CA1083060A - Process for the continuous hydrocarbonization of coal - Google Patents

Abstract

ABSTRACT

PROCESS FOR THE CONTINUOUS
HYDROCARBONIZATION OF COAL

Certain phenolic compounds are produced from coal by means of a fluidized bed. The coal particles are preheated in a dense phase and passed together with a hydrogen-rich, oxygen-free, conveying gas into the lower portion of a fluid-bed at 480°C to 600°C, passing the coal particles and conveying gas up-wards through the bed to produce a condensable vapour and solid char, maintaining the solids in the reaction zone for an average residence time of 6 to 60 minutes while maintaining the average hydrogen partial pressure at about 100 p.s.i. to about 1200 p.s.i., and withdrawing the product vapour and solids.

Description

r 76~6-1 Thl~ lnvent lon relates generally to a proces3 ~or the production of phenolic compounds from coal. In another aspect, this invent ion relates to a proces~ for preparlng char and gaseous and llquid fuel productY ~rom coal. More partlcularly, this invention concerns a method o~ reactlng coal with hydrogen in a manner such that the ratlo of phenolic compound~ produced to hydrogen consumed 1~ maximized. More partlcularly, thls invention also re-lates to a contlnuou~ hydrocarbonl2ation process employing a ~luid-bed reactlon zone ~or converting coal to char and gaseou~ and liquid fuel products.
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Increa~ing energyneeds have ~ocused attention on sol1d ~os~ll fue1s due to their availabllity ln the Unlted States ln a relatively abundant supply and thelr ~ po~entlal value when converted into more u~eful form~
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o~ energy and ~eedstock. Coal is k~own to be a pokential . 20 valuable source Or chemicAl compounds as well,and consider~ble e~ort ha~ been expended in an attempt to 1: .
de~lop a proGe~s ~or the e~icient production of such chemicals and such fuel product~. ~he ~irst processe3 j invo~ved the carbonization o~ coal in an inert atmosphere to produce only about 5 to 15 welght per cent, generally ~bout 10 to 15 welght per cent, ba~ed on the coal .
charged, of llquld product and about 70 to 75 weight per cent o~ a ~olld char.~ Since the productE were generally suitable only as ~uels, the~e processes were not commerclally ~ea~ible in ~hls country. The lo~ yield and poor quallty o~ product~ rendered thlm commeroially unattractive.

-2-76~6-1 The worth ol the unlt heatlng value of the solid char product even wlth all the gas and llquid product ~1as less than that of the coal charged.
In an e~fort to convert the bulk Or the coal to a llquld product, the hydrogenolysis proce~ses were devel-oped. In these processes a recyclable "pasting oll" was necessary to initially dis~olve or slurry the raw coal; the slurry of coal and usually a catalyst in oil was heated in the presence of hydrogen gas at 450 C to 550 G and about 2003 to lO,000 p.s.l.g., generally 5000 to 10,000 p.s.l.g.;
and up to 20 to 3~ per cent of the finely-dlvided unreacted coal and ash had to be ~iltered of~ or otherwise removed from the heavyl viscous primary 4il product. Although these processes were successful in that ~he amount of liquld products were substantlally increased, they were not commerclally acceptable because the lnvestment the operatlng co~ts and in particular the hydrogen requirements were too high ln comparison with the value o~ the products obtained.
They are oonsidered only in special economlc conditions where alternate energy sources such a~ crude oil are expensive or unavailable More recently, dry "hydrocarbonization" processes were developed wherein coal was heated with hydrogen gas.
However, these processes were generally batch-type processes and, because they were conducted at ~reatly elevated te~-perature~ and pressures, re~ulted in the productlon o~ - -hydrocarbon ga~es and liquids useful mainly as fuels.
Moreover, these batch proeesses were not convertible to operable contlnuous processes in any obvious manner~
Gr~atly elevated temperatures and pressure~ at which these .

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processes runctloned also made them di~icult to operate and lmpractlcal. Xt was shown ln U. S. patent 3,231,486 that a sub-bltu~inous coal, El~ol coal, may be carbonlæed under mild operating conditions in the presence o~ hydrogen in a ~luid-bed. Other processe~ were directed toward total gasl~ic~tlon rather than the production of both ga~ and oll.
Total gaslflcation requires large consumpt~on o~ -hydrogen a~ well as dl~ficult and costly operatlng condi-tlon~. For example, using the crude stoichimetric equa-tion, CHg ~coal)+ 1.6H2 CH4 as a basis for roughly calculatin~ hydrogen consumption, total gasificati3n o~
lOO pounds of ideallzed coal (CH 8) at 100 per cent e~fi- -ciency would require 2~5 pounds o~ hydrogen. This is a hydrogen consumption of about 25~ of the coal by weight.
The hydrogen could be suppliedg f~r example, by steam gasi-~lcatlon of an additional 57 pounds of ldealized coal (C~ 8)~
and the con~umptlon o~ an additional large quantity of coal, "
I depending on the proces~, a~ ~uel.
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The ob~ect of this invention is an improved pro-cess ~or the hydrocarbonization of coal where~n the primary products comprise a mlxture o~ both gaseou~ and liquid pro-ducts and wherein the proce~s consumes mode~ amounts o~
hydrogen amounting to about 1 to about 5 weight per cent o~ the coal charged. By the term "hydrocarbonization" as e~ployed throughout the specl~lcation, ls meant a pyroly~is or carbonization in a hydrogen-rich atmosphere under ~uch condition~ that signiflcant reactlon o~ hydrogen with coal and/or partially reacted coal and/or volatile reaction pro ducts of coal occurs.

-7646~1 The hydrocarbonizatlon process o~ thi~ lnventlonprovlde~ lmproved control ~ver product yield, quality and dlstribution. Although product distribution between gas, liquld and solld carbonaceous residue is to a certain extent a function o~ the nature of the particular coal charged, the pattern may be altered conslderably by variation in reaction cond~tions such as pressure, temperature, resldence time and type of recycle operatlon used. More-over, regardless o~ the yield and/or distrlbutlon, as a result of hydrocarbonization, the end products are also more stable than those obtained ~rom the same coal oy pyrolysls.
~ The process of this invention i9 an improved hy-drocarbonization process whereln the prlmary product, amounting up to about 5 to lO welght per cent of the coal charged, consists of valuable phenolic compounds. In addl-tion, the ratio o~ phenolic compounds and other liquid products to the amount of hydrogen consumed is considerabl~
higher Shan that o~ the prlor art proce~s, resulting, for the firs~ time, in an economl¢ally attractive method for obtaining che~icals, particularly phenolic compounds from ~oal. Moreover, when liquid and ~uel products are deslred,~th~ hydrocarbonizatlon process of this invention also provides a ratio o~ llquid and gaseous ~uel products compared to the amount of hydrogen consumed that ls con-~iderably higher than that o~ prior art processes, resulting in an economically attractlve process ~or converting coal to liquld and gaseou~ ~uel products.
In addltion, the amount of char is reduced from 70 to 75 per cent to le~s than 60 percent, and often a~
low as 3~ per cent of the coal charged. More slgnificantly, the lmproved control over product yield, quality and dls-tributlon in the hydrocarbonization process of this invention ma~es lt partlcularly adaptable and Lnte~ratable lnto an essentlally internally balanced process. Conversion to liquld and gas product~ may be controlled to produce an amount of char ~ust suf~icient to satlsfy other supportive n~ed~, such as hydrogen production, plant fuel and miscel-laneous high-level, heat energy requirements.
The proces~ of this invention, in its broade~t aspect, comprises continuou~ly feeding particulate coal and a hydrogen~containing, oxygen-free gas to a hydrocarbonizatlon zone under relatively mi~ conditions of temperature and pressure to convert 3aid coal to a vapor and a solid char, and continuously wlthdrawing the vapors and char from the hydrocarbonization zone. In this process, there is a continuou~ ~ovement of the solids in the fluldized bed ; throughout the hydrocarbonlzatlon zone, wlth the composition o~ sollds in the bed approximately that o~ the char.
The process of this inventlon, broadly 3tatedt , al3o comprise~ continuously ~luldizing a denRe phase flow o~ coal partlcles in a finel~-divided form; preheating the fluidized partlcle in an essentially oxygen-free atmosphere to a temperature below the ran~e where surface plasticity, or 9tlcklne99 i8 developed; introducing the pre-- heated~partlcleR into the bottom o~ a hydrocarbonization 20ne ;:
at a high velocity; ~luidizing the coal, partially reacted coal and char particle~ a~ a ~luid-bed in the zone wlth a hy-drogen containing, oxygen-free gas; reactlng the coal par-~ 6 : ' . _ .

7646-l ~3~16~

ticles with hydrogen under relatively mlld condltlona of temperature and pressure to convert the coal partlcles to a vapor and a solid char; and continuously ~ithdrawing the vapors and char from the hydrocarbonlzatlon zone. In thls process as well, there is a contlnuous movement of the solid~
ln the ~luidlzed bed throughout the hydrocarbonizatlon zone, wlth the composltion of the solids ln the bed appr~ximately that of the char.
The reaction products are hydrocarbon gases, most-ly saturated, non-h~drocarbon gases, princlpally carbon mon-oxide and carbon dloxlde, light hydrocarbon liquids, tar, water and char. The tar reaction products contain hlgh con-centrations o~ phenolic compounds, aromatlc hydrocarbons and precur~ors, and gasollne components or precursors. When desirable, the tar reaction products are readily convertlble to hydrocarbon ~uel products by methods well ~now to those s~ilIed in the art, such as h~drotreating. Tar yields in this hydrocarbonization process are at least approxlmately double those o~ carbonlzation in the absence of hydrogen .
~urthermore, the ta~ ylelds may be controlled over a range 2D by varying reaction conditions such as time, pressure and temperature.
It ha~ been discovered that expo~ure o~ coal to ~iæ~g conditlon~ during the various phases o~ operation reduces~tar yields upon hydrocarboni~ation of the coal_ In order to maximize th~ production o~ phenolic materials from coal, non-oxidizing cond~tions or substantially non-oxidiz- -.~ - .
lng condltion~ must be employed in all phases o~ the oper-ation such as durlng the mining, shipplng, storage, prepara-tion and reactlon of the coal employed especially where , 754~-1 ~ 3~16~
the lowest rank coals are used such as sub-bitumlnou~ coals par~lcularly those of khe non-agglomerating type e~pecially type~ ~uch as sub-bitumlnous C and lower ran~ed coals such as lignltlc coals. In general, therefore, substantially non-oxidlzing conditlons should be employed in minlng, shipplng, ~torage, preparation and in the process itself when it i8 deslrable to maximlze tar y~elds. On the other hand, it is recognized that a llmlted preoxidation may be bene~lcial to reduclng the agglomerating tendency o~ certain other coals such as, for example~ agglomerating, hlgh-- volative A, bltumlnous coals. In thl~ case, a trade-off exists between loss o~ desirable produc~s and reduced agglomeration. ~ -Coal has been classi~ied accorZing to rank a~ noted in the ~ollowing table, Table A.
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TA8LE A. Claa3i~1catlon Or Cosla by Rsn~.Q
5Legend: F.C. ~ flxed earbon; V.M. Y volatile ~atter; B.t.u. -Brlt~sb ther~al unlts) ... . _ -. _ _ .
C1aD8 Group Ll~lta Or tlxed cQrbon _ ~ . __ or B~t.u., ash rree b~als 1. Meta-antbracit~ Dry F.C., 9ô~ or ~ore (dry C,M., 2% or leas) 2. Anthraclte Dry F.C., 92~ or ~ore . And le88 than 98% (dry .M " ôS or 1e8D and I. Anthraelte ~oro than 2~)

3. 8e~1anthr~clte b Dry F.C., 86% or ~ore snd leas thnn 92~ (dry V.~., 14% or le38 ~n~
_ ~ oro thnn 8~) 1. Bo~-~olatllo bltu~l- Dry F.C., 78~ or ~ore ; nous co~l ~nd le88 than 36~ ~dry V.M., 22~ or lesa and moro thnn 14~) 2. Medlu~-~olatl~o bitu- Dry F.C., 695 or ~ore mlnous coal and le~8 than 78~, (dry V.~.,-31~ or less snd i d ~or~ than 22~ ) II. Bltumlnous 3. ~lgh-~ol~tllo A bitu- Dry F.C., less than 69~, mlnous eo~l (dry V.~., moro than 315)

