CA1195635A - Coal hydrogenation process using petroleum-derived slurrying oil - Google Patents
Coal hydrogenation process using petroleum-derived slurrying oilInfo
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- CA1195635A CA1195635A CA000415814A CA415814A CA1195635A CA 1195635 A CA1195635 A CA 1195635A CA 000415814 A CA000415814 A CA 000415814A CA 415814 A CA415814 A CA 415814A CA 1195635 A CA1195635 A CA 1195635A
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Abstract
ABSTRACT OF THE DISCLOSURE
A process for the simultaneous catalytic hydrogenation of coal and a petroleum-derived slurrying oil to produce predominantly hydrocarbon liquid products, employing an ebullated bed catalytic hydrogenation reaction step. In the process, particulate coal is admixed with the slurrying oil comprising from about 5% to 100% by weight catalytic cracker aromatic decant oil boiling in the range of about 300-1000 F. The coal-oil slurry is reacted with hydrogen in an ebullated bed of particulate hydrogenation catalyst to effect substantial conversion of the coal and the slurrying oil component to produce a range of liquid products including an increased percentage of C4-650°F boiling range fraction product. In an alternate embodiment of the process, the oil feed includes an increased percentage of petroleum-derived decant oil and heavy coal-derived recycled oil from the product liquids. If desired, some of the C4-400°F naphtha product fraction can be returned to the petroleum refinery catalytic cracker to produce additional gasoline product.
A process for the simultaneous catalytic hydrogenation of coal and a petroleum-derived slurrying oil to produce predominantly hydrocarbon liquid products, employing an ebullated bed catalytic hydrogenation reaction step. In the process, particulate coal is admixed with the slurrying oil comprising from about 5% to 100% by weight catalytic cracker aromatic decant oil boiling in the range of about 300-1000 F. The coal-oil slurry is reacted with hydrogen in an ebullated bed of particulate hydrogenation catalyst to effect substantial conversion of the coal and the slurrying oil component to produce a range of liquid products including an increased percentage of C4-650°F boiling range fraction product. In an alternate embodiment of the process, the oil feed includes an increased percentage of petroleum-derived decant oil and heavy coal-derived recycled oil from the product liquids. If desired, some of the C4-400°F naphtha product fraction can be returned to the petroleum refinery catalytic cracker to produce additional gasoline product.
Description
' ~g~35 HR-1273 COAL HYD~OGENATION PROCESS
-USI~G PETROLEUM-DERIVED SLURRYING OIL
~ACXGRo~'ND CF INVENTION
Field of Invention:
. . . _ This invention pertains to an improved process for coal hydrogenation to produce hydrocarbon liquids and gases and p~rtains particularly to a coal liquefaction and catalytic hydrogerlation process which utilizes a petroleum-derived aro-matic oil for slurrying the coal and increasing the yield of naphtha and other light hydrocarbon liquid product fractions.
Descri~tion of Prior Art Numerous methods have been proposed in the prior art for eec,ting the h~ydroconversion of coal into hydrocarbon liquid and gas products. Present commercial conversion methods con-~erltionall.y comprise subjecting a coal-oil sl'urry to cataL~tic hydrogenation at elevated temperatures and pressure c~orl~itions to produce a coal-derived synthetic oil and distillate products and gas. Typically, these rnethods utilize an ebullated bed catalytic reaction technique whereln a strea~ of the coal-oil slurry is admixed with gaseous hydrogen and passed upwardly through an ~bullated hed reactor containing a bed of particulate hydrogenation catalyst, thereby providlng for liquefaction and hydrogenation of the coal. ~xamples of such prior art caal conversion processes are those described in U. S. Patent Nos~ 3,519~555 to Keith et al, 3,540~995 to Wolk' et al, 3 791,957 to Wolk, 3,607,719 ~@~
3~i ```
to Johnson et al, 3,594,305 to ~ir~, 3,586,621 to Pitch,ord, et al 3,755,13~ to Schuman, and 4,054,504 to Chervenak et al.
Such techniaues, while aenerally effec-ti~e in convertino coal into desired liquid products, have characteristically been limited to conversion of the coal, while the oil pro-viding the slurrying liquid needed for preparing and handling the coal feed to -the pressurized reactor has remained substantially unconverted throughout the hydroyenation process. While the desirahility of effecting simultaneous conversion of both coal and heavy crude or residuum oll feed components in these ebullated bed procedures has been recognized, for example, to increase the conversion effi-ciencylof -the hydrogenation process nd to avoid reprccessing the sLurrying oil stream through the reactor and equipment trai.n, effective simultaneous conversion of the coal and spe-cial oiL feedstock components has been generally considered impracti.cal. Such consideratiGn was due in part to the dlf--erent reaction condltions believed necessary for the effec-~ive converslon of the separate components, and also due to the expectecl reLative incompatibility of the product Li~uids, particularLy those comprising fu]l range distillates ~,oiling up to about 1000F. Also, in coal liquefaction processes, it has been thought necessary to achieve solvent oil balance, i.e., to produce at least sufficient solvent oil -to slurry the coal feed to the reactor and thus enhance its liquefaction and hydrogenation reaction to produce desirable hydrocarbon liquid products.
~ owever, it has now been unexpectedly found -that certain petroleum-derived oils, such as clarified aromatic decant oil recovered from catalytic cracking of petroleum crude, can be ~19 5;~i3 5i advar.tac20usly used as a solvent or slurryina oil for the par.iculate coal feed in a coal hydroaenation process The une~ected bene.its of this process seauence is that a low cost ~etroleum derivative which is difficult to utilize, can be suc^ess'ullv used in the".~-Coal'~rccess to slurry t'ne coal feed anc also to enhance the production of naphtha an~ liaht distillate fractions by selective hydroconversion of the coal and the decant oil feed.
SUMMARY OF INVENTION
_ _ _ _ _ _ This invention provides a coal catalytic hydrogenation process for pr~ducing desirable hydrocarbon liquid and gas products, in whlch a ~etroleum-derived liquid fraction is advantageously used for at ~east part of the slurrying oil for the particulate coal feed to the catalytic reaction zone.
More specifically~ the invention comprises a process ~or the simultaneous catalytic hydrogenation of coal and a petroleum-derived oil component of a fluid coal-oil feed blen~, wherein both the coal and petroleum-derived oil components of the feedstream are converted to hydrocarbon liquid ~roducts and gases, and provides an increased Fercentage yield of the O
desira~le C4- 650F naphtha and disti.llate oil fractions product. Xn the invention, a fluid feedstock blend comprising particulate coal and a petroleum derived oil having a normal boiling range of about 300-lOO~F~ such as aromatic ~ecant oil obtained from a petroleum catalytic cracking step is contacted with hydrogen preferably in an ebullated bed of commer~ial hydrogenation catalyst particl`es, in general accordance with.conventional ebullated bed reactor ' . .
* Trademark ~ ~ 9 ~;i 6 3 Si operation, as descrihed in U.S. Patent Re. 25,770, Although the petroleum-derived oil fract.ion used has less desirable coal solv~nt characteristics compared to coal-derlved oils 7 it unexpectedly facilitates the coal hydrogenation reaction and increases the percentage yield of the naphtha and light distillate product fractions.
DESCRIPTION OF INVEMTION
In the invention, finely divided coal, which may suitably , .
comprise bitu~lnous, sub-bituminous or ]ignite-type coal, is admixed with sufficient petroleum-derived oil comprising at least about 5~ up to 100~ by weight of oil normally boiling in range of about 300-1000F to provide a fluid coal/oil blend. Hydroconversion of the coal and oil components of this blend is achieved by feeding the heated blend with hydrogen upwardly through a reaction zone, wherein it is contacted by an ebullated bed of commercial hydrogenation catalyst particles. In general, -the catalyst used may be any ~a~alyst useful for the hydrogenation of coal, and may comprise metal oxides selected from the group of cobalt, molybdenum, nickel, iron, tin, and tungsten, deposited on a base support com~rising alumina, magnesia, silica, or combinations thereof. Such particles are in the form of beads, extxudates or pellets, and have a particle size of 0.050-0.200 inch, a bulk density of 30-50 lb/ft3~ and total pore volume when fresh of 0.50 ~0,90 cc/gm.
