ining the metal crystallites are transported from one part of the bed to another, experiencing in an FBSG
process both oxidizing and reducing conditions, forming cryst~llitçs which become new, fresh catalytically active sites the net effect of which is to increase the catalytic activity of the solids of the fluidized bed on which the sites are formed. By a similar mtqch~ni.~m, a fresh catalyst can be formed by depositing a catalytic metal, or metals, upon a particulate refractory inorganic oxide support to from a catalyst ab initio.
In the FBSG process, the surface of the catalyst, or surfaces of the catalyst and solids diluent, melts and becomes sticky, gr~u~lly forming agglomerates of particles which cover over and hide the nrigin~l active metal sites, or form metal agglomerates, or both, which lessens the normal activity of the catalyst. As a result, the yield of hydrogen and carbon monoxide gr~d~ ly decreases. With reduced catalytic activity, less and less of the feed hydr~c~hl,ons react to form hydr~gen and carbon monoxide (or more and more of the feed hyd,~bons "leak" from the process without reacting with the steam and oxygen). Howeva, this loss of catalyst activity or "hydr~lJon leakage"
can be offset and the activity of the bed of catalyst gradu~lly increased, or the activity of the bed of catalyst ~ ol~ d, stabilized and ~ in~inP11 throughout the cycle of operation by addition of a d~Pcol.,po~hle col.lpound of the catalytic metal, or catalytic mPpllic metal, to the fl.)ir~i7pA bed. A catalytic metal co.--pould, or compounds, which decolll~ses at process conditions, or a finely divided form of the catalytic metal, can thus be added to the flui(li7ed bed to deposit the catalytic metal upon the surface of the catalyst, or upon the surfaces of all of the particles of the bed where a mixture of catalyst and solids diluent is employed to control the heats of reaction. At operating conditions the freshly added catalytic metal, when released, will migrate from the surface of one solids particle to another and become highly dispersed as new catalytically active metal sites to produce activity. In an FBSG operation, the catalytic metal col.lpound, or compounds, or a finely divided form of the catalytic metal, is preferably added to the fluidized bed to disperse fresh catalytic metal upon the surfaces of the agglomerating particles at a rate sufficient to balance the loss of active metal sites within the bed res~ nt from the agglomerate-forming reactions. Ideally, a steady-state operation is produced wherein the original catalytically active metal sites lost by normal operation, or operation without the added catalytic metal compound, or co-l-pounds. or finely divided form of the catalytic metal, is b~l~nced by the new catalytically active metal sites formed by addition to the reaction zone of the catalytic metal compound, or co--lpo~ ds, or finely divided form of the catalytic metal.
`- 21 7329S
Preferably, the deco,l,pos~ble metal cG,npound added to the reaction zone is con~tituted of a metal, or the added catalytic metal, is similar to that of the fresh, or original catalyst. The rate of ~ tic!n of the deco~ o~hle catalytic metal colll~und, or added catalytic metal, is sPlP~ted to supply fresh catalytically active metal sites e~se t;~lly equal to those lost in the bed by catalyst deactivation.
The catalyst formed in the ~lefelled practice of this invention is constituted of a refractory inorganic oxide carrier, or support, particularly ~lumin~, and more particularly alpha alumina, composited with a metal, or metals, suitably a Group VIII metal of the Periodic Chart of the Elements (Fisher Scientific Company; Copyright 1953) e.g., nickel, platinum, ruthenium, rhodium or the like, catalytic for the production of hydrogen and carbon monoxide from low molecular weight hydrocarbons contacted with a fluidized bed of the catalyst at high temperature hydrothermal conditions. Preferably, the catalyst is a nickel-on-alumina catalyst, more preferably a nickel-on-alpha alumina catalyst;
especi~lly one cont~ining from about 0.03 percent to about 10 percent nickel, preferably from about 0.3 percent to about 1 percent nickel, composited with the alumina support, based on the total weight of the fll~idi7P~d bed. Suitably, the catalyst is stabilized with one or more of a lanthanum series metal, or metals, component, e.g., l~nth~num, cerium, praseodymium, neodymium, etc. or mixture of these one with another, or with these and other components.