4. ~lgh-Yolatilo ~ bltu- MoiatC B.t.u., 13,000 or ~lnou~ eosl ~o~e ~nd less th~n l~,OOOe

5. ~lgh-Yol~tllo C bltu- Molst B.t.u., 11,000 or , ~ln,oua eoalr _ mor~ and les~ th~n l3~o-oo-e 1. ~ub-bltu~l~ous A c061 ~oiat B.t.u.~ 11,000 or ~or- ~nd le~ th~n 13,000 III. 8ub- 2. ~u~-bltu~inou~ B oo~l Molst B.t.u., 9,500 or ~or~
bltu~lnous sna le88 thnn ll,OOOe 3. gub-bituoinou3 C eo~l ~oi~t B~t~uo~ 8,300 or ~ore _ . ~nd le83 th~n 9.500~
1. ~lgnlte ~oist ~.t.u., leas th~n ' IV. Ll~ni~le 8,300 2. 3ro~n coal Mol3t B.t.u,~ 1083 than - __ _ ~. ~
8 ~ ~hl~ elasDl~ieation doo3 noe inolude a reY coal~ that h~Yo unu~ual ph~olenl and ebe~lcal properties an~ that co~o ~lthln t~e ll~its Or ~ d cJrbon or ~,e.u. o~ tho hlgh-~olatllj bltu~inou~ ~nd sub-bitu~lnou~ ra~k~. All o~ ~ho-o C0610 olth~r con~aln lens than ~8S
~ol~ure ~nd ~h ~roo rl~od e~rbon or hAYo ~ore ~han 15,500 rol~t, ~h ~r~c ~.t.u.
b - lr a~6lo~orstisB~ nl~y ln lov Yolatilo æroup Or th~ bltu~lnous c13~
e ~ ol"e ~ . ro~or~ to coal contnlning lbs n~tulrsl bod ~olseure ~ub~not lncludln8 vl~lble ~at~r on the sur~aoo o~ tho cosl.
a - ~t i~ roco5nl8~d th~ ~horo may bo DOnCa~in~ varietio~ in each RrUP 0~ the bltumlnou~ cl~os.
c _ Coal~ haTin6 69S or ~oro ~Oa carbon on tho dr~, ~ineral-~atter- ~ -rP~0 b~cl~ ~h~ll bo ela~sirl~d accordins to rl~cd cerbon, rcgard-o~ ~.1;.u.

- Thero ~rc t~ro~ ~arletle~ Or coal in tho high-~olatile C bitu~inous ebal~rou~, n~el~, Varice~ 1, ag~lo~eratln~ and non-Yentherin6;

Y~rloty 2, a3glo~ratin~ and no~tbsrln3; Ys~ioey 3, nona~glo~-orabinI ~nd uon-~eaehorln~.

80urce: A.S.~ 388_38 ~re~. 1).

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761~6_ 1 ~133~
Re~errlng to Table A above~ the pre~erred coals when lt 13 de~irable to maximlze the yield of tar reaction products quantitatlvely such a~ phenollc compounds `~ according to the proce~s of this lnvention, comprise the lowest ran~ed coals, the nonagglomerating, sub-bituminous and lignitio classes, III and IV.
For purpose~ o~ de~inition, the non-oxldizing condltions as used to de~cribe and claim the inventlon re~er to any conditlon of mlnlng, transport~tlon, storage, drying and reacting the coals, e~pecially the pre~erred - coals employed according to thi~ invention, the lowest ran~ed coals, ~hat allows ~or between 80 to about 99 per ~ :
cent especially about 90 to 9~ and preferably about 95 to .:
about 99 per cent o~ maxlmum production of phenolic com-pound~ or tar reactlon products in general, employing the ~ther enumerated and claimed reaction conditlon accordlng to thi invention. Maxlmum recovery or manu~acture o~
: phenollc com-pound~ or other tar reactlon products such as aromatic hydrocarbons and ga~oline precursors, employing the r~action condltions o~ the present lnvention i9 ba9ed on the phenolics or other tar r~action products recovered ~rom the coal ~spec~ally the pre~erred coals o~ the present lnventlon~ ~he lowest ranked coal~ which are at no times exposed or substantlally expo~ed to any alr or other oxidation condltions prior to hydrocarbonization.
~he coal employed in the process o~ this invention : : can be any coal which is non-agglomeratlng under the process :: condltlon~, such as the llgnites, sub-bituminous C coals and the li~e. Pre~erred non-agglomerating coals are those contalning at least 15 per cent oxygen, and pre~erably 18 '; ~ "
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761~6-1 3~

to 25 per cent oxygen, on an MAF basls.
Llghtly to moderately agglomerating coals may be used in the process o~ thls lnven~lon wlthout a separate pretrea~ment step added to prevent agglomeration Or coal partlcles in the ~luid-bed hydrocarbonization zone. Ordinar-ily, such a pretreatment would be nece sary in a continu-ou~ hydrocarbonlzation proce~s slnce even those coals con ldered to be non-agglomerating coal~ ~uch as llgnites or coals ~rom certain sub-bltumlnous seams are su~ceptlble to a~lomeratlon and tend to become stic~y ln a hydrogen-rich atmosphere. Moreover, ~eeding heavy liquid materlals to the rluid-bed hydrocarbonization zone is ~nown to cau~e de-~luldlzation of the bed due to particle agglomeration and plugglng. Such heavy liquld materials may be recycled heavy tar products to be converted to lower molecular .~ , welght product~ ht liquids and gases. Or they may be heavy-llquids from-an external source whlch have been added to enrich the normal gas and/or liquld product, or as a means o~ waste dlsposal. However, accordlng to the process o~ this inventlon, a separate pretreatment is not necessary ~or the handllng of the lightly to moderately agglomerating ~eed materials~
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Such reed materials may include the low rank c021s, ~uch as l$gnites and ~ub-bitum~nous C coals even ~ome mod-erately agglomerating bitumlnou~ coals and also recycle pro-duct~liqulds. Preferred coals whlch may be used according to the process o~ thi~ invention without any pretreatment step added to prevent agglomeration comprlse the lowest ran~ed coals, the non-agglomeratlng, sub-bituminous and lignltic clasaes, III and IV of Table A above, the ~Inon-ca~-lng" bltum$nous coals r~erred to in Table A and a ~ew ~ 0 8 3'~

moderately azglomerating or ca~in~coal~.
More highly agglomerating coals, such a3 mo~t bit-um~nous coal~, are strongly ag~lomerating in a hydrogen atmos-phere. They can not be handled conventionally even wlth a pretreatment ~tep. These coals may now be handled wlthout an lnJurlous degree o~ derluldlzation by the proces~ of thls invention alone or in combinatlon wlth a pretreatment step, 1~ nece~ary~ If a pretreatment step ls neces~ary, the needs for pretreatment are milder and co~t less. For example, even a~ter heavy conven~ional pretreatment, the use of a highly agglomerating coal such as Pittsburgh Seam Coal, in a ~ .
hydrocarbonlzation process, presents the problem o~ ag-glomeration occurring in the ~luid-bed hydrocarbonization æone. However, it 15 beneflcial to use the process o~ thls :Lnvention to overcome thi~ agglomerating problem.
- Those ~kllled in the art wlll recognlze that any number ~ sultable pretreatment steps may be applied ln combinatlon with the process o~ thi~ invention ~or the handling of coals which are either highly agglomerating or highly agglomerating in a hydrogen-rich atmosphere. The3e pretreatment steps include, for example, but are not limited .
to, chemical pretreatment, ~uch as o~ldation, or mlxlng with inert ~ollds such a~ recycle char. It ~hould be noted, however, that when coal i8 sub~ected to an oxidatlon type pre-treatment to pr~vent agglomeration in the hydrocarbon-i2atlon zone, the oxidation of the coal also result~ in a quantitatlve lo~s ln the maxlmum realizable amount of tar product. `
`' J Coal particle~ ln a particulate state may be used in the process o~ this invention. The coal ~iz~ can be . . . ' , 7646-1 1.083~!~;V

about 8 me~h or less, wlth particle sizes o~ less ~han about 20 mesh being preferred. Ihere i~ no need to remove very ~ine particles, but lt is deslrable to...minimize khem by approprlate selection o~ the grlndlng process.
According to the improved process o~ this invention, the coal particles are preheated before entering the hydrocarbonlzation zone. me coal partlcles are in a dense phase flow. By "den~e phase" as u~ed throughout the specification ls meant a concentration o~ solids in ~luid-. lO i21ng ~a~ o~ ~rom about 5 pounds to about 45 pounds o~ .
: solids per cubic foot o~ gas more typically from about 15 pounds to about 40 pounds of solids per cubic ~oot o~ gas.
A dense pha~e o~ coal particles ~hould be dlstln~uished ~rom the dilute phase wherein the concentratlon o~ solids luldlzing gas is typlcally ~rom about 1 pound to a~out 2 pounds of solids per cubic ~oot o~ gas. In coal conver-. slon processes emplo~ing a dilute phase ~low o~ coal par~icles preheating s~eps have generally involved pa~sln~ the coal particles around hot plpes or usi~g large quantities of ho~
20 ~ gaBes to lmpart heat to ~he coal particle~ directly. In-direct heat tran3~er in coal conversion pro~esses employing a dilute pha8e ~low o~ coal particles ls uneconomical and ~.
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impractical due to ~he lnherently ~oor heat trans~er coef-~icients o~ the pipelines ln dilu~e phase ~low" approximately 1 B~rU to 2 BTU per hour per F per square ~oot of inside -sur:~ace area o~ the plpellne. ~Iowever, it has been ~ound that a dense phase ~low Or coal particles may be convenien~ly and ec onomically preheated by indirect heat trans~er mean~ .
the hydrocarbonlzation process o~ thig inven-tlo~, the ~low o~ coa.l. particle~ in dense phase provlde~ the ~ollowing belle~its. ~he quantlty o~ coal trans~erred and .