The reaction zone conditions are maintained- at a tem-peràture within the range of about 750~to 900F, and pre-erably about 780~ to 8~0F, and at a hydrogen paxtial . , : . . .:
pressure of about 1000 to 5000 psia, and prefera'Dly about 1~00 to.4000 psig. The percentage of unconverted coal and ash solids in the reaction zone can be controlled within a desired ranye of 10 - 25 ~ ~ either by operating in a once-t~rough mode with sufficient slurryino oil, or by recycling to the reaction zone a portion of separator hottoms liquid from which solids have been partially removed.
The coal feed rate or space velocity for the coal/oil bLend contacting the catalyst particles ls maintained within the range of about 5 - 60 pounds coal/hr/ft3 reaction zone, a~nd preferably at L0 - 40 lb/hr/ft3. While some conversion of both the coal and oil components may occur at space velocities of the coal/oil blend above this specified range, it has been found that in order to achieve the unexpected improvement in the oil and coal conversion rates obtainable by the process of this .invention, space velocities below about ~0, and preferably within the range of about 10 to about 40 pounds of coal per hour per cubic foot of reactor voLume should be maintained. The reactor effluent materia.L
is wi.thdrawn overhead and passed to subsequent separation and ~ractlonation processing steps as desired.
In general, the proportions of petroleum-derived sl.urrying oil to coal-derived oil used in the feedstock blend are determined by product objectives and petroleurn-derived slurrying oil availability. Broadly, at least sufficient total slurrying oil is admixed with the particulate coal to provide a sufficiently fluid blend to permit pumplng the blend through the preheater and reaction system and to provide acequate f].uidization of the catalyst bed.
Typically, oil to coal weight ratios of from about 1.0 to 4 pounds of oil per pound- of coal are employed; preferably, : : 5.
E 3~;
from about 1.3 to about 3 pounds of oiL per pound-of coal are used to maximize 'nydroconversion efficiency for both the coal and oil components.
The petroleum-derived oil useful in this invention is preferably an aromatic distillate bottoms oil recovered. from a fluidized catalytic cracking. unit (FCC) of a petroleum refinery, and which after catalyst particles have been removed is also calLed clarified decant oil. Such oils usually have a broad normal hoiling range of 300-1000F and gravity of 3-6 API. Analysis of a typical suitable clarified decant oil is provided in Table 1 below.
Such use of clari~ied decant slurrying oi1 produces an increased percentage of naphtha and light distillate product ractions. Thus, rather than operating the coal hydrogena-tion process to produce sufficient coal-derived solvent or slurryiny oil to obtain solvent balance for slurrying the coal, we have urlexpectedly fo~nd that such clarified flecant olL from a petrole~m refining operation can be advan-tageously used as a slurrying oll stream for the coal fee-l, ~nd the process operating conditions and catalyst replace-ment r~te can be adjusted to maximize the desired production o naphtha and light oil (180 - 650F boiling range~
products As a percentage of total slurrying oil needed, usLng bFtween about 10% and 80~ petroleum-derived solvent with the balance being coal-derived oil is desirable.
In an alternate and preferred embodiment of this inven-tion, selected heavy coal-derived liqui~ fractions are.
. .
recycled for blending with the finely divided coal and the petroleum-derived decant oil. In this embodiment suf~icient . .coa.l-derived oil, preferably compr-isiny residuum-containing ~3.~5~35i oil having nor~al boilina temperature range of 700 975'F, is recycled to ~he coal blen~ing step to provide a total oil to coal ratio in the feedstock blend of at least about 1.3 pcunds of oil per pound of coal, and preferably a ratio of from aDout 1.5 to 3 pounds of total oil per pound of coal.
In practice, this embodiment of the nventicn can be employed when, for example, adequate petroleum-derived decant oil is available an~ it is desired to minimi~e the percenta~e of light coal-derived oil fraction used for slurrying ~he coal so as to increase the yielAs of lower-boiling hydrocarbon liquid products. In this event, an increased petroleum-derived oil fraction can be used, such as comprising20-80 W ~ of the total slurrying oil.. However, when insufficient ligh~ pçtroleum~derived slurrylng oil is available, a greater percentage of higher boilina coal-derived oil is recycled ~or use in slurrying the coal feed, to provide a welght ratio of slurrying oil to coal in the feedstock blend of at least about 1.5, ~/hich represents a total feed blend composition of about 40% coal and about 60%
o~l by weight. Also, if desired, some of the naphtha rac~ion product can be returned to ~he catal~tic cracking step to produce gasoline.
BRIFF DESCRIPTION OF THE DRAWIMGS
Figure 1 is a schematic ~iagram showing one embodiment o~
the process of this invention, illustrating the principal steps of the process when using a petroleum-derived oil for slurrying ~he coal feed.
Figure 2 shows an alternate embodiment of the process, illustratina the principal sters of the process when .
56~
slurrying the coal with a mixture of petroleum-derived decant oil and recycled heavy coal-derived oil.
Fisure 3 is a araph showing the general relationship between decant slurrying oil used and yields of naphtha and light distillate fraction products.
DESCRIPTION OF PREFERRED EM~ODIMENTS
As shown in Figure 1, bituminous coal such as Illinois No. 6, Kentucky No. 11, or Wyodak which has been ground to a parti.cle size smaller than about 50 mesh (U.S. Sieve Series) is provided at ].0 and passed to a slurry mixing tank 12. The cloal is blended with a petroleum-derived oil 14 from refinery 62, usually comprising clarifled decant oil obtained from a petroleum refinery fluidized catalytic cracking step and having a normal boiling range of about 350-900F. Such blending is in a weight ratio of oil to coal at least sufficient to provide a pumpable slurry mixture, and usually is in a weight ratio range of oil to coa]. hetween about 1.1 to abollt 4Ø
The coal-oil blend frorn s].urry rnixing tank 12 is pressurized by a pump 16, which pumps the hlend thro~gh con-duit 17 together w.ith hydrogen at ].8 and through heater 19 to an ebullated hed reactor 20 containing a bed 20a of par-ticuLate commercial hydrogenation catalyst. The coal-oil blend and hydrogen pass through flow distributor 21 and upwardly through the catalyst bed at sufficient velocity to expand the bed. The catalyst 20a, which may suitably comprise particles such as .060 diameter extrudates of nickel molybdate or cobalt molybdate on alumina or similar suppor~
material is e~panded by at least about 20~ and not over about 150% of its settled height by ~he upflowing fluids, and is '~ept in constant random motion during reaction by the u2ward velocity of the coal-oil blend and hydrogen gas.
The coal-oil blend is passed upwardly throuah the reactor 20 in contact with the catalyst at a space velocity of about 5 to 60 pounds of coal/hour/cubic foot, and preferably from about 10 to 40 pounds of coal/hour/cubic foot of reactor volume. Reaction conditions are preferably within the range of 780-870F temperature and 1200-4000 hydrogen partial pressura. Reactor li~uid is recycled through downcomer conduit 22, recycle pump 22a and upward through distributor 21 to mainfain sufficient upward llquid veLocity to expand the bed and maintain the catalyst in random motion in the liquid to assure intimate contact and complete reaction.
Fresh catalyst is usually added to the reactor at connection 23 as needed and used catalyst removed at 24.