In start up, as practiced in a typical FBSG oper~tion~ a catalyst is ~dmil~Pd with a solids diluent to control the heat of reaction.
g Typically, a catalyst co~ ;nin~ from about 1 per~ent to about 20 percent nickel, ~refe.dbly from about 5 percent to about 20 percent nickel, based on the weight of the catalyst, is ^~lmilred with the solids diluçnt suitably a particulate refr~tory inorganic oxide solids ~liluent~ preferably ~lumin~
and more pref~l~bly alpha ~lumin~, of particle size distributions coll~onding to that of the catalyst, to form the fluidized bed of the reaction zone. Generally, in terms of bed dyn~mics, at least about 80 percent by weight to about 95 percent by weight of the particles of the bed are of ~ meters ranging from about 20 microns to about 130 microns, preferably from about 30 microns to about 110 microns. Generally also, the bed is constituted of from about 10 percent to about 99.9 percent, preferably from about 80 percent to about 99.5 percent, of the solid diluents colllponent and from about 0.1 percent to about 90 percent, preferably from about 0.5 percent to about 20 percent, of the catalyst, based on the total weight of the particulate solids constituting the fl~ i7ed bed.
Hydrogen and carbon monoxide are formed in the FBSG
reaction zone by reaction between a low molecular weight hydrocarbon, or hydrocarbons, suitably a mixture of Cl-C4 ~lk~nes, predominantly methane, e.g., natural gas, steam, and oxygen, over the fluidized bed of nickel-on-an ~lumin~ based catalyst, or catalyst and solids diluent, at tel~lpeldtures ranging from about 1500F to about 1900F, preferably from about 1600F to about 1800F, in a net reducing atmosphere. A
deco~ ?osable nickel compound, or m-ot~llic nickel, is added inte~ y or continuously to the FBSG reaction zone at a rate suffi~ ient to increase the catalytic activity of the flui~i7~1 bed, or stabilize and m~int~in the catalytic activity of the fluldized bed, throughout the cycle of operation.
21 7~29$
In other words, the deco~ osable nickel coll,~ound, or mPt~llie nickel, is added periodically to the reaction zone while the reaction is continl)ed to raise the activity of the bed back to a given level after a decline in catalyst activity, or added continllously to ~ in a constant level of catalyst activity for the bed during the operation. Thus, fresh catalytic metal reaction sites are added to the total solids of the bed to exce~d, or b~l~nce the loss of catalytic metal sites which occurs without such additions.
Exemplary of the catalytic metal cG"lpound, or compounds useful as sources of the catalytic metal in the practice of this invention are those which contain, e.g., nickel, platinum, rhodium, ruthenium or the like, i.e., such oxides and salts as: nickel oxide, nickel acetate, nickel acetylacetonate, nickel carbonate, nickel propionate, nickel formate, nickel nitrate, platinum pentanedionate, platinum oxides, rhodium acetate, rhodium nitrate, ruthenium nitrosylnitrate, rushPnillm carbonyl and the like; or a mixture of these and other oxides and salts. Finely divided m~t~llit~. metals, e.g., nickel, ruthenium and the like, can also be employed as a source of the catalytic metal. The catalytic metal source, e.g., catalytic metal compound, or compounds, is added to the fluidized bed of the reaction zone in concentration suffi~ ient that the decomposing co~"pound that is dispersed upon the catalyst, or ~uppoll, provides sufficient activity to balance the activity lost due to the agglomerating solids, and agglomerating original- catalytic metals components of the catalyst.
The invention will be better understood by lef~ence to the following clelTon~tr~tion, and non-limiting e~ ...pl~s All parts are given in terms of weight units except as otherwise specified- ~es~ .s are ~ -11- 21 73~95 given in terms of pounds per square inch absolute, and te,llpel~lu~s are t;Apless~d in terms of degrees Fahrenheit.
The following demon~tration shows that in an FBSG
reactor, at FBSG opeld~ g co~ditions, nickel has the ability to move from one solids particle to another to disperse, and spread throughout the fluidi7ed solids bed to rorm catalytically active nickel metal sites on the particles even where the source of nickel is a fresh nickel cat~lyst.
Demonstration A catalyst characterized as a 50 cc sample of 1 wt. % Ni on tabular o~-AI203 particles (106 to l50~m) was loaded into a small FBSG
reactor, or fluidized bed reactor having a fli~eng~ging zone at the top, and an internal filter to limit the loss of solids. Gases were fed to the reactor through small refractory nozzles at the bottom of the reactor; a mixture of steam and natural gas through one set of nozzles and oxygen through a second set of nozzles. The molar ratios of the components of the feed gas were mçth~ne/steam/oxygen at about 211/1. The reactor was operated at 1800F and 360 psia. The fluidized bed was operated near equilibrium conditions.