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heated per unit Or pipe cross-sectional area not only ex-ceed~ that obtainable in dllute phase rlow but also use~
le~s power. A cubic ~oot o~ gas conveys 15 to 30 time~
more coal partlcles in dense phase ~low ~han in dilute phase ~low. The use of a comparatively small amount o~ conveying gas ln dense phase flow may be extremely bene~iclal downstream i~, for example, ~lue gas or nltrogen gas is used a~ the con-~eylng gas. Large amounts o~ conveying gas other than hydro-gen-rich gases or recycle gas are undersirable in the ~luld-~ed hydrocarbonization zone and mu~t be separated ~rom the coal particle~ before entering the ~luld-bed by sultable equipment uch as a cyclone ~eparator or the li~e. Mo~eover, ir ~uch a 9eparation ls desired, in dense phase the coal particles are more easlly separated from the conveying gas be~ore entering the fluid-bed hydrocarbonization zone, Also, `~ power requlrement~ are intrlnsically smaller in dense phase flow due to lower carrier gas velocities. In dllute phase ~1OWJ the Iinear velocity of carrier gases is be~ween 50 and . 100 feet per second to prevent entrained coal particles ~rom settling out ln pipelines. ~owe~er, in dense phase rlow~ the llnear velocit~ of carrler ~ases may be about 20 feet per second and su~taln steady flow in the pipellnes. -~
According to the process of this invention, a dense phase ~low o~ coal particles i~ preheated by indlrect heat tran~rer means to a temperature up to about 420 C.
For example, ~ den~e phase o~ coal particles may flow through a multiplicity of parallel plpelines whlch are externally heated. The heat tran~er coef~lclent of the pipellne has been ~ound to approximate that found ln heat transfer through the walls of a ~luld-bed, about 20 to about 40 BTU
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per hour per square rood o~ ln3ide sur~ace area ~r F. The externally heated pipellnes wh~ch the coal partlcle~ pa~s through are heated to a predetermined temperature su~lcient to rai~e the temperature o~ the dense phase of coal particles up to a temperature o~ about 400 C upon exiting the externally heated plpelines.
The ob~ect Or preheating the coal 1~ to satls~y partially bhe enthalpy demand of the adiabatic-type . hydrocarbonlzatlon reactlon. Additonal heat i~ supplied-by the heat o~ reaction and by preheat added to process gases. The enthalpy demand conslsts o~ the heat required to ralse the temperature o~ coal and proces~ gas ~rom their inltlal value to reaction temperature plu~ ~mall heat los~es. The actual temperature to whlch the coal ~eed must be preheflted 1~, th~re~ore, a ~unction of the preheat added to proce~s gasesJ and ln the extreme may be amblent temperakure l.e., ~ero preheat.
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- Arter being preheated to the desired temperature, the dense-phase flow of coaI partlcles is reacted with hy-drogen in the rluid-bed hy~rocarbonlæation zone. Both agglomeratlng and non-agglomerating type coals may be employed in the contlnuous proces~ o~ thls invention with- ::
out de~luldization o~ the ~luid-bed and p1u~ging type pro-blem~. Agglomeratlon o~ coal particles ln a ~luid-bed may be substantlally prevent~d by introducing solid coal parti-cle~ into the ~luld-bed hydrocarbonization zone at a high velocity.
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76~6-1 ~083~
Coal particlz~, especlally ca~in~, ~welllng or a~glomeratlng coals become sticky when heated in a hydrog0n-rich atmosphere. Even non-ca~lng, non-~welling and non-agglomeratlng coals become stic~y when heated ln such an atmo~phere. Coal particles begin to become stic~y at tem-peratures ln the range of about 350 C to about 500 C, de-pending on the specl~ic propertie~ of the coal, the atmo~-phere and the rate of heating. The stic~iness re~ults - due to a tarry or plastic~ e material ro~mlng at or near the ~ur~ace o~ each coal particle, by a partlal melting or decompo~itlon proce~s. On ~urther heating over a time period, the tarry or plastic~ e materlal 19 ~urther trans-~ormed lnto a substantially p~rous, solid material referred to a~ a "char". The length o~ thls time perlod, generally ln the order o~ minutes, depend~ upon the actual temperature o~ heating and is ~horter with an increase in temperature.
"pla~tic tran~formation" a~ u~ed throughout the specl- _ ~ication is meant the hereina~ove de~crlbed process wherein ~ur~ace~ of coal partioles being heated, particularly when heated ln a hydrogen atmo~phere~ develop stickine~s and trans~orm lnto ~ubstantlally ~olld char, non-stic~y æur~aces.
"Plastlc tran~ormation" i~ undergone by both normally ag- ~
glomerating coals and coals which may develop a sticky sur- :
face onl~ in a hydrogen-rlch atmosphere.
Agglomerating or caklng coals partially so~ten and become sticky when heated to temperatures between about ; 350 C to about 500 C over a perlod of mlnutes. Component~
of the coal particles so~ten and ga~ evolves because of de compo~ition. Stic~y coal particles undergolng plastlc trans-~ormation tend to adhere to most surface~ whlch they contact such as w~lls or baf~le~ in the reactor, particularly relatively , ,: ' 76~6-1 ~ ~ 3~ 6~

cool walls or baffles. However, contact with other sticky particles while undergoing plastic transformation results in gross particle growth through adherence of sticky particles to one another. The formation and growth of these agglomerates interferes drastically with the maintenance of a fluid-bed and any substantial growth usually makes it impossible to maintain fluidization.
In particular, entrance ports and gas distribution plates of equipment used in fluid bed coal conversion pro-cesses become plugged or partially plugged. Furthermore, even if plugging is not extensive, the sticky particles tend to adhere to the walls of the vessel in which the operation i5 conducted. Continued gross particle growth and the formation of multi-particle conglomerates and bridges interferes with smooth operation and frequently results in complete stoppage of operation.
Agglomeration of coal particles upon heating depends on operating conditions such as the heating rate, `
inal temperature attain~d, ambient gas composi~ion, coal type, partic~e size and total pressure. When heated in a hydrogen atmosphexe, even non-agglomerating coals~ such as ~ -lignites or coals from oer~ain sub-bituminous seams, are susceptible to agglomeration and tend to become sticky in a hydrogen atmosphere. mus ~ agglomeration of coal particles i8 accentuated ~n a hydrocarbonization reactor where heating in the presence of a hydrogen-rich gas actuslly promotes formation of a stlcky surface on the coal particles reacted.

' ' ' .'' ~ -17 - -76~6-1 ~ ~ ~ 3~6~

The fluid-bed is conventionally maintained by passing a fluidizing medium through finely~divided solid particles. "Introduction velocity" as used throughout the specification means the velocity of ;~ carrying gas through a device which causes the solids or liquid velocity to approach the maximum theoretical ratio to gas velocity, i.e., 1 to 1. By a high velocity is meant a velocity sufficient to rapidly and uniformly disperse fresh coal particles entering the fluid-bed at a temperature below the plastic transformation temperature within a m~rix of non-agglomerating particles in the fluid-bed. The non-agglomerating particles preferably are the hot, partially reacted coal particles and char par~icles situated within the fluid-bed reaction zoneO Due to the difference of temperature between ~he entering coal particles and the reaction zone, the entering particles tend to agglomerate as heat transfers from the reaction zone to the entering coal particles. However9 it has been fou~d that when introduced in the fluid-bed at a high velocity, the entering coal particles rapidly and uniformly disperse within a matrix o~ non-agglomerating particles within the fluid-bed before being heated up to the plastic transformation-temperature range.
By this process, the entering, sticky or potentially sticky coal particles are rapidly distributed ~ ~ -and brought into intimate association with non-sticky, hot particles situated within the 1uid-bed reaction zone.
The entering particles do not substantially adhere to the .
. .

. .

~ 7646-l 3~6~
charry surfaces o~ the~e non~agglomeratlng hot particle~
which have passed through the plastlc tranærormation-temperature range or are inherently non-agglomeratlng.
The hot, non-agglomerating particles at bed temperature rapidly trans~er heat to the entering coal particles causing them to traverse the plastic trans~ormatlon-i temperature range swlftly without contacting ~igni~icant numbers o~ o~her stlc~y coal part~cles beforehand.
A veloclty rate use~ul in the method of thlslO invention m~y be obtalned by any suitable means. For example, a narrow inlet port or any other lnlet means which narrow~ or nec~s down the cross-sectlonal area o~ the pa~sageway to the lnlet where the fresh coal particles enter the reactor may be employed t~ accelerate the coal particles ~o a hlgh velocity. In additlonJ process gas may be physically added to the fluidized stream o~ ~resh coal at a polnt be~ore the ~luidlzed stream enters the reaction zone.
The addition o~ process gas lncrea es the flow rate o~ the ~luidlzed ~tream and hence the velocity o~ the coal partlcles, An amount o~ process gas su~flcient to achieve the desired entrance velocity Or coal particles should be used.
Since the ~luid~zed coal particles are transported through the lines in a dense phase ~low, hlgh veloclty flow rates are u~ually unnecesary and undersirable due to the ; abra~lve~characteristics o~ coal. A high veloclty, dense phase flow or coal partlcles throughout the lines would have requ~red wear plates ta be installed throughout the llnes to control the otherwi~e rapld ero310n rate of the llnes, sùch wear plates being an un~esirable expense. How-ever, according to the present invenki3n, only a small . ' , .
-lg-, '. .. :: . ' . . . ' . . - .
. - . . . ..

761~

3~

surface area will be exposed to abra~ive wear and thl~
part may be replaced readlly and economically wlth little or no downtlme of the system.
By malntainlng the distance for tran~port between feeder and reactor minlmal, a high veloclty dilute phase or an lntermediate dllute phase flow may be employed in the line or lines connecting the ~eeder and reactor. The increa~ed wear and/or need for wear-resiætant materlal i9 of~set by the increased separatlon and dllutlon of coal part-icles on lntroductlon lnto the reactor at a high velocity.
ThiR ma~e~ ~ome addltlonal contrlbutlon to avolding agglomer-atlon~
For example, an lnlet means comprlslng a material having a wear-reslstant surface may pref~rably be employed ln thls inventlon a~ a means for increaslng the veloclty of ; coal partlcles entering the reaction zone and as a means ~` Or con~rolllng the manner of entry l.e., in a solid stream or ~n a fan-llke unlPorm dlstribution. U~e of such an inlet mean~ ~engthen~ the wear time o~ the surface exposed to the high erosion rate caused by the hi~h velocity flow o~ coal partlcles.
Sultable wear-re~i~tant sur~aces would be compo~ed of materlal~ such as tungsten carblde, ~ilicon carbide or other wear re~lstant materials known ln the art in any combination or mixture thereof. For clarity and 11-lustrative purpo9es~0nly, the descrlption of thi~ lnvention will be mainly directed to the use o~ tungsten carblde as the wear-resistant ~urface o~ khe material that reduces ero~ion in the lines although any number of other wear-resistant materials can be used ~uccessfully according to this inventlon.

. , . :' ~ ., . ' , .: : :

An inle~ means such a~ a no~zle whlch compri~e~ ~
transfer llne havlng a reduced or constricted cross-sectional area may be employed ln the method of this invention. The length to crosq-sectional area ratio o~ the nozzle should be su~ficiently large enough so that the desired velocity o~ in~ection ~or the solid coal partlcles or non-vaporizable recycle oil may be achleved A length to cross-sectional area of this ~ection of transrer llne of greater ; than about S to 1 is desirable, greater than about 10 to 1 pre~erable, and greater than about 20 to 1 more preferable.
~his allows for a ~inlke dlstance whlch the coal particles and/or non-~aporizable recycle oil require for acceleration ko the velocity approaching that o~ the carrying gas.
According to this inventlon, it i~ preferable to lntroduGe a fluidized ~tream o~ coal partlcles lnto the lower ~nd of a ~luid-bed hydrocarbonizatlon zone. More preferably the partlcle~ are introduced into the hydrocarbon-ization reactor through at least one inle~ in the reaGtor in a verticall~ upwards direction. The inlet is situated sub~tan-tially in the vicinity o~ the vertlcal axi~ at or near the reactor bottom. The coal particles are introduced at a ~Jelo-city~sur~icient to mi~ the ~resh coal having a temperature below the plastic tran~ormation-temperature rapidly with non-agglomeratlng partlcles such as partially reacted coal and char part~cles in the reaction zone at the reaction ; temperature thereby substantially preventing agglomeration o~ the r~ uid?b~d.
In the reactor which preferably is substantially vertical, the natural circulation of coal particles within the ~luid-bed hydrocarboniz~n zone i9 a complex flow pat~ern.

-- , , , ' "~ : ' ' ' , . ,,' ~ ', , .

~ ~ 3~

However, lt may be de~cribed appro.ximately by dlvidlng the hydrocarbonization zone lnto two concentrlc sub-zones, an inner sub-zone and an outer sub-zone surrounding the inner sub-zones.
; In the inner sub-zone which is situated substan-tlally withln the axially central portion of the reactor, coal particles flow ln a generally a~cending path. In the outer sub-zone, which 1~ sltuated substantially near the walls Or the reaotor, coal particles flow in a generally descending path. Advantages of introducing the coal particles into the fluid~bed of the reactor in an essentially vertically up-wards direction are that the natural circulation o~ coal par-. tlcles in the ~luid-bed is enhanced and the coal particles .-. get at lea~t a minimum residence tlme. Introductlon o~ coal --particles into the fluid-bed o~ the reactor promotes a channeled circulation of particle~ within the hydro--~ carbonlzatl.on zone along the natural circulation path.
. Circulatlon eddies, are thus en~a~cedand promote the dls-perslon o~ the enterln~ coal particle~ within the fluid-bed hydrocarbonlzatlon zone. Moreover~ when ~ntroduced in this manner, the coal particles are en~ured of not immediately and directly ~tri~cing the sides of' the ves~el whereln the : hydrocarbonization occurs, a result which could lead to un-necessary and undesirable agglomeration.
The fluidlzed coal particles should be introduced :: into thi~ inner sub-20ne, the central up~low zone within ~he reactor. The central upflow zone extends radially from the vertical axis of' the reactor to an area where the outer-sub-. . -zone, the peripheral down~low æone begins . It is essential tha~ the coal particles be introduced into the central upflow ~.

-22- .
. ,, ' ' .