In the reactor 20, simultaneous hydrogenation and con-version of the coal and slurrying oil occurs with consumption ~f ~ome hydroqen. Also, because the petroleurn-derived oil contains aromatLc compounds and has significant solvent propertles affecting the coal, the hydrogenation reactions may be achieved at a somewhat lower reaction temperature than would otherwise be necessary.
From the reactor 20 effluent stream 25 is passed to hot phase separator 26. The resulting gas portion stream 27 is passed to hydrogen purification step 30, from which recovered hydrogen 31 is recycled to the reactor along with make-up hydrogen at 3~a as needed.
.
Liquid stream 28 is withdrawn, pressure-reduced at 29 and passed to liquid--solids se~aration system 32, which can 5~;~,5 - `_omprise hydroclone or a solvent preclpitation system.
Overflow stream 33 containina reduced concentration of solids is passed to fractionation system 34, wherein the liquid is fractionated into product streams comprising gas naphtha, liaht and middle range distillatesj and heavy residuum boilina range oils containina unconverted coal and ash.
Specifically, streams from the 'ractionator 34 are withdrawn as product gas at 35, C4-400 naphtha fraction at 36, distillate liquid at 37, and a heavy fuel oil at 38. A por-tion of bot~oms stream 38 from fractionator 34 can be recycled to the reactor 20 via conduits 39 to help control the percen-tage of unconverted coal and'ash solids in the reactor within, a de~ired ran~e, typic,ally about 10 ~o 25 W %.
From separation step 32 underflow stream 39 is passed to vacuum distillation at 40. Vacuum overhead stream 41 is combined with stream 38 and vacuum bottoms material at 41a can be used for coking7 or as feed material for hydrogen production.
With reference to Figure 2, al alternate process embodi-,ment is shown which ~s slmilar to Figure 1 but utilizes bothpetro].eum-derived decant oil and a heavy coal-derived recycle oi..l for slurrying the coal feed. Sirnilarly as described above, coal 10 and decant oil 14a obtained from fluidized catalytic cracker 64 are blended in the mixing zone 12 pressurized by pump 16, and passed to the reactor 20 along with hydrogen provided at 18. Similarly as for the Figure 1 embodiment, the coal-oil blend undergoes nydrogenation reactions while passing upwardly through the ehullated bed of catalyst particles. ReIatively simultaneous conversion of the coal, petroleum~derived decant slurry oil and heavy coal-derived oil occurs with the consumption of some hydrogen to : produce lower boiling hydrocarbon liquids and gas.
: . . ~ - . . . - . .
3~i . From the reactor 20 effluent strea~ is removed via con-duit 25 and passed to hot phase separator 26. Resulting gas stream 47 is passed to hydrogen recovery system 30, from which hydrogen s-tream 31 ls recycled to the reactor 20 along with fresh make-up hydrogen at 31a as needed From separator 26 the liquid portion is withdrawn as stream 28 and passed to low pressure separator 42. The bot-toms liquid stream 43 goes to a liquid-sollds sepa.ration ~tep 44,. whi.ch preferably co~pri.ses mul.~iple hydrcclone~. A
portion 45 of the overflow stream containing reduced solids concentration is returned to coal slurrying zone 12, and the remainder 47 is passed to fractionation system 54.
Underflow stream 48 from solids separation step 44 is passed to vacuum distillation at 60, from which a bottoms material stream is removed at 61.
From the low pressure separator 42, the overhead liquid is condùcted via a.conduit 53 to fractionation system 54 or ~ractionation into gas stream 55, naphtha fraction strearn S~, and light or heavy distillate oil products 57. Bottoms màterial 58 is withdrawn from the fractionator 54 and can be recycled to the slurry tank 12 via conduit 59 as required.
In this Figure 2 embodiment of the invention, a portion 56a of naphtha fraction 56 from the fractionator 54 is passed -to re~inery catalytic cracking step 64 to increase .. . . .
the production of gasoline at 66- Also, a selected portion of the product distillate from -the fractionator 54 can be recycled to the slurry mixing zone 12 via conduit 59, to pro~ide a portion of-the slurrying liquid for the coal. The selected recycled oil portion, which preferably cornprises residuum-containing oil, is recycled as required to provide ~ , . . . . . .
i3S
a total oil to coal weight ratio within the slurrying tank 12 of about 1.0 to 4, and preferably about 1.3 to 3.
This invention will be furt'ner described by reference to the followin~ examples, which should not be regarded as restricting its scope.
CoaL hydrogenation operations ~ere conducted in a bench . - - , ~ . . . .
scale unit using Illinois No~ 6 coal mixed with slurrying oil containing various percentages of .clarified petroleum~
derived decant oil recovered from a petroleum catalytic cracker unit. The slurrying oil/coal weight ratio used was about 2.~. A typical analysis for the Illinois No 6 coal feecl is provlded in Table 1, and Table 2 provides typical properties of the clarified decant oil used.
TYPICAL AMALYSIS OF ILLINOIS NO. 6 COAL
Moisture, ~7 ~ 1.60 Ultimate Ana]ysis, W ~ (Dry 3asis) Carbon 67.25 Hydrogen 4.~1 Nitrogen 1.02 Sulfur 4.85 Ash 9 93 Oxygen (Difference) 12.14 ,, , . . . :
TYPICAL PROPERTIES OF CLARIFIED DECANT OIL
Ash <0.1%
Conradson Carbon 6.5~
Ramsbottom Carbon 5.33%
Viscosity, SSU @ 100F 1123 Viscosity, SSU @ 210F 59 Hydrogen type analy~is by high resolution ~MR
% aromatic H2 - 25 aliphatic H~ 75 Compound types by Mass Spectometer analysis . . .. .aromatic, V ~ . ~7 8 saturates V % 2.2 Gravity, API 4.4 5.0 5 3 5.1 True Boiling Point, F ! !
I~P 410 332 364 407 10~ 608 556 571 589 30~ 688 672 685 692 50% 760 756 768 766 70% 830 832 ~50 843 90~ 932 941 969 955 Carbon, W ~ 89.398a . 9089.39 89.72 Hydrogen, W ~ 8.68~.37 8.50 8.36 Nitrogen, W ~ -- 0.32 0.37 0.33 Sulfur, W % 1.391.04 1.05 1.06 The oiL-coal slurry and hydrogen were preheated and fed into the lower end of an ebull.ated bed cataly-tic reactor about 0.8 inch inside diameter by 10 fee-t ~ong. '~e cata-}yst us.ed was a commercial arade containing cobalt-molybdenum on alumina material. The reaction conditions maintained for a straight-through operation without use of recycle oll to the reactor and the average resul~s achieved are provided in Table 3 beLow.
. .. . . :
~ 3~;
BE~CH SCALE H-COAL OPERATIONS
USI~G PETROLEUM DECANT GIL FOR SLUPRYING COAL
Run .~o. 1 2 3 a Slurrying Oil Used, W %
Decant 25 12 8 2 Coal-Derived 75 88 92 98 Weight ~atio Slurrying Oil/Coal 2 2 2 2 Reactor Temperature, F 840850850 850 H2 Partial Pressure, psig 18401850 1842 1835 Coal Space Veloci-ty, lb/hr/ft3 31.231.2 31.2 31.2 Catalys~ Age, , ilbs coal/lbs cataLyst........ 580. .700 .~890. 10Q0.