Intel",;l~el-tly the fluidized bed reactor was shut-down, a sample of the bed uas removed for activity determination, and the removed sample was replaced with pure, uncatalyzed ~lllmin~ The activity of the bed sample removed from the FBSG reactor was dele-,l~incd in a ~;xed bed reactor operation operating at 1800F and 360 psig. The fixed bed reactor used a 1 cc sample of catalyst and employed a rapid quench to allow sampling of the product gas without back reaction. Feed to this reactor was a post partial o~ tioll~ or POX gas ~ ule and contained CH4/H2lCO/H2O in a molar ratio of 1/1/1/2.
The activities of the catalysts taken from the fl~ 7ed bed over about a 70 day period showed a drop in activity for the catalyst spe~imPn~ placed in the fixed bed reactor. However, when the activity was adjusted for nickel loading (some nickel being lost from the fluid bed and also removed and diluted because of sampling), the activity was found to remain constant. An end of run bed sample from the FBSG reactor unit was analyzed on a Sc~nning electron microscope using energy dispersive x-rays to look at nickel dispersion on the solids. It was found that nickel was evenly dispersed on all particles even though over 30% of the bed was replaced with uncatalyzed ~lllmin~. In a continuous run with a fresh catalyst in a fixed bed it was found that the catalyst activity decreased by about two orders of m~nitude over a 90 day period. This decrease is due to loss of active nickel sites because of sintering. In contrast a relatively stable activity was found in the FBSG, or fluidized bed reactor due to redispersion of the nickel.
In the examples which follow, the effectiveness of various sources of catalytic nickel added to an FBSG reactor are demonstrated.
Examples Activity increases for the steam reforming of m~th~ne were observed in an FBSG reactor with the ~ ition to the reactor of nickel from various sources. The FBSG reàctor was ~e~dted at about 1750F
and 360 psia with an alpha ~lllmin~ bed m~t~ri~l Cont~ining from about 0.3 to 1% nickel; the particles of the bed having an average particle , rli~mlotrr of about 70 ,~m. The ratios of the molar gas feeds to the unit were ~etl~n~/steam/oxygen of about 2/1/1. In the oper~ti~n of this unit, various nickel col.t~inin~ m~trri~lc, i.e., NiCO3 and NiO powders and 60 ~m Ni metal particles, were added to determine their catalytic effectiveness at re~iucin~ the m~oth~ne leak (reduçing the meth~ne conc~nl.dlion in the product gas by catalyzing steam reforming). Thus, if the nickel-cont~ining co---ponent added is active, the mPth~nto concentration will decrease; and the pelrol",ance of the added component is defined by the observed decrease of m~th~ne divided by the quantity of nickel added.
The performance index, CH4 decrease . wt. added Ni, for the various nickel-containing compound additions, and metallic nickel, is shown in the last column of the Table. This performance index was 0.55 for NiC03, an average of 0.54 for NiO, and 0.12 for Ni metal particles.
An 8.6 wt. ~ nickel-on-alumina catalyst was also used as a nickel source, for purposes of comparison. These data show that the performance of these added nickel-cont~ining, or metallic nickel, m~tçri~lc are very good when compared to the performance of the fresh, supported, nickel reforming catalyst. As shown in the Table the pe,Çol--.allce index for the 8.6 wt.% Ni on ~-Al203 catalyst was 0.14. The fact that the d~i~iiLiUnS of these non-~uppolled nickel m~trri~l~ to the reactor give catalytic pelfor~ res co-,-p~dble to suppol~ed nickel catalysts is surprising and llnP-~pected 21 732q5 _ z o o o o o o o ~4 .~
x x oo o ~ ~ c o o o _ ~
~ ~ ~ e O ~
~ ~ -- C ~
,C-~ -- C
_ c a.~ ~
~ oo x x ~ ~ 8 ~ .e :~ m ~ x oo ~ ~
~ n n Z o o ~ ~ -- ~
6 s c~ ~ .~
c~ -- c . C 01~
.~ ~ X _ ~ ~ O v~ 3 B i~ o ~ ~ ~ C
O .