. ~0~33~

zone ln order to avold ~trlking the walls ~ the reactor or enterlng the peripheral down~low ~one. Pref'erably, the coal par~icles are introduced through the base or bottom of the reactor at one or more inlets situated in the vlcinlty o~ the polnt where the vertical axis o~ the reactor lnter~ects the ba~e o~ the reactor.
It has been discovered that introduclng a fluldized stream of coal particles into a dense phase, ~luld-bed hydrocarbonlzation zone at a veloclty of more than about 200 ~eet per ~econd in a manner described hereinabove ~ubskantially prevents agglomeration or ca~ing of the ; ~luid-bed. When a lower in~ectlon veloclty, for example, about 100 feet per ~econd i~ used, agglomeration o~ the ~luld-bed 1~ not prevented. In order to substantially prevent agglomeratlon of the fluid-bed hydrocarbonizatlon zone~ coal should be introduced at a high velocity lnto the zone in a high velocity stream, i.e.g at a velocity more than about 200 feet per secondJ and pre~erably more than about 400 feet per second in the manner described hereInabove.
The hydrocarbonization zone ls maintained at an average temperature o~ ~rom about 480 C to about 600 C by known heaking~ethods. Pre~erably, a comblnatlon of pre-heat and heat 4~ reaction i8 used to maintaln ~he hydro-carbonlzation ~one adlabatically at these temperatures.
; Although any convenlent source of heat can be employed, it has been ~ound that, when the ~eed coal i~ preheated in the range o~ about 250 C to about 300 C,preferably between about 250C and about 420C, the exothermic heat of reaction in the hydrocarbonization zone ls su~icient to malntaln the ~ desired reaction temperature. It is also desirable to : :

' ' 761~6-l ~83~

similarly preheat the proce~s gas Although temperatures of less than 480 C can be employed, they are ~enerally n~t desirable because the rate of reaction 3~ coal with hydrogen ls too slow for a practical process. The temperature must not exceed about 600 C, however, ~or at these more elevated temperatures, several deleterious reactlons occur during even the minlmum residence times ^ practicable in the ~ind of reactlon described. Oxygen ls more completely converted to rwater and carbon oxides, heavy liquid products are converted to co~e and lighter liqui~s and gases, and hydrogen consumption increa~es.
The temperature Or reaction may be contr~lled at a desired point within the operating range of 480C to 600C by cholce o~ and control of the preheat condit i3n8 .
Temperatures in the range o~ 520 C to 580 C are pr~erred.
The gas employed can be pure hydrogen or hydrogen in admixture with an inert 8a~ such as nitrogen or the li~e.
F'or khe purpo~es o~ this reactlon, recycle gases such as methane and ethane may be con~ldered to be e~sentially inert.
However, the hydr~gen partlal pressure in the hydrocarbon-. .
izatlon zone hould be between about 100 p.s.l. to about 1200 p.s.i. At partial pressure o~ less than 100 p.s.i. the rate of reaction with the coal i3 too slow, and at partial pressures of greater than 1200 p.s.i. the amoun-t o~ hydrogen con9umed is too great ~or an ~conomical process and the dif~iculties of avoidlng agglomeratlon become too great for a prackical and economlcal pro¢ess. Hydrogen partlal pressures o~ ~rom about 300 to about 500 p.s.l. are pre-~erredl and ~r~m about 200 to about 800 p.~.~ desirable.
By the term "hydrogen partial pressure"~ as employed in the . . . ~ . :

~ ~ ~ 3~ 6 speclfication and claim~, i9 meant ~he log mean average o~
the hydrogen partlal pressure in the feed and product gas streams.
The coal, when it ls fed lnto the hydrocarbon-izatlon zone, i9 rapidly hydrocarbonlzed, leaving a 301id partic~late char ln the bed, which ls then wlthdrawn from the bed. The coal is ~ed at a rate such that the average ~olid resldence time in the hydrocarbonlzati~n zone ls from about 1 to 30 minutes9 pre~erably 3 to 12 mlnute~, and may be from about 5 to about 60 mlnutes, more preferably about 8 to about 30 minutes. By the term "solid residence time" as employed in the speci~lcation is meant the time needed to fill the empty reaction zone with reacting coal.
It is calculated by multiplyln~ the volume of the reacting zone by a fluld-bed density of coal per unit volume typically 30 to 38 pound~ per cubic foot, and dividing this by the coal ~eed rate.
In the hydrocarbonization zone, the coal is con-verted to hydrocarbon-rich ga~, to oil and to char in pro-portlons whIch can be varied by varying temperature, time . . . .
~ and pressure. Preferably, char yleld i~ the minimum amount .~ , su~lclent to ma~e the hydrogen and plant fuel. Ma~e char may be dropped through an over~low pipe to valved hot receivers, which may be intermittenly depressurlzed and dumped. En-trained char may be removed rrom the vapor overhead by cyclones or the ll~e and returned to the bed. Oil, water and gas products may be separated by methods well ~nown in the art such a~ staged condensation and the ll~e.
As ~ndicated above, lt is the obJect of this lnventlon to maxlmize the amount of liquid products, part-.

761~6- 1.
~3~

lcularly phenolic compounds, lncludlng phenols, cre~ols, xylenols, eth~l phenol~ and the like in proportion to the amount of hydrogen consumed. It ls also the ob~ect of thl~
lnventlon to maxlmlze the amount of llquid and gaseous fuel product~ in proportion to the amount of hydrogen consumed.
lt has been discovered by thls lnvention that, to obtaln these obJectlves, not only must the process conditions be maintained withln the limits set forth above, they also depend upon each other.
This lnter-d~pendence o~ proces~ condition~ results because of the e~fect o~ each variable on product yields and - hydrogen consumed. For example, the yleld of tar increases ~' with lncreasing time, but ~ends to level off at a limit, which i.s dependent on temperature and pres~ure, above which there ~.s little or no increase in tar yield~ This llmit is about 10 minute~ at above ~40 C, and may be, at tlme~ about 15 minutes at about 540 C, but decreases to a~ low as 8 minute~
o at 570 C~ The preci~e llmlt will vary, of course, depending on the particular coal or hydrogen partial pressure employed.
On the other hand, the amount of hydrogen consumed increases oontinuously with increaslng residence time. Both the yleld o~ tar and the amount o~ hydrogen consumed increase with lncreasing hydrogen pressure, with the amount of hydrogen consumed lncreasing proportionately faster.
Other desirable product mixes may be obtalned by ~electing approprlate operatlhg conditions. For example, product gas yields may be lncrea~ed at the expense of higher hydrogen consumption at a constant residence time and hydrogen partial pressure. As temperature increases a~ described aboveJ llquid yield ~irst lncreases~ then ~ 7646-1 , ~33~

reaches maximum and decreases. Gas product ~ay be lncreaE;ed at the expense of liquld product by recycllng all or part o~ the latter. On the o~her hand, at mlld operating con-dltions whereln hydrogen consumption is less than about 2 per cent o~ the welght Or the MAF coal, llquid yield will be hlgh when compared to gas yield.
The varlable having the greatest e~fect on tar and phenolic yield per unik of hydrogen con~umed is tem-perature. In generalJ the yleld o~ tar increases slowly wlth temperature to a maxlmum, and then decreases because of hydrocrac~ing of tar components to uncondensable gases and coke. On the other hand, the amount Or hydrogen con-sumed increases very rapidly with temperature. In addition, ~he amount of oxygen in the char decreases with temperature and, once the char i8 depleted o~ oxygen, ~urther reaction o~ char and hydrogen will not procluce the desired phenolic product~. As a result, the yield o~ tar and phenols per unit of hydrogen consumed remains hlgh up to a maximum temperature depend~n~ on residence time and pressure and then rapidly decreases.
Accordlngly, to maximize the yield Or phenols and tar per unit Or hydrogen consumed~ the process variable~
must conform to the relationshlp defined by the equation:
. - o. o6~ o. o6 ~I) SH= T(P) (t) whereln SHis the hydrocarbonizatlon severlty ~actor having a value o~ from 530 to 640, preferably ~rom 560 to 630;
T is the average hydrocarbonlzation temperature in C;
P is the log mean average hydrogen partial pressure in pos.i.

divided by 1000; and t is the solids residence time in mlnutes. When this relationshlp is observed, the weight :

. ~ . .

~ 7646-1 ratio of phenolic compounds boiling below 230C to hydrogen consumed will generally be about 3.5 to about 5 or higher.
This is true for the preferred class III and IV coals.
Furthermore, to maximize yield of total liquid products, the operating range for S should be 550 to 700, preferably 600 to 680.
Many products produced by the hydrocarbonization of coal in accordance with this invention are cresols and other substituted phenols which may desirably be dealkylated to form phenol. Although the dealkylation can be accom-~; plished in a step separate from the hydrocarbonization~
it has been found by this invention tha~, if the vapors produced by the hydrocarbonization are retained in the fluidized bed for from about lO seconds to about 250 seconds preferably from about 30 to about 150 seconds 7 ~:
- considerable dealkylation of the substituted phenols occurs.
It has been further found that the presence of the char in the fluidized bed acts as a catalyst for the dealkyla~ion permitting a degree of dealkylation equivalent to that obtained at higher temperatures in the absence of the char.
For optimum results from this dealkylation step, it has been found that the temperature and vapor residence time must conform to the following equation:
(II~ Sc = T(~)0'048 w~erein Sc is a cracking severity factor having a value of from 640 to about 750, preferably 650 to 710; T is the temperature in C; and 0 is the vapor residence time in seconds. In other circumstances, when it is preferable ~o maximize total liquid product and minlmize hydrogen consumption, it may be desirable to operate at the lowest ,, 2~-. - - - , . .
.. . . . . ..
: .

. 7646-1 ~'0 ~ 3~

practical ran~e Or Sc from 600 to 690.
The product gas comprises vapor products ~rom the hydrocarbonization and consists mainly of ga~eous products s~ch as water carbon dioxide, ~arb~n monoxide methane and the ll~e, e.g other hydrocarbons, as well as unreacted hydrogen, and condenaable "tar" fraction. The tar ~raction can be readily distilled to recover valua~le chemlcals, includ~ng phenols~ The tar contains a - ~izeable quantity o~ materlal bolling at temperatures in exce~s Or about 230 C which i9 uBeful malnly as a fuel. It has been found by this invention, however, that this hi~-h bolllng material can be recycled to the hydrocarbonization zone to be hydrocrac~ed to compounds boiling below ~30 C, thereby permltting substantially all of the vapor products produced by the hydrocarbonization to be recovered as valuable, low-bolllng chemicals. The high-boiling material i~ fed to the hydrocarbonization zone at a point su~ficient to permit conver~ion o~ about 25 to 40 percent of the recycled materlals to products boiling below about 230 C.
~20 In thi~ manner the over-all yield o~ low boiling phenolic materials iY increase~ and the ratio of phenols produced .
to hydrogen consumed ig also increased. Because thls material will fIa~h vaporize when ~ed to the hydrocarbon-lzation zone, the hydrocarbonlzation i~ still conducted ln the dry pha~e. By thi modiflcatlon, the three process ~tep~ of hgdrocarbonization, deal~ylation o~ substituted phenols, and a ~econdary hydrocrac~ing of coal tars are conducted imultaneou~ly. ~ -It ha~ also ~een found by this invention that thls tar or fraction of it may be recycled to the hydro-..

.