Product Yields, lb/100 lb coal Cl-C3 hydrocarbon gas 8 2 8.99.5 12.9 C4-400F naphtha 28~1 25 822.~ 15.5 40q-650F light distillate 18.416.9 14.5 16.1 65d-975F fuel oil 10.9 10.08.6 12.3 975~F+ residuum 8.4 12.620.8 18.6 Unconverted coal 4.8 4.23.5 4.1 Ash 10.5 10.510.5 10.5 Vent Gases and Water10.7 10-110.4 10.0 H2 Const~ption 6.5 5.66.0 _ 5.8 'r~al~ 106.5 105.6 106.0 105.8 The yield results for light oil fractions are also shown plotted in Figure 3 vs. weight percent decant oil in the sLurrying oil, It is noted that resu~ts of these runs showed a definite trend for increased yields of -the ~esirabLe C4-400F and C4-650F product fractiorls with increasing percentage decant oil used in the slurrying oil.
. - . ,, ~ : . . 1'1 , 35i The percentage of C4-650F naphtha and distillate oil fraction produced was increased by more than wou].d have been e~pected due to the a~lded petroleum decant oil alone, thus indicating that an unexpected synergistic effect occurred due to the reactions of the aromati.c decant oil in the catalytic reaction zone to hydroconvert more of the coal residuum oil to naphtha and light distillate product fractions.
I . . . . . ........ . . .......................... . ..
Addltional larger pilot plant scale coal hydrogenation operations were conducted using Illinois No. 6 coal mixed with a slurrying oil containing an increased percentage of petroleum-derived clarified decant oil reco.vered from a petroleum refinery catalytic cracker uni-t. The oil/coaL
slurry and hydrogen were preheated to about 650F and fed into the lower end of an S foot inside diameter ebullated hed catalytic reactor operated in a recycle operational mode, i.e. with some recyclQ of heavy hydrocarbon liquid fraction to the coal slurrying step. The catalyst us~d was the same specification cobalt-molybdenum on alumina support material used in Example 1.
Table 5 shows a comparison of the feedstock slurries and reaction conditions used and resultant product yields obtained in the-hydrogenation,and conversion of the ~lend of Il.linois No. 6 coal and petroleum-derived decant oil reco vered from a catalytic crac~er unit.
' ~ , . . . . ~ . - . .
H-COAL PROCESS OPERATIONS
USI~G PETROLE~M DEC~NT OIL FOR SL~RRYI G COAL
Coal-Derived Coal-~erived Oil plus _ Oil Decant Oil Slurrying Oil Used, W %
Decant 0 44 Coal-Derived 100 56 Weight Ratio ~Slurrying Oil/Coal 1.65 1.65 Decant Oil to Total Feed, W ~ 0 27%
Reaction Temperature, F840 840 H2 Partial Pressure, psig1600 1600 Coal Space.Velocity, . .. ..
lb/hr/ft3 reactor 31.2 31.2 CataLyst Age, lbs coal/lb catalyst 1000 8~0-1000 Product Yields, lb/100 lb coall Cl-C3 gas - l l 11.2 11.2 C4-400F naphtha 18.4 23.1 400-650F light distillate 13.5 15.3 650-975F heavy distillate 7.0 8.4 975F+ residuum oil 26.7 21.4 Unconverted coal 3.5 3.5 Ash 11.2 11.2 Vent Gases and Water8.5 5.. 9 Hydrogen Consumption5.3 5.1 TotaLs 105.3 105.1 Based on the results shown in Table S, it is seen that und~r very similar reaction condit.ions significant].y mor.e oE
t~e desirable C4-400F naphtha and 400-650F light distillate ractions were produced w~en petroleum-derived decant oil was used for slurrying the coal than when coal~
derived slurrying oil was used alone. Furthermore, it is noted that `all yields and. comb.inations of yields were increased when using about 44 W % decant oil in the coal slurrying oil as compared to using all coal-derived slurrying oil- The yield resu~ts are shown plotted in ~, . . . ~ .
Figure 3, .and -confirm the- trend o lncreased yie]ds of C4-~50F ~roduct oil fraction with increasing percentage of decant oil used in the slurrying oil.
; .. ~.. . ... -3~
.~
.~lthough we have disclosed certain preferred embodiments of our invention, it is recognized that various modifica-tions can be made thereto, all within the spirit and scope of the invention which is defined by the following claims.
. . .
.
- . . ,. , ~ . . .
-USI~G PETROLEUM-DERIVED SLURRYING OIL
~ACXGRo~'ND CF INVENTION
Field of Invention:
. . . _ This invention pertains to an improved process for coal hydrogenation to produce hydrocarbon liquids and gases and p~rtains particularly to a coal liquefaction and catalytic hydrogerlation process which utilizes a petroleum-derived aro-matic oil for slurrying the coal and increasing the yield of naphtha and other light hydrocarbon liquid product fractions.
Descri~tion of Prior Art Numerous methods have been proposed in the prior art for eec,ting the h~ydroconversion of coal into hydrocarbon liquid and gas products. Present commercial conversion methods con-~erltionall.y comprise subjecting a coal-oil sl'urry to cataL~tic hydrogenation at elevated temperatures and pressure c~orl~itions to produce a coal-derived synthetic oil and distillate products and gas. Typically, these rnethods utilize an ebullated bed catalytic reaction technique whereln a strea~ of the coal-oil slurry is admixed with gaseous hydrogen and passed upwardly through an ~bullated hed reactor containing a bed of particulate hydrogenation catalyst, thereby providlng for liquefaction and hydrogenation of the coal. ~xamples of such prior art caal conversion processes are those described in U. S. Patent Nos~ 3,519~555 to Keith et al, 3,540~995 to Wolk' et al, 3 791,957 to Wolk, 3,607,719 ~@~
3~i ```
to Johnson et al, 3,594,305 to ~ir~, 3,586,621 to Pitch,ord, et al 3,755,13~ to Schuman, and 4,054,504 to Chervenak et al.
Such techniaues, while aenerally effec-ti~e in convertino coal into desired liquid products, have characteristically been limited to conversion of the coal, while the oil pro-viding the slurrying liquid needed for preparing and handling the coal feed to -the pressurized reactor has remained substantially unconverted throughout the hydroyenation process. While the desirahility of effecting simultaneous conversion of both coal and heavy crude or residuum oll feed components in these ebullated bed procedures has been recognized, for example, to increase the conversion effi-ciencylof -the hydrogenation process nd to avoid reprccessing the sLurrying oil stream through the reactor and equipment trai.n, effective simultaneous conversion of the coal and spe-cial oiL feedstock components has been generally considered impracti.cal. Such consideratiGn was due in part to the dlf--erent reaction condltions believed necessary for the effec-~ive converslon of the separate components, and also due to the expectecl reLative incompatibility of the product Li~uids, particularLy those comprising fu]l range distillates ~,oiling up to about 1000F. Also, in coal liquefaction processes, it has been thought necessary to achieve solvent oil balance, i.e., to produce at least sufficient solvent oil -to slurry the coal feed to the reactor and thus enhance its liquefaction and hydrogenation reaction to produce desirable hydrocarbon liquid products.
~ owever, it has now been unexpectedly found -that certain petroleum-derived oils, such as clarified aromatic decant oil recovered from catalytic cracking of petroleum crude, can be ~19 5;~i3 5i advar.tac20usly used as a solvent or slurryina oil for the par.iculate coal feed in a coal hydroaenation process The une~ected bene.its of this process seauence is that a low cost ~etroleum derivative which is difficult to utilize, can be suc^ess'ullv used in the".~-Coal'~rccess to slurry t'ne coal feed anc also to enhance the production of naphtha an~ liaht distillate fractions by selective hydroconversion of the coal and the decant oil feed.
SUMMARY OF INVENTION
_ _ _ _ _ _ This invention provides a coal catalytic hydrogenation process for pr~ducing desirable hydrocarbon liquid and gas products, in whlch a ~etroleum-derived liquid fraction is advantageously used for at ~east part of the slurrying oil for the particulate coal feed to the catalytic reaction zone.