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Claims (20)
1. A process for the production of a catalyst useful in fluidized bed syn gas and partial oxidation which comprises forming in a reaction zone a fluidized bed of (i) particulate refractory inorganic oxide solids, or (ii) a deactivated, or deactivating, catalyst composite, or (iii) mixture of a deactivated, or deactivating, catalyst composite and particulate refractory inorganic oxide solids, heating the fluidized bed while maintaining temperatures ranging from about 1500°F to about 1900°F, feeding a low molecular weight hydrocarbon feed, steam and oxygen into the fluidized bed, and adding, intermittently or continuously, to the fluidized bed of the reaction zone a decomposable compound of a catalytic Group VIII
metal, or catalytic Group VIII metallic metal, to disperse said metal upon the surfaces of (i) the particulate inorganic oxide solids, (ii) the deactivated, or deactivating catalyst composite, or (iii) mixture of a deactivated, or deactivating catalyst composite and particulate refractory inorganic oxide solids, as crystallites which provide catalytic sites sufficient to form a catalyst, to increase the catalytic activity of the fluidized bed, or stabilize and maintain the catalytic activity of the fluidized bed.
metal, or catalytic Group VIII metallic metal, to disperse said metal upon the surfaces of (i) the particulate inorganic oxide solids, (ii) the deactivated, or deactivating catalyst composite, or (iii) mixture of a deactivated, or deactivating catalyst composite and particulate refractory inorganic oxide solids, as crystallites which provide catalytic sites sufficient to form a catalyst, to increase the catalytic activity of the fluidized bed, or stabilize and maintain the catalytic activity of the fluidized bed.
2. The process of Claim 1 wherein the catalytic Group VIII
metal is nickel, and the particulate inorganic oxide solids of the fluidized bed is alumina.
metal is nickel, and the particulate inorganic oxide solids of the fluidized bed is alumina.
3. The process of Claim 1 wherein at least about 80 percent to about 95 percent by weight of the solids particles of the fluidized bed on which the catalytic Group VIII metal is deposited is of diameter ranging from about 20 microns to about 130 microns.
4. The process of Claim 3 wherein the catalytic metal deposited on the solids particles is nickel.
5. The process of Claim 1 wherein the decomposable compound of the catalytic Group VIII metal added to the fluidized bed is an oxide or salt of nickel.
6. The process of Claim 1 wherein the metal component of the decomposable compound of a catalytic Group VIII metal, or catalytic Group VIII metallic metal, added to the reaction zone is nickel, the fluidized bed of the reaction zone is particulate refractory inorganic oxide solids, and nickel is deposited on said particulate refractory inorganic oxide solids to form a catalyst useful in situ or ex situ to the reaction zone in which the catalyst is formed.
7. The process of Claim 6 wherein the particulate refractory inorganic oxide solids is alumina, and the catalyst formed is a nickel-on-alumina catalyst.
8. The process of Claim 7 wherein the catalyst is comprised of from about 0.03 percent to about 10 percent nickel, based on the weight of the catalyst.
9. The process of Claim 1 wherein the metal component of the decomposable compound of a catalytic Group VIII metal, or catalytic Group VIII metallic metal, added to the reaction zone is nickel, the fluidized bed of the reaction zone is a deactivated, or deactivating, catalyst composite, or mixture of a deactivated, or deactivating, catalyst composite and particulate refractory inorganic oxide solids, and nickel is deposited on the particulate solids of the bed to form a catalyst useful in situ or ex situ to the reaction zone in which the catalyst is formed.
10. In a process for the production of hydrogen and carbon monoxide from a low molecular weight hydrocarbon by contact with a fluidized bed of a supported catalytic-metal catalyst at high temperature in the presence of steam and oxygen in a reaction zone operated in a net reducing atmosphere sufficient to progressively deactivate the catalyst during the reaction, the improvement comprising adding to the reaction zone a decomposable compound of a catalytic-metal, or catalytic metallic metal, the metal at reaction conditions being dispersed upon the catalyst sufficient to increase the catalytic activity of the fluidized bed, or stabilize and maintain the catalytic activity of the fluidized bed, during the reaction vis-a-vis a fluidized bed of a similar catalyst at similar reaction conditions except that the decomposable compound of the catalytic-metal, or catalytic metallic metal, is not added to the reaction zone.
11. The process of Claim 10 wherein the catalytic metal catalyst is a Group VIII metal-on-alumina, the decomposable compound of a catalytic metal is a Group VIII metal compound decomposable at process conditions, and the catalytic metallic metal is a metallic Group VIII metal.