76l~ 6-~lO83a6V

carbonization reaction and thereby converted to lower boll-ing llqulds, gases and char. Such recycle can be accom-pl~hed without agglomerating the rluld-bed l~ the recycle llquid is in~ected at a su~lciently high veloclty as de-s ~ bed above to admix it rapldly with partlally reacted coal and char particle and at such an angle as to avold lts stick-lng to the walls or lntervals o~ the bed before reacting or vaporlzing.
The char produ~ed by the hydrocarbonization pro-cess of thi~ invention i~ very reactlve and conta1ns fairly large quantlties of hydrogen, generally about 4 weight per cent on an MAF basls. It has been ~ound that 1~ the char is heated to a temperature of 800 to 900 C or ; higher,.. pre~erably 840 to 800 CJ one can obtain a gas stream - :
containlng about 75 to 85 volume per cent hydrogen, with the balance comprising mainly carbon monoxide and methane.
This h~drogen stream~ after removal o~ the contamlnants, i can be employed as the ~luidizing ~as, thereby substantially lessenlng the requirement ~or hydrogen ~rom ~ome other source. It 19 prePerred that this "calcination" process be conducted ~n a ~luidized bed~ employlng, for example steam as the fluldlzlng medlum. The pres~ure is preferabl~
atmospheric, The ~olid re~idence time in the calclnation zone can vary from about 2 to about 10 minutes, and is pre~erably ~rom about 3 to about 7 minute~ When steam ls ; the ~luldizatlon ~as~ partial reactlon occur~ augmentlng the hydrogen and carbon monoxide yields. It ls not intended to re~trict the method of u~lng the char to this process, however~ for the char 1~; ~uitable as feed to any of several commerclal or propo~ed gasi~ication processes. :

, ~ 7646-1 1~83~6~

The manner ln which the -lnventlon 19 carrled out will be more ~ully under~tood ~rom the ~llowing descript1~n when read with reference to the accompaying drawings whi~h represent semi-~iagrammatlc views of embodiments of a system ln ~hich the process of thls inventlon may be carrled out.
Flgure 1 lllustrates coal supply vessels 10 and 16 a coal ~eeder 22, preheater 30 and reactor vessel 40.
Line$ are prov~ded for conveying ~inely divided coal through ; 10 the vessel~ in sequence. A llne 26 conveys the coal from the . pick up chamber 18 to preheater 30. A line 34 conveys the coal ~rom prehea~er 30 into reackor vesæel 40. A llne 44 conveys devolatized coal (termed "char"~ from reaction .
ve~sel 40 for recovery as olid produc~ ~r ~or recycle. A
: line 42 i9 provided rOr conveying llquid and vapor products . ~rom reactlon ve sel 40 ~or ~urther processing and/or re-. cycle~
According to the process of this lnvention, the ~eed coal i9 in particulate ~orm, havlng been crushed, ground, pulverized or the li~e to a size finer than about tyler mesh, and pre~erably ~iner than about 20 Tyler me h. Furthermore, while the feed coal may contain adsorbed water, lt i~ pre~erably substantially free o~ sur~ace . moi~ture. Any ~uch adsorbed water will be vaporlzed during preheat. Moreover, any ~uch absorbed water must be included as part o~ the in~ert carrying gas and mu~t not be in such large quantitles as to give more carrying gas than required.
Coal particles meeting these condltlons are hereln re~erred :~
to as "~luidizable".
.

- , . .
-31 .

.

76~6-1 ~Cl 83'~

The coal supply ves3elq 10 and 16 each can hold a bed o~ ~luidizabIe coal particles, which are employed in the process. Coal supply ves~el 10 1~ typlcally a lock-hopper at essen~ially atmo3pherlc pr-essure. Coal supply vessel 16 i5 typically a loc~-hopper in which fluidized coal can be pressurlzed with process gas or other deqired fluidization gaqes .
Operatlon of ve~el 10, 16 and 22 can be illus-trated by describlng a typlcal cycle. With valves 14 and 17 closed, loc~-hopper 16 i8 ~llled to a predetermlned depth with coal from lock-hopper 10 through open value 12 and line 11 at essentlally atmospherlc pressure. Then, wlth valves 12 and 17 closed, loc~-hopper 16 1~ pressurlzed to a pre-determinedpre3sure above reactlon sy~tem pressure through open valve 14 and line 13. Valves 12 and 14 are then closed and ooal i~ introduced into ~luidized ~eeder vessel 22 through open valve 17 and llne 20. The cycle about loc~-, hopper 16 i9 then repeated. A typical time ~or such a ; cycle is from about 10 to about 30 minutes. With value 17 cloRedJ ~luidized coal i~ ~d at a predetermlned rate through llne 26 to the downstream-process units. Other variations o~ the feeding cycle to the ~luidized feeder are po~slble, o~ cour~e, but they are not lllustrated herein slnce they;do not form the inventive steps o~ this pr~cess.
In ~luidized ~eeder 22, a ~luldlzing gas passeq through line 2~ at a low veloclty Quf~lcient to entrain the ~luidized coal and convey it in dense pha~e ~low through l~ne 26 and into the bottom o~ coal preheater 30, or directly to llne 34 lf no preheat i~ requlred. Alternately, additional gas could be added to the llne conveying the coal ln a dense ~, ". -.
. : . . .

~ ~ 3~3~

pha~e ~low through line 26 to assi~t in the conveyance.
Any non-oxldizing gas can be used a~ the rluldizing gas, e~g. ~uel gas, nitrogenJ hydrogen, steam and khe li~e.
However, it is preferable, in general, to u~e reaction pro-ce~ ga3 or recycle product ga3.
Coal preheater 30 i~ a means to rapidly preheat, when de~lrable~ the ~lnely dlvlded coal partlcles, under ~luldLzed conditions, to a temperature below the minimum temperature for ~ortening of signl~icant reaction range, in the sub~tantial ab~ence o~ oxygen. Preferred temperatures ; are ~rom about 200 C to about 375 C and partlcularly pre~erred are ~rom about 325 C to about 375 C, The s~ream o~ gas-~luldized coal ln dense phase i~ heated upon passing rapidly through the heater having a very favorable ratio of :, heating sur~ace to lnternal volume. The coal is heated in heater 30 to the desired temperature by any convenient means of heat exchange, e.g. by mean~ o~ radiant heat or hot flue gas such a~ depicted in Figure 1 a~ entering the bottom of ~. .
heater 30 through line 28 and exitlrlg at the top of the heater ves~el 30 through line 32. It i8 recognlæed, however, ~hat th~ amount o~ coal preheating needed may be minimized by pre-~ heating proces~ ga~ to an elevated temperature.
i Preheated ~luldized coal particles exit preheater 30 throu~h line 34 and enter the lower end o~ the reactor . ~ . .
~ ves3el 40 ~ubstantlally near the center o~ the bottom i . e .
., .
where the vertical axls intersect~ the bottom of reactor 40.
According to thi~ invention~ the coal particles are intro~
: ::
duced into the lower end of the fluid-bed reaction zone at ; a high veloclty. Thls high velocity may be achieved by acceleratlng the ~luldiz.ed stream o~ coal particle3 to the .

~33_ .

~ ~ 8 3~ ~

deslred veloclty along a constricted path of conrlned cross-section. A nozzle, narrow lnlet port, tapered channel, or any lnlet means whlch narrows, constrlct~ or necks down the cross-sectional area of the passageway to the inlet where the ~luidized coal particles enter the reactor may be used to accelerate the ~luldlæed stream of particles to the de~ired veloclty. The stream of preheated, fluldlzable coal partlcles i9 lntroduced lnto the central up~low zone of the fluid-bed wi~-~n th~ reaction ve~sel at a high velocity in an es~entially vertlcally upwards direction into and through the substantially axially central portion of the bottom o~ the reaction vessel.
Recycle oll may be bed into reactor 40 through line 36. InJection o~ the recycle ls al~o pre~erably at a stream velocity of about 200 ~eet per second or greater, and more pre~erably aboub 400 ~eet per second or greater lnto the lower end of the ~luid-bed reactlon zone within the reactor vessel in an essentlally vertlcall~ upwards direction. Llke ; the entering coal partlcles, the recycle oil stream ~113~s a æub~tantlally ascending path about a sub~antially axially central portion of the reactor vessel. In the ln~ection of the recycle oil and fluldlzable coal particles9 lt is es~ential that they be introduced into the reactor vessel in ~uch a w y that they do not i~medlately and directly s~ri~e the walls o~ the reactor ves~el, a res~lt which could lead .
to unnecessary and undersirable agglomeration. ... :~ -Only one lnlet each for entry of the preheated : coal particle3 and the recycle oil ls shown in Figure l.
ThPs~ lnlets may also repre~ent a multiplicity of inlets ~or ease of operation o~ ~his process. A multiplici~ of ~ ~
inlets may be desirable, ~or e2sample, where the reactor is ~ ~--34- ~-. . .. . . . . . .
: . - '.. . . . ~ '', 761~6- 1 ~83~6al large or when ~epara~ recycle stream~ o~ oil are bein~
inJected separately lnto the reactor. The entry polnt~ ~or the coal particles and/or recycle oll are pre~erably situated near the lnter~ection o~ the vertlcal axls wlth the reactor bottom. Each stream o~ coal particles and/or recycle oil 1B preferably lntroducted at a hlgh velocity at each inlet ln an esqentlally vertlcally upwards dlrectlon, the lnlet ~ltuated at or near the reactor bottom, pre~erably ln the vicinity o~ the vertical axls, In this manner, the sep~rate lO~tream o~ entering carbonaceous material are ~ept separate and apart until rapldly mlxèd ln the fluid-bed wlth partially reacted coal and ch~r p&rticleæ.
.
Char ~rom reactor vessel 40 is continously removed t~hrough llne 44 to valved hot receivers (now ~hown), whlch are intermlttently depre~surlzed and dumped.
--( Char product i8, in fact partlally reacted coal, whlch at the temperature of the reactor ls continulng to ~volve ~mall quantitles o~ tars and other vapors. It i8 .. . .
nece~sary to seal the ga~eR a~ vapors o~ the reactor from ;~ 20entering lnto the char recelver by use Or a blowbac~. Also at the~temperature of ~he reactor, between about 480C and ~bout 600 C, de~lgn and operation of the hot valves between reactor and char recei~er are ordlnarily extremely dl~ficult.
~or thls reason, it i~ necessary to lower the temp~rature o~ the product char below the reaction temperature, preferably to a temperature between about 300 C and about 375~C.
-Lowerlng char product temperature prevents evo- ~ -lutlon o~ tars which otherwise plug line~ and valves of the char recelve~, and allows continuou~ operation of the hot valves. It 13 al~o, de~irable to main~ain at least minlmum ~35~

,., . . ; ~ . ~ - - . :
.~. . ~ .

~ ~ 3~

fluidization in llne 44 charryl.ng produc~ char from re~c~or 40 to receiver. This may be accompl:Lshed by lntroducirlg a small, calculated flow o~ ~;quid water or other IlOn-charring volatile liquid into the take-off lin~ 44 at one or more points directly above the hot valve or valves ~not shown). The steam or vapor generated by vaporization of the added water or other liquid, may serve the ~luidlzation and blow-back needs alone or augmented by small amounts of suit-able blowback gases, such as product recycle gas, hydrogen or steam.
Liquid and vapor products are removed ~rom the reactor vessel through line 42. Entrained car may be removed from the vapor overhead by cyclones (not shown) and returned to the bed and injected at high velocity, if desired, to assist in reducing agglomerating of the fluid-bed to hydrocarbonization zone. Oil, water and gas products may be separated by staged condensation. The oil stream may be quenched to cool the stream down to a temper- ~-ature wherein the light gases and low boiling liquid and water vapor go to the top of a column and the heavy oil goes to the bottom. A heat exchanger, for example, may be used to cool a heavy quench oil cycle and manufacture steam. The bulk of the phenolic product remains with the ~-~
heavy oil, and water and part of the phenolics remaiIls with ~;
the light oil which may be recycled through line 36. The `-~
water product contains phenolics, bases and the like and needs to be decontaminated or cleaned up with or without - :-recovery of the phenols and or base for sale befor~ being dumped or reused. If phenol and cresols are desired as 3~ separated products, this produ~ wat~r may ~e tlSed în a ~, . ,' .
'" ;, ,.
-36~

~ ~ ~ 3~ 6 phenol~ extraction atep.
Fluidlzation gas ls fed into the reactor vessel 4 through line 38. The ga~ preferab:Le is a hydrogen-rich oxygen-~ree gas.
The following examples are illustrative of the concept o~ thls invention, demonstrating the method of preventing a~glomeration of coal in fluidized bed processes via the high velocity inJection of coal particles into a reaction zone.
EXAMPLE I
The apparatus employed, shown schematically in Flgure 1 Or the drawings, comprise two coal feed loc~-hoppers (10,16) connected in parallel to a fluidized feeder 22, a preheater 30 and reactor 40. The entire coal conveying line was constructed o~ 3/8-lnch I.D. by 5/8-inch 0. D. tubing, , . ~
~he tw~ coal ~ed loo~-hoppers (10,16) that ~ed the fluldlzed ~eeder alternately each had a 7-inch I.D. and he~ght of 8 ~eet. The ~luidized ~eeder 22 had a 24-inch I.D. and height of 20 feet. The preheater 30, a lead bath heated by "surface combustion" burners had a 24~inch I.D. height of 12 feet.
The reactor 40 had an Il-inch I.D. ~luid-bed, a bed depth of 17-1/2 ~eet and lnside cross-sectlonal area of o.66 sq. feet.
The average velocity through the dense phase coal feed line wa~ not particularly high, the maximum velocity being approximately 40 feet per second at the lnlet to the reactor and only 15 feet per second at the outlet Or the coal ~eeder, erosion o~ the pipe at these velocities ~till remaining at an acceptable level. Attempt~ -to feed the coal into the reactor at velocities o~ approx-imately 100 feet per ~econd resulted ln agglomeration and ~37-~ . 7~1i6-1 3~6~
co~ing-up of the fluid-bed. A 15/32-lnch diameter tung~ten-carblde n~zzle wa~ used to lncrease the rate at which coal and hydrogen were introduced lnto the reactor to 200 feet per second and provlde an erosion resistance surface.
In operatlon, the reactor was fllled with coal and slowly heated up toward the target condltions and gas flows and pressures were establl~hed. Hydrogen was employed as the gas phase. When the target conditions were established the coal ~eed was begun. On the termination o~ the run the reactor was opened up. No large agglomerates or co~ particles~were found. The operating conditions during the hydrocarbonization are shown ln Table I below:
, . .
~. .