More specifically~ the invention comprises a process ~or the simultaneous catalytic hydrogenation of coal and a petroleum-derived oil component of a fluid coal-oil feed blen~, wherein both the coal and petroleum-derived oil components of the feedstream are converted to hydrocarbon liquid ~roducts and gases, and provides an increased Fercentage yield of the O
desira~le C4- 650F naphtha and disti.llate oil fractions product. Xn the invention, a fluid feedstock blend comprising particulate coal and a petroleum derived oil having a normal boiling range of about 300-lOO~F~ such as aromatic ~ecant oil obtained from a petroleum catalytic cracking step is contacted with hydrogen preferably in an ebullated bed of commer~ial hydrogenation catalyst particl`es, in general accordance with.conventional ebullated bed reactor ' . .
* Trademark ~ ~ 9 ~;i 6 3 Si operation, as descrihed in U.S. Patent Re. 25,770, Although the petroleum-derived oil fract.ion used has less desirable coal solv~nt characteristics compared to coal-derlved oils 7 it unexpectedly facilitates the coal hydrogenation reaction and increases the percentage yield of the naphtha and light distillate product fractions.
DESCRIPTION OF INVEMTION
In the invention, finely divided coal, which may suitably , .
comprise bitu~lnous, sub-bituminous or ]ignite-type coal, is admixed with sufficient petroleum-derived oil comprising at least about 5~ up to 100~ by weight of oil normally boiling in range of about 300-1000F to provide a fluid coal/oil blend. Hydroconversion of the coal and oil components of this blend is achieved by feeding the heated blend with hydrogen upwardly through a reaction zone, wherein it is contacted by an ebullated bed of commercial hydrogenation catalyst particles. In general, -the catalyst used may be any ~a~alyst useful for the hydrogenation of coal, and may comprise metal oxides selected from the group of cobalt, molybdenum, nickel, iron, tin, and tungsten, deposited on a base support com~rising alumina, magnesia, silica, or combinations thereof. Such particles are in the form of beads, extxudates or pellets, and have a particle size of 0.050-0.200 inch, a bulk density of 30-50 lb/ft3~ and total pore volume when fresh of 0.50 ~0,90 cc/gm.
The reaction zone conditions are maintained- at a tem-peràture within the range of about 750~to 900F, and pre-erably about 780~ to 8~0F, and at a hydrogen paxtial . , : . . .:
pressure of about 1000 to 5000 psia, and prefera'Dly about 1~00 to.4000 psig. The percentage of unconverted coal and ash solids in the reaction zone can be controlled within a desired ranye of 10 - 25 ~ ~ either by operating in a once-t~rough mode with sufficient slurryino oil, or by recycling to the reaction zone a portion of separator hottoms liquid from which solids have been partially removed.
The coal feed rate or space velocity for the coal/oil bLend contacting the catalyst particles ls maintained within the range of about 5 - 60 pounds coal/hr/ft3 reaction zone, a~nd preferably at L0 - 40 lb/hr/ft3. While some conversion of both the coal and oil components may occur at space velocities of the coal/oil blend above this specified range, it has been found that in order to achieve the unexpected improvement in the oil and coal conversion rates obtainable by the process of this .invention, space velocities below about ~0, and preferably within the range of about 10 to about 40 pounds of coal per hour per cubic foot of reactor voLume should be maintained. The reactor effluent materia.L
is wi.thdrawn overhead and passed to subsequent separation and ~ractlonation processing steps as desired.
In general, the proportions of petroleum-derived sl.urrying oil to coal-derived oil used in the feedstock blend are determined by product objectives and petroleurn-derived slurrying oil availability. Broadly, at least sufficient total slurrying oil is admixed with the particulate coal to provide a sufficiently fluid blend to permit pumplng the blend through the preheater and reaction system and to provide acequate f].uidization of the catalyst bed.
Typically, oil to coal weight ratios of from about 1.0 to 4 pounds of oil per pound- of coal are employed; preferably, : : 5.
E 3~;
from about 1.3 to about 3 pounds of oiL per pound-of coal are used to maximize 'nydroconversion efficiency for both the coal and oil components.
The petroleum-derived oil useful in this invention is preferably an aromatic distillate bottoms oil recovered. from a fluidized catalytic cracking. unit (FCC) of a petroleum refinery, and which after catalyst particles have been removed is also calLed clarified decant oil. Such oils usually have a broad normal hoiling range of 300-1000F and gravity of 3-6 API. Analysis of a typical suitable clarified decant oil is provided in Table 1 below.
Such use of clari~ied decant slurrying oi1 produces an increased percentage of naphtha and light distillate product ractions. Thus, rather than operating the coal hydrogena-tion process to produce sufficient coal-derived solvent or slurryiny oil to obtain solvent balance for slurrying the coal, we have urlexpectedly fo~nd that such clarified flecant olL from a petrole~m refining operation can be advan-tageously used as a slurrying oll stream for the coal fee-l, ~nd the process operating conditions and catalyst replace-ment r~te can be adjusted to maximize the desired production o naphtha and light oil (180 - 650F boiling range~
products As a percentage of total slurrying oil needed, usLng bFtween about 10% and 80~ petroleum-derived solvent with the balance being coal-derived oil is desirable.
In an alternate and preferred embodiment of this inven-tion, selected heavy coal-derived liqui~ fractions are.
. .
recycled for blending with the finely divided coal and the petroleum-derived decant oil. In this embodiment suf~icient . .coa.l-derived oil, preferably compr-isiny residuum-containing ~3.~5~35i oil having nor~al boilina temperature range of 700 975'F, is recycled to ~he coal blen~ing step to provide a total oil to coal ratio in the feedstock blend of at least about 1.3 pcunds of oil per pound of coal, and preferably a ratio of from aDout 1.5 to 3 pounds of total oil per pound of coal.
In practice, this embodiment of the nventicn can be employed when, for example, adequate petroleum-derived decant oil is available an~ it is desired to minimi~e the percenta~e of light coal-derived oil fraction used for slurrying ~he coal so as to increase the yielAs of lower-boiling hydrocarbon liquid products. In this event, an increased petroleum-derived oil fraction can be used, such as comprising20-80 W ~ of the total slurrying oil.. However, when insufficient ligh~ pçtroleum~derived slurrylng oil is available, a greater percentage of higher boilina coal-derived oil is recycled ~or use in slurrying the coal feed, to provide a welght ratio of slurrying oil to coal in the feedstock blend of at least about 1.5, ~/hich represents a total feed blend composition of about 40% coal and about 60%
o~l by weight. Also, if desired, some of the naphtha rac~ion product can be returned to ~he catal~tic cracking step to produce gasoline.
BRIFF DESCRIPTION OF THE DRAWIMGS
Figure 1 is a schematic ~iagram showing one embodiment o~
the process of this invention, illustrating the principal steps of the process when using a petroleum-derived oil for slurrying ~he coal feed.
Figure 2 shows an alternate embodiment of the process, illustratina the principal sters of the process when .
56~
slurrying the coal with a mixture of petroleum-derived decant oil and recycled heavy coal-derived oil.
Fisure 3 is a araph showing the general relationship between decant slurrying oil used and yields of naphtha and light distillate fraction products.