12. The process of Claim 11 wherein the Group VIII metal is nickel.
13. The process of Claim 10 wherein the fluidized bed is constituted of a mixture of the supported catalyst and a particulate solids diluent.
14. The process of Claim 13 wherein at least about 80 percent to about 95 percent by weight of the particles of the bed are of diameters ranging from about 20 microns to about 130 microns, and the bed is comprised of from about 10 percent to about 99.9 percent of the solids diluent component and from about 0.1 percent to about 90 percent of the catalyst component.
15. The process of Claim 10 wherein the temperature of the reaction zone ranges from about 1500°F to about 1900°F.
16. In a process for the production of hydrogen and carbon monoxide from a low molecular weight hydrocarbon by contact with a fluidized bed of a nickel-on-alumina catalyst, or mixture of said catalyst and a particulate solids diluent, at temperature ranging from about 1500°F
to about 1900°F in the presence of steam and oxygen in a reaction zone operated in a net reducing atmosphere sufficient to progressively deactivate the catalyst during the reaction the improvement comprising adding, intermittently or continuously, to the reaction zone a decomposable nickel compound, or metallic nickel, which at reaction conditions causes the nickel to become dispersed upon the catalyst, or solids diluent, or both the catalyst and solids diluent, sufficient to increase the catalytic activity of the fluidized bed, or stabilize and maintain the catalytic activity of the fluidized bed, during the operation vis-a-vis a fluidized bed of a similar catalyst at similar reaction conditions except that the decomposable nickel compound, or metallic nickel, is not added to the reaction zone during the operation.
to about 1900°F in the presence of steam and oxygen in a reaction zone operated in a net reducing atmosphere sufficient to progressively deactivate the catalyst during the reaction the improvement comprising adding, intermittently or continuously, to the reaction zone a decomposable nickel compound, or metallic nickel, which at reaction conditions causes the nickel to become dispersed upon the catalyst, or solids diluent, or both the catalyst and solids diluent, sufficient to increase the catalytic activity of the fluidized bed, or stabilize and maintain the catalytic activity of the fluidized bed, during the operation vis-a-vis a fluidized bed of a similar catalyst at similar reaction conditions except that the decomposable nickel compound, or metallic nickel, is not added to the reaction zone during the operation.
17. The process of Claim 16 wherein at least about 80 percent to about 95 percent by weight of the particles of the bed are of diameters ranging from about 20 microns to about 130 microns, and the bed is comprised of from about 10 percent to about 99.9 percent of the solids diluent component and from about 0.1 percent to about 90 percent of the catalyst component.
18. The process of Claim 17 wherein the particles of the bed are of diameter ranging from about 30 microns to about 110 microns, and the bed is comprised of from about 80 percent to about 99.5 percent of the solids diluent and from about 0.5 percent to about 20 percent of the catalyst component.
19. The process of Claim 17 wherein the catalyst is comprised of nickel stabilized with one or more of a lanthanum series metal.
20. The process of Claim 16 wherein the decomposable nickel compound added to the fluidized bed is an oxide or salt of nickel.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US41832595A | 1995-04-07 | 1995-04-07 | |
| US418,325 | 1995-04-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2173295A1 true CA2173295A1 (en) | 1996-10-08 |
Family
ID=23657645
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002173295A Abandoned CA2173295A1 (en) | 1995-04-07 | 1996-04-02 | In situ catalyst formation in fluidized bed syn gas operations |
Country Status (2)
| Country | Link |
|---|---|
| AU (1) | AU707435B2 (en) |
| CA (1) | CA2173295A1 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2546606A (en) * | 1948-05-10 | 1951-03-27 | Phillips Petroleum Co | Synthesis gas preparation |
| US5160456A (en) * | 1991-06-07 | 1992-11-03 | Exxon Research And Engineering Company | Catalyst/heat-transfer medium for syngas generation |
| US5143647A (en) * | 1991-06-07 | 1992-09-01 | Exxon Research And Engineering Company | Synthesis gas generation startup process (C-2556) |
-
1996
- 1996-04-02 CA CA002173295A patent/CA2173295A1/en not_active Abandoned
- 1996-04-04 AU AU50545/96A patent/AU707435B2/en not_active Ceased
Also Published As
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| AU707435B2 (en) | 1999-07-08 |
| AU5054596A (en) | 1996-10-17 |
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