' ~

.

: . :
.
. . :

~, ~
' ,, : , ' .:
, . .
.
.. .. .

' : .
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-38- :

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oO ~L~83~6~
h C) a . u~
rJ I ~ ~ ~ h ~ ~:
u~
R. C~ ~ O O ~ E~
o O ~ S
~t o o Lr\ o~a O ~t O N O ~ /:)~ O
t~ O ~

"
__ _ L~
. U . h ~ o O S tq ~ ~ .
~1 o I ~ a~ ~ s~ :
,Q
u~
lq `
o o ~ o s~ ,q ~ ~ c~
O ~ ~ O ~ ~ ~ e 3~
.. ~ O ~ O ~ ~ S
~1 C~ ~1 0 0 C~ ~D ~ C~ ~ ' :
I o Ir~ I ~ S 5 ~ O
O O N O~:1 0 1 ~
O CO O ~ 00 0 C~ O ~ O
:~ 5::~ O ~ N~1 S :~ F ~
_ ~o I a)O
. S ~ S
¢ O R O ~ O ~
O N C) O ~ a~ 3 tD 1--1 c~ ,~ Lr~ ~ o O F ~ N
. bO 6~ 0~: 0 0~r~ 0~ 0 . ~rl I ~ Nl~ ~ ~ ~ ~ r~
~ o 0 ~ ~ ~ m ~: ~ ~ Q U ~1 1O O ~1 3 a.~ ~ O ~ ¢
~`t~ ~ O O ~/ ~ ~ N ~ C) E-~rl O O U~ O~ ~ O I a ~1 11 o t-- O :~ ~t O 00 h O O S:~
~ 5:1 \~ ~ O ~ ~ f~ N~--1 C) O S O ~rl :, O , :~
~1 C.) : .~
`~ `C bG . : U ~ O N
.
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o a3 h E
H ~ : ~: ~ ~ O
a~
. h d ~ t4 ' ~ O ` ' b~ ~ ~ C~ a ~ ~ tq 0~ ~ h u~ u~
.~ ¢ Cq O ,D ~ 0 0 ~` E I P~ O ~1 ~
N C~ a) 5 O 1-~ ~ O Q) ~: h ~1 C~ 0 o S~ ~ C~ O
U a3 h ~ ~ s::
~ ~ b~ ::1 ,: ~ I o o c~ ~ S ~a O O ~ N ~ ~
O o Lt~ O ~ o I ~ ~ h S
. o t-- O ~ O 0 In 3 o~1 ~ O ~ a~
~ ~ u~ ~ sc~
o ~ ~ ~ o ~: o o o O 3 h tq O~rl ~ ~ C~
O ~ ~ ~U~
1 ~ ~1 a~ Q) J~ ~1 . J~ ~ r~l h Q~
a) ~ d O rl a~
h ~ Q~ q :5 o ~ ~ ~1) O J~ ; ~rJ ~ 1~ ~ a~
h ~ d) O ~ 3 0 q) S
~t h ~ aJ S ~ u~ H
u~ o ~ ~ O P~ O ~ L1 .~
h ~ O *
a) ~ E~ tq ~:
- ~ ~ ~11 O ~ ~rl E~ h ~ N ~ ~ ~1 :Y O O ~rl ~ ~ S ~~I td a ~z; ~ ~ ~ ~ ~ E~
c) c~ ~ ~ ~ bO
d ~
:~a) ~L)~1 o ~ U O O
; ~ r~ u ~ z I -917gL

TABLE II - LAK~ DE SMFT COAL, WYOMING
SUBBITUMINOUS C (ANALYSIS~
Moisture and Ash ~ ~eight P~rcent C 72.0 1 .0 o 20.4 Ash11.9 (dry basis) Water30 (as received5 .~ ,. ~ EXAMPLE II
. .
Two additional runs were conducted employin~
apparatu~ and procedures simllar to those employed in Example I, except that oil~ the higher boiling ~ractiorls of the liquid products, was recycled to the reactor. These additional runs were conducted to determine whether a high -~
veloclty lnJectlon o~ heavy oil could be ~ed t~ the rea-tor wlthout agglomerating the ~luid bed. The oil recycle equip-ment added to the pllot plant apparatus comprised a stora~e tank~ to hold the recycle oil, an oil preheater to preheat the oil prlor to in~ectlon into the reactor.
The main hydrogen stream to the reactor was split into two roughly equal streams, each of which was preheated to 300 C to 350 C. The heavy recycle oil was pumped lnto one o~ these hydrogen streams and injected into the reactor -~
through a 1~4-inch dlamet~r tungsten carbide nozzle at approximately 400 ~eet per second. The nozzle, which polnted vertically up the reactor, was located in the center of the reactor bottom 5 feet about the coal inlet The other hydrogen stream was mixed with the preheated Goal~ and lntroduced lnto the bottom o~ the reactor through a 15/32-inch dia~eter tungsten-carbide nozzle at approx-4~_ ' ' ' ~ ' .

~ . ... .. .... . . . . . .. . . .. . . ... . .

76~6-1 ~015 3~6~

imately 160 ~eet per second ln a vertlcally up~ard~ directlor).
The date for these runs are summarlzed below ln Table III.

TABLE III
Run Coal Feed Rate lOOO lb/hr 1003 lb/hr Coal Feeder Pressure llOO pslg llOO psig Reactbr Pre~sure500 psig 500 pslg Reactor Temperature550 C 580 C
Reactor Fluldlzation Veloclty 0.5 ~t/sec 0.5 ~t/sec Length of Run 5 hrs 5 hrs Recycle 011 ~eed Rate 100 lb/hr 240 lb/hr Coal - H2 irlet v~l~cl~y 160 ~t/sec 160 ft/sec Oil - H2 ~nlet velocity 420 ~t/sec 420 ft/sec ~' .
Mo problems were enclountered in ma~ing these runs.
There was no evidence o~ agglomeration in the fluid bed, even when lnjectlng oil at the 240 lb~hr rate.
... .
EXAMPLE III
j The bench-sc~le apparatus employed ln thls exam~le .
ZO comprised a pulverized soIid hopper having a solid's capacit~
of 4.5 llters and constructed from a 3-inch diameter by ., . .
4-~oot high~schedule 80 carbon steel pipe; a reactor was made of l-inch I.D. by ~-inch high stainless steel tube h~v-ing a l/4-inch wall thickne~ and e~panded head 4-inches high and 2 lnches I.D.; solids over~low line constructed o~
1/2-lnch Schedule 40 plpe; a vapor line constructed from 3/8-inch 00 D. stainless steel tubing; and a solids feeder.
Two liquid ~eed pumps, Lapp Micro~low Pulsafeeders were used, one to feed the liquid being investigated and the other to ~eed water for steam generation. Elec~rically heated liquid and water vaporizer and superheaters con-structed of l/4-lnch O.D. qtainless steel tubing were in-stalled bet~Jeen the ~eed punp~ and the ~eed lnJection nozzle ~ ~ 3~ 76~6-1 to the reactor. Thermocouple located 3,6,8 an~ lnche ~rom the bott~m of the reactor were :Lnstalled ln a 1/4-lnch O.S. thermowell placed axially in the center of the reactor.
The lower three thermocouples were in the fluldized bed wnlle the upper thermocouple was ln the vapor space above the bed.
In operatlon, tars boiling above 235C obtained from hydrocarbonization of La~e de Smet Coal were employed as the feedstoc~ ko the reaction zone for conversion to oils boing below 230 C. The tars were dlstilled ~rom the whole llquid product obtained from the hydrocarbonization - int~ various dlstlllation fractions and a blend of the3e -~
distlllation fractions used ~n thi~ example had a nominal atmospheric temperature range ~or 75~ oP the tar betwee~
235 C and 460 C. The remainlng 25~ boiled abo~e 4~0 C.
The solids feed hooper was filled with La~e de Smet hydrocarbonlzation char as described herein above. The water and ~ar feed reservoir~ were ~illed and heated to operating ~emperature. During the heat up perlod, a predetermined flow of hydrogen passed through the empty reactor. As 800n as operating conditions were approached, the char feed and water ~eed (superheated steam by the time it entered the reactor thr~ugh the in~ectlon ori~ice) were started. The three thermocQuples located in the fluidized bed, at the levels indicated hereinabove, served as an indication of bed behavior. Attemp~ to feed thls tar stream at velocities of 100, 200 and 300 ~eet per second resulted in rapid agglomeration of the fluidized reactor bed. A 26-gauge hypodermic needle wa~ used to achieve a 400 ~eet per second inlection velocity o~ the whole tar ~eed. Using thi~ inlet velocity for the whole feed, coking up of the -42- , . .

~ ` 7646~1 ~3~

~luidlzed bed wlthin the reactor was prevented under the followlng operatlng conditions contained in Table IV.
TABLE IV - OPERATING CONDITIONS -LAKE DE SMET COAL
. . .

Pressure 150 psig Hydrogen Partlal Pressure 115 psig Residence time of Vapors in char bed based on superflclal llnear velocity 1.33 sec Char Feed 250 g/hr Oil Feed Rate 2 ml/min Water (as steam) Feed 3 ml/min Hydrogen Flow to Reactor 35 SCFH
Moles Hydrogen/Moles Water 45/1 Temperature 650 Superficlal Linear Velocity of Hydrogen 0.5 ft/sec Time o~ Run , 5 hrs.
Fluidiz~ng Gas ~ H~drogen .

, ..~ .

~ .
-43- :

';

. : . . . . . ~ . : ~ -. ..
.

764~-1 83~6!0 EXAMPLES IV_- XXII
The apparatus employed ln these examples ls sho~/n schematlcally ln Figure 2 of the drawings, and consisted essentially o~ coal hopper 1~1 having a 350~-gram capacit~
constructed from a 3-lnch diameter by 4-foot high schedule 80 carbon steel pipe; reactor 103 comprislng reaction zone 105 constructed rrom a l-lnch I.D. by 9-inch high stainless steel tube having a 1/4 inch wall thic~ness and expanded head 107 c3nstructed from a 2-inch diameter by 18-inch high schedule 80 pipe; steam-cooled condenser 109; two water-cooled condensers 111 and 113; and gas recycle c~m-pressor, not shown. To ensure removal of condenslbles from the vapor stream, the system also employed either solverlt scrubber 115 or activated carbon trap 117. Reactor ~03 was equipped with an axially-mounted thermo~Jell, not shown, containing ~our thermocouples located one, four, seven and twelve inches from the bottom o~ react~r 103.
In operation, hopper 101 i~ charged wlth a weigheu amount of 40-100 mesh subbituminous C coal whlch wa~ mined and lmmediately store under water. The coal is brought to the reactor and dewatered and ~ried under non-o~idizin~
conditions. The sy~tem is purged of air, reactor 1~3 ls heated to about the desired reaction c3nditions and gas ~lows and pressures are established. Hydrogen ~rom gas c~llnders is employed as the gas phase. When the desired temperature, pressure and gas ~low rates are e~tabli~hed, the coal feed ls begun and continued until the hopper is emptyJ at which time the system isshut down and cooled. -~
During the run, char iSJ removed ~r~m reactor 103 throug~
overflow line 11~ and collected in char receiver lcl, and -4~_ .~.

cl ~.
: ' . ' . , ' '.' ~ ,' ' ,::

3~ 6~

tars and water are allowed ~o accumulate in condensers 1~, 111 and 113 and scrubber 115, if employed.
On the termination of the run, the char receiver is emptied and the char is weighedO The condensers ar~
drained into a common receiver 123 and the product is filtered, with the fllter cake being added to the char ~or purposes of determinlng yields. The ~iltrate is then stripped to remove solvent, if present, and water, to ~ettle temperature of 200 C. at atmospheric pressure. Any light oil which distilled of~ with the water is separated ~rom the distillate by decantation and ret~lrned to the still.
The tar i9 then distilled to recover four fractions: (1) a first fraction boing below 130 C at atmospheric pressure and a reflux ratio o~ 3 to 1; (2) a second fraction, or "light oil", bolng at 130 C. to 260 CO at 50 mm. and a reflux ratio of 6 to 1; (3) a third fraction, or "middle 3il, 1l boi~g at 260 C. to 340 C. at 10 mm. and a reflux ratio Or 3 to 1; and (4) a residue consisting o~ pasting oLl (boiling at 340 C. to 350 C. at 10 mm.) and pltch. ~-Tar fraction~ are analyzed by titration-or ga~
chromatographic analysi~ for the presence o~ phenolic materials or "tar ac~ds."
The data ~or these experiments are summarized in tQbular form below: -:
~45 .