DESCRIPTION OF PREFERRED EM~ODIMENTS
As shown in Figure 1, bituminous coal such as Illinois No. 6, Kentucky No. 11, or Wyodak which has been ground to a parti.cle size smaller than about 50 mesh (U.S. Sieve Series) is provided at ].0 and passed to a slurry mixing tank 12. The cloal is blended with a petroleum-derived oil 14 from refinery 62, usually comprising clarifled decant oil obtained from a petroleum refinery fluidized catalytic cracking step and having a normal boiling range of about 350-900F. Such blending is in a weight ratio of oil to coal at least sufficient to provide a pumpable slurry mixture, and usually is in a weight ratio range of oil to coa]. hetween about 1.1 to abollt 4Ø
The coal-oil blend frorn s].urry rnixing tank 12 is pressurized by a pump 16, which pumps the hlend thro~gh con-duit 17 together w.ith hydrogen at ].8 and through heater 19 to an ebullated hed reactor 20 containing a bed 20a of par-ticuLate commercial hydrogenation catalyst. The coal-oil blend and hydrogen pass through flow distributor 21 and upwardly through the catalyst bed at sufficient velocity to expand the bed. The catalyst 20a, which may suitably comprise particles such as .060 diameter extrudates of nickel molybdate or cobalt molybdate on alumina or similar suppor~
material is e~panded by at least about 20~ and not over about 150% of its settled height by ~he upflowing fluids, and is '~ept in constant random motion during reaction by the u2ward velocity of the coal-oil blend and hydrogen gas.
The coal-oil blend is passed upwardly throuah the reactor 20 in contact with the catalyst at a space velocity of about 5 to 60 pounds of coal/hour/cubic foot, and preferably from about 10 to 40 pounds of coal/hour/cubic foot of reactor volume. Reaction conditions are preferably within the range of 780-870F temperature and 1200-4000 hydrogen partial pressura. Reactor li~uid is recycled through downcomer conduit 22, recycle pump 22a and upward through distributor 21 to mainfain sufficient upward llquid veLocity to expand the bed and maintain the catalyst in random motion in the liquid to assure intimate contact and complete reaction.
Fresh catalyst is usually added to the reactor at connection 23 as needed and used catalyst removed at 24.
In the reactor 20, simultaneous hydrogenation and con-version of the coal and slurrying oil occurs with consumption ~f ~ome hydroqen. Also, because the petroleurn-derived oil contains aromatLc compounds and has significant solvent propertles affecting the coal, the hydrogenation reactions may be achieved at a somewhat lower reaction temperature than would otherwise be necessary.
From the reactor 20 effluent stream 25 is passed to hot phase separator 26. The resulting gas portion stream 27 is passed to hydrogen purification step 30, from which recovered hydrogen 31 is recycled to the reactor along with make-up hydrogen at 3~a as needed.
.
Liquid stream 28 is withdrawn, pressure-reduced at 29 and passed to liquid--solids se~aration system 32, which can 5~;~,5 - `_omprise hydroclone or a solvent preclpitation system.
Overflow stream 33 containina reduced concentration of solids is passed to fractionation system 34, wherein the liquid is fractionated into product streams comprising gas naphtha, liaht and middle range distillatesj and heavy residuum boilina range oils containina unconverted coal and ash.
Specifically, streams from the 'ractionator 34 are withdrawn as product gas at 35, C4-400 naphtha fraction at 36, distillate liquid at 37, and a heavy fuel oil at 38. A por-tion of bot~oms stream 38 from fractionator 34 can be recycled to the reactor 20 via conduits 39 to help control the percen-tage of unconverted coal and'ash solids in the reactor within, a de~ired ran~e, typic,ally about 10 ~o 25 W %.
From separation step 32 underflow stream 39 is passed to vacuum distillation at 40. Vacuum overhead stream 41 is combined with stream 38 and vacuum bottoms material at 41a can be used for coking7 or as feed material for hydrogen production.
With reference to Figure 2, al alternate process embodi-,ment is shown which ~s slmilar to Figure 1 but utilizes bothpetro].eum-derived decant oil and a heavy coal-derived recycle oi..l for slurrying the coal feed. Sirnilarly as described above, coal 10 and decant oil 14a obtained from fluidized catalytic cracker 64 are blended in the mixing zone 12 pressurized by pump 16, and passed to the reactor 20 along with hydrogen provided at 18. Similarly as for the Figure 1 embodiment, the coal-oil blend undergoes nydrogenation reactions while passing upwardly through the ehullated bed of catalyst particles. ReIatively simultaneous conversion of the coal, petroleum~derived decant slurry oil and heavy coal-derived oil occurs with the consumption of some hydrogen to : produce lower boiling hydrocarbon liquids and gas.
: . . ~ - . . . - . .
3~i . From the reactor 20 effluent strea~ is removed via con-duit 25 and passed to hot phase separator 26. Resulting gas stream 47 is passed to hydrogen recovery system 30, from which hydrogen s-tream 31 ls recycled to the reactor 20 along with fresh make-up hydrogen at 31a as needed From separator 26 the liquid portion is withdrawn as stream 28 and passed to low pressure separator 42. The bot-toms liquid stream 43 goes to a liquid-sollds sepa.ration ~tep 44,. whi.ch preferably co~pri.ses mul.~iple hydrcclone~. A
portion 45 of the overflow stream containing reduced solids concentration is returned to coal slurrying zone 12, and the remainder 47 is passed to fractionation system 54.
Underflow stream 48 from solids separation step 44 is passed to vacuum distillation at 60, from which a bottoms material stream is removed at 61.
From the low pressure separator 42, the overhead liquid is condùcted via a.conduit 53 to fractionation system 54 or ~ractionation into gas stream 55, naphtha fraction strearn S~, and light or heavy distillate oil products 57. Bottoms màterial 58 is withdrawn from the fractionator 54 and can be recycled to the slurry tank 12 via conduit 59 as required.
In this Figure 2 embodiment of the invention, a portion 56a of naphtha fraction 56 from the fractionator 54 is passed -to re~inery catalytic cracking step 64 to increase .. . . .
the production of gasoline at 66- Also, a selected portion of the product distillate from -the fractionator 54 can be recycled to the slurry mixing zone 12 via conduit 59, to pro~ide a portion of-the slurrying liquid for the coal. The selected recycled oil portion, which preferably cornprises residuum-containing oil, is recycled as required to provide ~ , . . . . . .
i3S
a total oil to coal weight ratio within the slurrying tank 12 of about 1.0 to 4, and preferably about 1.3 to 3.
This invention will be furt'ner described by reference to the followin~ examples, which should not be regarded as restricting its scope.
CoaL hydrogenation operations ~ere conducted in a bench . - - , ~ . . . .
scale unit using Illinois No~ 6 coal mixed with slurrying oil containing various percentages of .clarified petroleum~
derived decant oil recovered from a petroleum catalytic cracker unit. The slurrying oil/coal weight ratio used was about 2.~. A typical analysis for the Illinois No 6 coal feecl is provlded in Table 1, and Table 2 provides typical properties of the clarified decant oil used.
TYPICAL AMALYSIS OF ILLINOIS NO. 6 COAL
Moisture, ~7 ~ 1.60 Ultimate Ana]ysis, W ~ (Dry 3asis) Carbon 67.25 Hydrogen 4.~1 Nitrogen 1.02 Sulfur 4.85 Ash 9 93 Oxygen (Difference) 12.14 ,, , . . . :
TYPICAL PROPERTIES OF CLARIFIED DECANT OIL
Ash <0.1%
Conradson Carbon 6.5~
Ramsbottom Carbon 5.33%
Viscosity, SSU @ 100F 1123 Viscosity, SSU @ 210F 59 Hydrogen type analy~is by high resolution ~MR
% aromatic H2 - 25 aliphatic H~ 75 Compound types by Mass Spectometer analysis . . .. .aromatic, V ~ . ~7 8 saturates V % 2.2 Gravity, API 4.4 5.0 5 3 5.1 True Boiling Point, F ! !
I~P 410 332 364 407 10~ 608 556 571 589 30~ 688 672 685 692 50% 760 756 768 766 70% 830 832 ~50 843 90~ 932 941 969 955 Carbon, W ~ 89.398a . 9089.39 89.72 Hydrogen, W ~ 8.68~.37 8.50 8.36 Nitrogen, W ~ -- 0.32 0.37 0.33 Sulfur, W % 1.391.04 1.05 1.06 The oiL-coal slurry and hydrogen were preheated and fed into the lower end of an ebull.ated bed cataly-tic reactor about 0.8 inch inside diameter by 10 fee-t ~ong. '~e cata-}yst us.ed was a commercial arade containing cobalt-molybdenum on alumina material. The reaction conditions maintained for a straight-through operation without use of recycle oll to the reactor and the average resul~s achieved are provided in Table 3 beLow.
. .. . . :
~ 3~;
BE~CH SCALE H-COAL OPERATIONS
USI~G PETROLEUM DECANT GIL FOR SLUPRYING COAL
Run .~o. 1 2 3 a Slurrying Oil Used, W %
Decant 25 12 8 2 Coal-Derived 75 88 92 98 Weight ~atio Slurrying Oil/Coal 2 2 2 2 Reactor Temperature, F 840850850 850 H2 Partial Pressure, psig 18401850 1842 1835 Coal Space Veloci-ty, lb/hr/ft3 31.231.2 31.2 31.2 Catalys~ Age, , ilbs coal/lbs cataLyst........ 580. .700 .~890. 10Q0.
Product Yields, lb/100 lb coal Cl-C3 hydrocarbon gas 8 2 8.99.5 12.9 C4-400F naphtha 28~1 25 822.~ 15.5 40q-650F light distillate 18.416.9 14.5 16.1 65d-975F fuel oil 10.9 10.08.6 12.3 975~F+ residuum 8.4 12.620.8 18.6 Unconverted coal 4.8 4.23.5 4.1 Ash 10.5 10.510.5 10.5 Vent Gases and Water10.7 10-110.4 10.0 H2 Const~ption 6.5 5.66.0 _ 5.8 'r~al~ 106.5 105.6 106.0 105.8 The yield results for light oil fractions are also shown plotted in Figure 3 vs. weight percent decant oil in the sLurrying oil, It is noted that resu~ts of these runs showed a definite trend for increased yields of -the ~esirabLe C4-400F and C4-650F product fractiorls with increasing percentage decant oil used in the slurrying oil.
. - . ,, ~ : . . 1'1 , 35i The percentage of C4-650F naphtha and distillate oil fraction produced was increased by more than wou].d have been e~pected due to the a~lded petroleum decant oil alone, thus indicating that an unexpected synergistic effect occurred due to the reactions of the aromati.c decant oil in the catalytic reaction zone to hydroconvert more of the coal residuum oil to naphtha and light distillate product fractions.
I . . . . . ........ . . .......................... . ..
Addltional larger pilot plant scale coal hydrogenation operations were conducted using Illinois No. 6 coal mixed with a slurrying oil containing an increased percentage of petroleum-derived clarified decant oil reco.vered from a petroleum refinery catalytic cracker uni-t. The oil/coaL
slurry and hydrogen were preheated to about 650F and fed into the lower end of an S foot inside diameter ebullated hed catalytic reactor operated in a recycle operational mode, i.e. with some recyclQ of heavy hydrocarbon liquid fraction to the coal slurrying step. The catalyst us~d was the same specification cobalt-molybdenum on alumina support material used in Example 1.
Table 5 shows a comparison of the feedstock slurries and reaction conditions used and resultant product yields obtained in the-hydrogenation,and conversion of the ~lend of Il.linois No. 6 coal and petroleum-derived decant oil reco vered from a catalytic crac~er unit.
' ~ , . . . . ~ . - . .
H-COAL PROCESS OPERATIONS
USI~G PETROLE~M DEC~NT OIL FOR SL~RRYI G COAL
Coal-Derived Coal-~erived Oil plus _ Oil Decant Oil Slurrying Oil Used, W %
Decant 0 44 Coal-Derived 100 56 Weight Ratio ~Slurrying Oil/Coal 1.65 1.65 Decant Oil to Total Feed, W ~ 0 27%
Reaction Temperature, F840 840 H2 Partial Pressure, psig1600 1600 Coal Space.Velocity, . .. ..
lb/hr/ft3 reactor 31.2 31.2 CataLyst Age, lbs coal/lb catalyst 1000 8~0-1000 Product Yields, lb/100 lb coall Cl-C3 gas - l l 11.2 11.2 C4-400F naphtha 18.4 23.1 400-650F light distillate 13.5 15.3 650-975F heavy distillate 7.0 8.4 975F+ residuum oil 26.7 21.4 Unconverted coal 3.5 3.5 Ash 11.2 11.2 Vent Gases and Water8.5 5.. 9 Hydrogen Consumption5.3 5.1 TotaLs 105.3 105.1 Based on the results shown in Table S, it is seen that und~r very similar reaction condit.ions significant].y mor.e oE
t~e desirable C4-400F naphtha and 400-650F light distillate ractions were produced w~en petroleum-derived decant oil was used for slurrying the coal than when coal~
derived slurrying oil was used alone. Furthermore, it is noted that `all yields and. comb.inations of yields were increased when using about 44 W % decant oil in the coal slurrying oil as compared to using all coal-derived slurrying oil- The yield resu~ts are shown plotted in ~, . . . ~ .
Figure 3, .and -confirm the- trend o lncreased yie]ds of C4-~50F ~roduct oil fraction with increasing percentage of decant oil used in the slurrying oil.
; .. ~.. . ... -3~
.~
.~lthough we have disclosed certain preferred embodiments of our invention, it is recognized that various modifica-tions can be made thereto, all within the spirit and scope of the invention which is defined by the following claims.
. . .
.
- . . ,. , ~ . . .
Claims (19)
1. A process for catalytic hydrogenation of coal and petroleum-derived hydrocarbon liquid material to produce hydrocarbon liquid and gas products, comprising (a) mixing the coal in particulate form with sufficient slurrying oil containing a petroleum-derived oil fraction having normal boiling temperature range of about 300-1000°F to provide a pumpable mixture;
(b) contacting the coal-oil slurry with hydrogen-rich gas in a reaction zone containing a hydrogenation cata-lyst at reaction temperature within the range of 750-900°F, 1000-5000 psig hydrogen partial pressure, and at coal space velocity of 5 to 60 pounds coal/hour/ft3 reaction zone volume to hydrogenate and convert the feed material mixture to lower boiling liquids and gases; and (c) recovering hydrocarbon gaseous and Liquid products including an increased percentage yield of C4-650°F
boiling range fraction material.
(b) contacting the coal-oil slurry with hydrogen-rich gas in a reaction zone containing a hydrogenation cata-lyst at reaction temperature within the range of 750-900°F, 1000-5000 psig hydrogen partial pressure, and at coal space velocity of 5 to 60 pounds coal/hour/ft3 reaction zone volume to hydrogenate and convert the feed material mixture to lower boiling liquids and gases; and (c) recovering hydrocarbon gaseous and Liquid products including an increased percentage yield of C4-650°F
boiling range fraction material.
2. The process of claim 1, wherein said hydrocarbon slurrying oil and said particulate coal are mixed together in a weight ratio of oil to coal. ranging from about 1.0:1 to about 4:1.
3. The process of claim 1, wherein the petroleum derived slurrying oil is catalytic cracker decant oil and constitu-tes between about 5 and 100 W % of the total slurrying oil.
4. The process of claim 1, wherein the coal-oil feed mixture is passed upwardly through an ebullated catalyst bed.
5. The process of claim 1, wherein the coal feed is bituminous coal, and the slurrying oil comprises a mixture of petroleum-derived clarified decant oil obtained from a petroleum catalytic cracking step and coal-derived oil frac-tion having a normal boiling range of 550-975°F.