76~
33~

o ~ ~ c~ ~ o o o a~
c~l ~ ~ o c~
,~

_1 O ~ O ~ a~ 'I
~1 o ~ cr~ ~ c:, ~ ~ a) u~
r~

u~ 0 C`l u~ ~1 0 C~ ~'7 ~ OCO 1 .
~D ~ ~ O O~ O ~ O O ~ ~ O
, . . . o . . ~ o~ ~
ul ~1 ~1 ~ ~ ~ Ul ~ ~ 00 U~ -r~

` C~ o C~ o ~o o o . ... . . . o o o GO ~ U~ C~ ~ 00 00 U~ O ~ 00 CO
, 1~~1 ,~ ~1 , .
, . .. .
, ' .
, 1~ ~ ~ ~1 ~i O OC~ 00 ~ ' : ' S~ ~ V ~
, r`_1 _1 ~1 ' '~ . -~ : . .
0 0 1~ U~ O :CO ~ _~
.... - - ~ L~ O
: , ~ ,,, . _, , r~
~o ~ ~ o c~ 0 : 4~ , . ' C~ l O C10 CO L~ O O O ' 0~ 10 ~ ~.1 ~1 ' ' . :, .... - - ~8 ~ O
~;~ C~ U~

1 o ~ a~
~ ~ 0~
a~ g ~ û s~
æ ~ o ~ ~ ~ V 0 ~q U
- ,~, ~ ~ o s~
_I J~ r.o ~ (U ~ ~1 o c~
_~ ~ ~ ~ O P~ O ~ ~
,,, m ~ c~ ~: ~n ,., e~ ~ :

_~6-, ~ . .. .

7646- l 3~6~

~ C`l ~ O ~ U~ ~ O ~ c~
N ~i U~ l O a~ U~ O at O Ct~

r-l , ~) ~ O ~ o ,~ O u, o In o u~ ooo ~ c~ ~D

U'l ~ O O~ ~ C~ ~ 0 11 - O ~ l O cr~

QO C~ ID ~ O ~t ~ ~1 ~4 ~ U~ ~ ~ O ~ ~O

~ D O U'l O ~ _l ,QO

O ~1 ~ C`l ~ C~l ~O o o U~ ~ o U'~ C`J o~ ~ C~ O oo o o U~ r~ ~

. .
' ' O O 1~ 0 ~0~ 00 0 1~ Co'~ O
. ,, ~ ~ o~ o~
: :
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C ~ J¦ ~ o ~ o ~ h .
. ~ - . ,: , . . ~

761~6- 1 33iU6~

Results 4 5 6 7 8 9 10 . .
Produc t Yields Wto~ ~AF Coal Char . 58 . 2 49 . 5 54 . 2 44 . O b,4, 648 . 4 35 . 8 Tar 15.3 23.4 17.0 27.6 25.419.5 28.0 Gas 12.0 13.0 11.9 18.5 19.916.5 19.9 Water 15 . 6 13 . 6 18 . 0 14 . 7 13 . 515 . 6 18 . 3 Ultimate Arlalyses ~F
C 87.3 - 89.0 89.2 89.194.0 92.0 3.7 - 3.8 4.5 4.34,3 4.~
N 1.4 - 1.3 1.3 1.31.7 1.2 S 1.0 - 1.0 103 ~ .1 0.7 0 6.6 ~ 409 3.7 4.2(-1.1 )1.6 Tar Ac~d~, wt. ~b -MAF Coal 0-~60 C. 4.5 - 407 5.8 - 4.4 260-340 C. 0.9 - 1.5 1.6 ~ 1.1 ~-Total 5 . 4 - 6 . 2 7 . 4 - 5 . 5 E[ydrogen con3umed9 w~/O MA~ Coal 1.1 1.9 1.2 2.1 2.21.9 2.2 Tar/H~ r tio 13 . 9 12 . 3 14 . 2 13 .1 11. 510 . 3 12 . 7 ~ ~
Tar Acit/H2 ratiD 4.9 - 5.2 3.5 - 2.9 - ;
. ' ' '`
~.

-~8-.;

7645- l 33~0 ~::ontinued) Results _ 11 12 ;l3 14 _ 15 16 Produc t Yields W~.% ~F Coal Char 50 . 7 45 0 0 50 . 4 44 . 140 . 250 . 3 Tar 22.3 25.6 21t,3 20.8 25.3 21 0 Gas 14.9 18.0 13.7 19.5 17.5 13 7

6~a~er 12.8 15.3 16.0 16.7 16.7 16.5 Ultimaee Ana1yses MAF
88.1 9002 90.1 91.2 91.8 90.5 H 4.1 4.2 3.9 3.9 4.3 3 8 N 1.3 1.5 1.2 1.3 1.4 1 5 0.6 1.1 1.0 1.3 1,4 0.7 0 5.9 3.0 3,8 2.3 1,1 3.5 Tar Acids, wt. %
P [Al? Coal 0-2~0 C 5.0 - 5.1 - 4.4 5.5 2~0-340 C. 1.7 - 1.5 - 1.9 1.5 Total 6.7 - 6.6 - 6.3 7.0 Hydrogen ~onsumed, w~O% MAF Coal 1.8 2.4 1.4 2.8 2.5 1.5 Tar/H2 ratiO 12,4 10.6 15.2 7.4 10.1 14.0 Tar Acid/H2 r~tio 3.7 - 4.7 - 2.5 4.7 , . . . - , . .

~ ~ ~ 3 (Continued) Re~ult~ 7 18 19 20 21 22 Product Yield~
W~.Z MAF Coal Char 3906 38.5 37.5 39.8 33.3 38.4 Tar 27.8 28.4 29.1 27.3 27.3 29.0 ~as 22.5 21.8 21.0 17,9 2107 19.2 ~a~er 16.6 15.8 15.0 15.2 19.3 16.2 Ul~imate Analyses MAP~
~ 92.5 93.0 93,5 92.0 94.0 93~0 H 4.1 4.2 4.2 4.0 3.7 3.8 N 1.6 1.4 1.2 1.3 1.1 1.3 S 1.3 1.2 1.~ 0.6 1.2 0.6 0 0.5 0.2 0.0 ~.1 0.0 1.3 Tar Acids, wt. %
MAF Coal 0-260 C. - 5.7 - 6.3 - 7.6 260-340 C. - ~.4 - 0.8 - 0.8 To~al - 7.1 - 7.1 - 8.4 Hydrogen cons~med, :
wt.% MAF Coal 3.3 3.4 3.5 2.9 4.1 3,5 Tar/H2 ratio 8~4 8~4 8~3 9r4 6~8 9~4 Tar Acid/H2 ra~o - 2.1 ~ 2.4 - 2.4 3~l60 7646-:L
EXAMPLE XXIII and XXXIV

Two addltional run~ are conducted elnplc,~in!~ appara-tu~ and procedures simllar to those elrlployed in Exa~npl~, IV-XXII except t,hat the product gas ls not recycled to the reactor. These additional runs are conducted to determine the e~ect o~ the carbon dioxide present in the recycle gas on hydrogen con~umption. The data for these runs are summarized below.

Coal Ultlmate Analysis, MAF
C 73.7 73-~
H 5.1 5.1 N 1.0 1.3 S 1.0 1.0 0 1~.2 19.6 Ash, moisture free 8.5 8.5 Reactlon Conditions Temperatur~, C. 544 531 Pr~ssure Total, psig, 600 600 Hydrogen, psi. (partial pres~ure) 600 600 : Sol~d~ residence time, ml~utes 13.2 14 8 Total ~ime ~r. . 12.4 11 3 SH . 624 615 Results Product Yields Wt~ MAF coal Char 45.6 48.5 Tar 2~.6 25.2 Gas 16.0 14.2 Water 16.8 13.7 . Char-Ultlmate Analysis, MAF
C ~0.5 90.4 ~:
H 3.9 4.1 N . 1.2 1.2 . ~
S 0.9 ~ 9 :- :
o 3 5 3 4 Tar Acids, ~ MAF Coal : 0-260~C. 6.3 ~ 1 260-340CC. 1.3 1 5 Total 7.6 7.6 . .
.. ... ~ :
, 761~6-1 ~ 6~

Hydrogen consumed, % MFA Coal 2.0 1.6 Tar/H2 ratio 11.8 15.8 Tar acid/H2 ratlo 3.8 4.7~

By comparison o~ the amount~ of hydrogen consumed and tar and tar acids produce~ per,unlt hydrogen consumed in the~e examples wlth tho~e runs employing recycle having ~imilar severity factors (SH) it can be seen that improved results are o'otained when no gas recycle is employed. Thu~, at a sever~ty factor o~ 624 wlthout recycle (Example 23) the amount o~ hydrogen con~umed ls only 2.0 per cent of the `' coal~ as compared with 2.9 to 3.5 ~or Examples 19 and 23. ~' In addltlon, the ratlos of tar and tar acids to hydrogen consumed i9 11.8 and 3.8, respectlvely, ln Example 23. In contrast, the tar to hydrogen ratios in E~amples 19 and 2.~
is 803 to 9.4, and the tar acid to hydrogen ratio of Example 20'was only 2.4.
These improved results are due to the avoldance of ' the followlng reactions.
, H2 ~ C2 ~ 2~ ~ C0 ' 3H2 ~ C0 --~D CH~ + H20 becau~e o~ the presence o~ carbon dioxide or monoxide ln the system in significant amounts due t3 recycle.
EXAMPLE XXV ~.' Empl3ylng te,chnlques similar to those empl3yed in the preceding examples, a pilot-plant ~un is made o~er a~out ;
one wee~. The 'reactor in thls run is 11 lnches in diame~er .
and 2~ reet high. The hydrocarbon1zation temperature is 540C., the hydrogen parti.al pressure is 397 p~i and the ~ :~
~, . .
sollds residence t.ime is 14.3 minutes, for a hydrocarbonizat-ion ~actor (SH) o~ 606.

.~ .

' _52~
. .