6. The process of claim 4, wherein said hydrocarbon oil and said particulate coal are premixed in a weight ratio of oil to coal from about 1.3:1 to about 3:1.
7. The process of claim 4, wherein the feed coal is Illinois No. 6, the slurrying oil comprises 20-80 W %
petroleum-derived clarified decant oil, and the coal-oil slurry is contacted with hydrogen gas in the presence of the catalyst particles at a temperature of about 780 to 870°F, a hydrogen partial pressure of about 1500 to 4000 psig, and a space velocity of 10 to 40 pounds coal per hour per ft3 reactor volume.
petroleum-derived clarified decant oil, and the coal-oil slurry is contacted with hydrogen gas in the presence of the catalyst particles at a temperature of about 780 to 870°F, a hydrogen partial pressure of about 1500 to 4000 psig, and a space velocity of 10 to 40 pounds coal per hour per ft3 reactor volume.
8. The process of claim 4, wherein the liquid product constitutes increased yields of C4-400°F naphtha fraction and 400-650°F light distillate oil fraction.
9. The process of claim 4, wherein the hydrocarbon slurrying oil comprises a mixture of petroleum derived cata-lytic cracker decant oil and heavy coal-derived recycled oil fraction having a normal boiling range of 700-975°F.
10. A process for catalytic hydrogenation of bituminous coal and a petroleum-derived oil to produce hydrocarbon liquid and gas products, comprising the steps of:
(a) mixing the bituminous coal in particulate form with a slurrying oil comprising a catalytic cracker clarified decant oil having normal boiling range of 350-970°F and coal-derived oil having normal boiling range of 550-975°F to provide a pumpable mixture (b) contacting the coal-oil slurry mixture with hydrogen-rich gas in a reaction zone containing an ebullated bed of a hydrogenation catalyst at reaction con-ditions of 780-870°F temperature, 1500-4000 psiq hydrogen partial pressure, and a space velocity of 10 - 40 pounds coal per hour per cubic foot reactor volume to hydrogenate and convert the feed material to lower boiling liquids and gases;
(c) recycling a hydrocarbon liquid fraction to the coal-oil mixing step;
(d) recovering hydrocarbon gaseous and liquid products including an increased percentage yield of C4-650°F
boiling range fraction, and (e) returning the naphtha fraction to the catalytic cracking step to produce increased gasoline product.
(a) mixing the bituminous coal in particulate form with a slurrying oil comprising a catalytic cracker clarified decant oil having normal boiling range of 350-970°F and coal-derived oil having normal boiling range of 550-975°F to provide a pumpable mixture (b) contacting the coal-oil slurry mixture with hydrogen-rich gas in a reaction zone containing an ebullated bed of a hydrogenation catalyst at reaction con-ditions of 780-870°F temperature, 1500-4000 psiq hydrogen partial pressure, and a space velocity of 10 - 40 pounds coal per hour per cubic foot reactor volume to hydrogenate and convert the feed material to lower boiling liquids and gases;
(c) recycling a hydrocarbon liquid fraction to the coal-oil mixing step;
(d) recovering hydrocarbon gaseous and liquid products including an increased percentage yield of C4-650°F
boiling range fraction, and (e) returning the naphtha fraction to the catalytic cracking step to produce increased gasoline product.
11. A continuous process for the catalytic hydroconver-sion of a fluid blend of coal and liquid hydrocarbon material comprising the steps of:
(a) premixing finely divided coal with a sufficient amount of a hydrocarbon liquid consisting essentially of petroleum-derived aromatic oil having normal boiling range of 300-1000°F and coal-derived oil fraction having normal boiling range of 550-975°F to provide a flowable blend;
(b) contacting the coal-oil blend with hydrogen-rich gas at elevated temperature and pressure conditions in the presence of an ebullated bed of hydrogenation catalyst particles at space velocity between about 20 and 150 pounds coal and oil per hour per cubic foot reactor volume to convert the coal and liquid feed substantially to lower boiling hydrocarbon liquids and gas; and (c) recovering, gaseous and distillable liquid hydrocarbon products including and increased percentage yield of C4-650°F boiling range fraction product.
(a) premixing finely divided coal with a sufficient amount of a hydrocarbon liquid consisting essentially of petroleum-derived aromatic oil having normal boiling range of 300-1000°F and coal-derived oil fraction having normal boiling range of 550-975°F to provide a flowable blend;
(b) contacting the coal-oil blend with hydrogen-rich gas at elevated temperature and pressure conditions in the presence of an ebullated bed of hydrogenation catalyst particles at space velocity between about 20 and 150 pounds coal and oil per hour per cubic foot reactor volume to convert the coal and liquid feed substantially to lower boiling hydrocarbon liquids and gas; and (c) recovering, gaseous and distillable liquid hydrocarbon products including and increased percentage yield of C4-650°F boiling range fraction product.
12. The process of claim 11, wherein the total slurrying oil to coal feed ratio is from about 1.0:1 to about 4.0:1 and the reaction temperature within the range of 750-900°F
and 1000-5000 psig hydrogen partial pressure.
and 1000-5000 psig hydrogen partial pressure.
13. The process of claim 11, wherein the hydrocarbon slurrying oil includes 10-80 W % petroleum-derived aromatic oil with the remainder being coal-derived oil.
14. The process of claim 11, wherein the total slurrying oil to coal feed ratio is from about 1.3:1 to about 3:1.
15. The process of claim 11, wherein the petroleum-derived slurring oil is decant oil recovered from a refinery fluidized catalytic cracking reactor, and a portion of the increased naphtha fraction product is returned to the cata-lytic cracker to produce additional gasoline product.
16. In a process for the catalytic hydraconversion of coal to produce gaseous and liquid hydrocarbon products, wherein the coal in particulate form is slurried with a coal-derived slurryinq oil, and reacted in an ebullated catalyst bed reactor at temperature within the range of 750-900°F, 1000-5000 psig hydrogen partial pressure, and coal feed rate of S to 60 pounds coal/hr/ft3 reactor volume, the improvement comprising adding to said slurrying oil a petroleum-derived aromatic oil having a normal boiling tem-perature range of 300-1000°F and comprising at least about 5 W % of the total slurrying oil to produce an increased percentage yield of C4-650°F boiling range fraction product.
17. The process or claim 16 wherein the coal feed is Illinois No. 6 coal and the petroleum-derived slurrying oil is catalytic cracker bottoms clarified decant oil having normal boiling range of 350-950°F.
18. The process of claim 16, wherein the coal feed is Kentucky No. 11 and the petroleum-derived slurrying oil is catalytic cracker bottoms decant oil having normal boiling range of 350-950°F.
19. The process of claim 17 or 18, wherein a portion of the naphtha product fraction is returned to the catalytic cracking step to produce additional gasoline product.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US32235081A | 1981-11-18 | 1981-11-18 | |
| US322,350 | 1981-11-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1195635A true CA1195635A (en) | 1985-10-22 |
Family
ID=23254499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000415814A Expired CA1195635A (en) | 1981-11-18 | 1982-11-18 | Coal hydrogenation process using petroleum-derived slurrying oil |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA1195635A (en) |
| ZA (1) | ZA828311B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104087339A (en) * | 2014-06-19 | 2014-10-08 | 北京宝塔三聚能源科技有限公司 | Hydrogenation co-processing method for mixed oil, coal and coal tar |
-
1982
- 1982-11-12 ZA ZA828311A patent/ZA828311B/en unknown
- 1982-11-18 CA CA000415814A patent/CA1195635A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104087339A (en) * | 2014-06-19 | 2014-10-08 | 北京宝塔三聚能源科技有限公司 | Hydrogenation co-processing method for mixed oil, coal and coal tar |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA828311B (en) | 1983-09-28 |
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