761~6- 1 ~ ~ 3~ ~ ~

The product yie]dsg basecl on MAF coal, are 53 per cent char, 19 per cent tar, 15.5 per cent gas arid 15.2 per cent water at a hydrogen consumptlon of 1.74 per cent ~asec~
on MAF coal. Tar acids boillng below 230 C. amounted t3 5.~0 per cent of MAF coal. Thus, the ratio of tar to hydrogen consumed ls 10.9 and the ratlo of tar aclds bolling below 230 C. to hydrogen consumed is 3.22.
On recycle of tar boiling above 230 C., the yield o~ tar acis boillng below 230 C. ls increased from 5.61 per cent to 7.04 per cent o~ MAF coal at a total hydrogen consumptlon of 1.93 per cent of MAF coal, for a low tem-perature tar acld to hydrogen ratlo o~ 3.65 as compared to .22 wlthout recycle.
The data of thls example, when compared with that of Example 15 also lndlcates the effect o~ simultaneous deal~ylatlon of alkylphenols on product dlstribution. The vapor resldence tlme in the small reactor of the previous ex-amples ia too short to permit the occur~ence o~ slgnificant deal~ylatl~n. In this example, however, the vapor residence time is 18.5 seconds, ~or a sev~rity factor (Sc) of only 640, which ls below the pre~erred range. Nevertheless, the proportlon o~ tar acid boillng below 260 C. to all tar acid bolling below 3~0 C. lncreased from 70 per cent in Example 15 to over 81 per cent in this example. ~ -The coal employed ln several o~ the following ex- ~
-, periments is generally ~nown as La~e DeSmet coal. This coal Is taken from an unusual formation in Northern Wyoming and exlsts ln the form o~ lens of coal with thic~nesses up to 200 ~eet. This deposlt of coal lies near the surface o~ the ground, and in the time past has partially burned :: :

-53- ~

.. .
.. . .. ,, ~ , , 7646~1 ~83~

out rormlng a basln now ~illed with water. Thi~ ls ~nown as Lake De Smet. The coal employed wa~ ta~en ~rom the land next ad~acent to the Southern border o~ the lake.
The coal ls o~ subbituminous C ran~.
It has been ~ound in one aspect of the present inventlon that even mild exposure o~ the low ran~ Lake de ~met coal to air oxidatlon result~ in a marked decrease in process yield~ o~ phenollc compounds. For example, drying the coal in a commercial vacuum oven at 50 C. and grindlng and screenin~ the dried coal in air reduced the tar yield by about 50 per cent with a proportionate loss of phenolic compounds~
Exam~le XXVI
~DROCARBONIZATION OF IA Æ DE SMET COAL
......... ~_.~.
In the hydrocarbonization of La~e de Smet ~oal, it ls found that extreme care is necessary ln order to prevent oxidation and obtaln truly representative ylelds ~rom this low-ran~ coal.
A sample o~ Lake de Smet coal i~ care~ully protect-ed ~or shipment by placing the wet cores in polyethylene bags and surrounding the bags as they were packed in a box with wet core cutting~. On arrival at the research laboratory, an aliquot ~amp~e of the cores i plcked, partially dr~ed at ambient temperature ln a vacuum desiccator, ground and analyzed. The balance of the core samples ls placed in a commercial vacuum drylng oven and dried over-night at 50 C. The cores are then ground to yield suffi-cient 40-100 mesh coal ~or tow experimental runs. The hydrocarbonization unlt and the operating procedure employed in thi~ and ln all succeeding experiments in this report ~ ~ 3 are descrlbed ln Examples 4-22, The analysls of the allquot sample and the sample prepared ~or experlmental use are shown in Table V. The operatlng condit~ons and the product yields are shown ln Table ~.

' ', ~ .

, ; 5 : ~

7~46- 1 ~3,3 ~ROPERTIES OF I~K:E DE SMET COAL

Allquot Sample Proximate Analysis Weight Per Cent as Experimental __Received Sample Volatlle Matter 33.8 38.2 Fixed Carbon 35.8 45.9 Molsture 19.3 1.5 A~h 11.1 14.4 Ultimate Analysi, Weight Per Cent MAF - - .
C 72.4 72.2 H 5.3 4.3 N 1.6 1.5 -- 106 1.7 O ( by dif'~erence ) 19 .1 ~O . 3 _56_ , 76L~6- l TABLE VI
CARBONIZATION AND HYDROCRABONIZATION OF LAKE, DE SME* COAL
. . .
~e~5=r~9 Col. (1) Col.(2) Col. (3) Experlmental Experimental Non-Oxldized SampleSample Non-Air Dried La~e ~e Smet C.~al .. . . .
Fluidization Gas NltrogenHydrogen Hydrogen Pres~ure, psig 200 400 500 Temperature, ac. 515 515 539 Hydrogen Part la 1 Pre~ure, p81. nil 320 450 Y ld~elght Per Cent MAF Coal Char 76 . 6 68.9 48. 4 Tar 5.9 8.9 19.5 Gas 9.0 11.6 16.5 Water 8 . 5 11. 5 15 . 6 Hydrogen ~ -0 . 9 -1 . 9 00oO 100.O 100.O
.

76~6_l ~ ~ 8 3 Discu~sion of Results .. .. . . _ The yield o~ tar rrom theexperimental supply o~
lake de Smet coal is only 5.9 per cent MAF csal when carbon-ized in an inert atmosphere as ~hown in Column (l), Table VI. The char yield i8 76.6 per cent. Furthermore, Column (2) shows that ln a hydrogen atmosphere, at a hydrogen partial pressure of 320 p91., the tar yleld increases to only 8.9 per cent. Interpolation Or data shown in column (3) obtalned ~rom unoxidlzed coal ln succeeding runs at the l~ same operatlng condltions~ shows that the tar ~ield should be about 1700 per cent and 57.07% char. The char yleld is 68.9. Turning to the ultlmate analyse~ given in Table V, it is apparent that the experimental supply of coal lost h~drogen, down from 5.3 to 4.3 per cent and galned oxygen, up from l9.9 to 20.3 per cent durlng the drylng and grlnd-lng operations. The adverse e~fect of oxldatlon on the tar ylelds from these experiments shows that extreme care ls required in handling the coal ln order to obtain maxlmum ylelds of phenollcs.
~0 ~
., ~ .
Combus~lon processes to produce hot ~lue gases usually are run w~th an excess of oxygen (alr) to ensure complete combustion Or the fuel~ In the tentatlve design for a commercial hydrocarbonizatlon plant, hot ~lue gas contain-ing 2 per cent free oxygen i8 used to dry and preheat the -pulverized coal. Two separate f~uldized vessels are used, a dryer operating at lO0 C. and preheater operating at 285 C.
- A study is made to define the e~fect of using a ~lue gas contalnlng 2 per cen~ oxygen in drying and preheating coal '- ' 761~6~ 1.
33~

upon the tar yleld durln~ sub~equent hydrocarbonlza~lor,.
The method chosen to evaluate the tar yield o~ the treated coal 13 the Fischer Assay test. (U.S.Bureau of ~ines Bu11etln 530, 1953, "Low Temperature Carbonization Assay Or Coal in a Preclslon Laboratory Apparatus," by Go~dman, ~B., Gomez, M., Parry, V~F.., and Landers, W.S.).

The Lake De Smet coal ln this example i9 ta~en rrom a 55-gallon drum in whlch the coal had been covered with water from the time it had been shipped. The wet lurnp coal i9 sur~ace dried, pulverized, screened to obtain a 40-lO0-mesh ~raction) and ~tored under positive pressure nitrogen untll ready ~or u~e. A molsture determination of 29.5 per- -cent shows that thls coal has been little more than surface drled during preparatlon, slnce the molsture content of coal a~ mlned is approximately 30 percent. A 3-quart sample ~f thl~ prepared coal ls put in a l-gallon metal sample can, ~lushed wlth nltrogen, and the lid soldered on. This sample ~No. 1) i used to establish the ba3e yield of tar by the Fi~cher A~3ay, The other sampIes, Nos. 2, 3, and 4 are pre-pared ln the aforementioned hydrocarbonization unit prevlously de~crlbed ln Examples IV-XXII. The pertinent operat ing con-ditlon~ used t~ prepare Samples 2, 3J and 4 are as ~ollows:
. ..... . .

' :

' ' .g ~ .

761~6- 1 ~83~

Notes .__ Samele 1. Raw La~e de Smet Coal; sample contains 29.6 per cent moisture (xylol method) and 6.1 per cent ash.
2. Drled La~e De Smet coal; sample dried at 1~0 C.;
~luldization gas: nitrogen. Sample contalns 5.8 per cent moisture (xylol) and 8.2 per cent ash.
3. Dried ~ake de Smet coal; ~ample drled at 100 C.;
rluidlzation ga~- 2 per cent oxygen and ~8 per cent nitrogen.
~ample contains 404 per cent moisture (xylol) and 8.8 per cent ash.
4. Dried La~e de Smet coal sample dried at 285 C.;
fluidizatlon gas: 2 per cent oxygen and 98 per cent nitrogen.
Sample contains 1.1 per cent mol~ture (xylol) and 8.6 per cent a3h.
~ ' . .
:
Hydrocarbonizatlon ylelds are determined for samples of Wyodak coal. (a subbituminous C coal from a strip mine near Glllette~ WyDmlng.) and Texas and North Da~ota lignites.
The result~ are compared to the results obtained from Lake de Smet coal at simllar operatlng oonditlons.
The experimental æpparatus and the operating procedure are the same as used in Examples IV-XXII and addit~o~lly, alr oxidatlon o~ ~he coal and lignite is also avoided~
Experlments are made to determine the hydrocarbon-izatlon yield~ ~rom Wyodak coal and Texa3 and North Dakota .9 lignltes at 1000 p~ig, 510-535 C. and a residence time o~ 8 - to 10 minutes. For comparison~ the hydrocarbonization yields :

~60-.

`
. .
.. . . . . . .

76L~6_ 1 ~ ~ 3~V

for La~e de Smet Coal, at slmilar operatlng condltlon~, ar~
presented.
The analyses o~ the feed coals and llgnltes and the hydrocarbonized chars are given ln Table VIII. The operating conditlons, yields and hydrogen consumptlon are given ln Table IX. Table X gives the gas ylelds and composi-tlon. The physical properties of the tars are given ln Table XI.

_61-:, . . :, . . . -., . : .

8 3~

Samples 2 ~ ~
Drying Temperature, C. 100 100 285 Coal Feed R~te, g/Hr. 250 250 580 Re~idence Time, mln. 15 15 7 Fluidlzatlon Ga9 Hlgh Purity 98~ Nitrogen ~ Nitr~gen Nitro~en 2~ Oxygen Z~ Oxygen Gas Flow, SCFH 5.6 5.6 5.6 Weight Percent Oxygen Relative to Coal 0 1.7 0.7 The coal receiver i~ allowed to co ~ to room temperature under a positive pressure o~ hlgh purlty nltrogen. The cold sample~ are ~hen assayed by the Fischer Assay test.
~ .
The complete assay results are glven in Table VII.
The pertinent assay results are ~ummarlzed as follows:
Sample Numbers ~- 2 --3 4 Char Yield, ~ MAF 67.6 66.3 66.4 67.8 Tar and Llght 011, ~ MAF 10.4 10.3 9.6 8.8 % Loss ~n Tar Yield -- 1.0 7.7 15.4 The result~ o~ this study show that the Lake de Smet coal 19 sen~itive to as little as 2 per cent oxygen in the ga~ used rOr drying and preheatlng the coal.

., ' ' ' ' -~2~

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~ ~1 o ~ 3 ~
~ ~1 ~, o ~ O ~ ~ ~ ~ o ~ O _I O

H ~il U~ o ~ ,~

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H ~ I o o C~ ~ a I ~
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3~ 76L~6- 1 TAE~I,E VIII

AN_YSES OF FEED COAL AND LIGN ES AND HYDRCCAR~AR
COa1 Or La~Ce de Smet TeXa8 NOrth Da~Ota WYOda~
g , L1gn1te L1gn1te COa1 Ultimate Analysis ~ We1gLht ~er Cent MAF
Feed E1ement C 72.3 1 74.8 1 72.0 173.8 5.2 1 5-7 ~5- 1 5-3 N 1.7 11.6 ¦1.0 ¦1.0 S 1.2 I1.6 I1.1 I0.6 O( bY di~fer~ ~
enCe )19 . 6 ¦16 . 3 ¦20 9 ¦19 3 % ASh, drY
ba~1S18.~ .6 ¦7.6 ¦5.8 C 89.2 18705 ;880,6 I '89.0 H . 4.5 I 4.2 I4.1 4.0 N 1.3 1 2.0 ¦1,3 1.3 S .1.3 I 1.6 I0.8 0.6 0~ by di~er- I I .
enCe~ 3-7 I 4-7 I5.2 5.1 :

- ' ' -.

'~ , :
.
: ' , : , , , . ., :, . - -. . :. .

D~ 76~

TABLE IX
HYDROCARBONIZATION OF_LIGNITES AND WYODAK COAL
OPERATING CONDITIONS AND YIELDS
Operatin~ Conditions Coal or La~e De Smet Texas N.D. Lignlte Wyoda~
Lignlte Lignite Hydro-carboniza~lon T~mperature,C.511 512 510 535 System Pressure, p81g lOOO lOOO 1000 lOOO
Fluidization Hydrogen Hydrogen HydrogenHydrogen Gas Avg. H2Part-ial Pre~ure, p~i. 920 8go goo 920 Residence Time ( de~ined time _rec~uired to fill the carbonizer with ~resh ~eed at 30 lbs/rt~ ~luidized denslty), minutes 8.2 -8~1 9.8 9.8 Length of Run, hrs. ~ 7.83 6.58 7.92 8.42 ~ . .
Char 44. 0 43 . 0* 48 . 3 48 . 1 ~ :
l~ar 27.6 31.2 27.0 26.~ .
Gas 18~5 18.7 14.7 15.3**
Water 14.7 9.6 15.1 11.7 ~:
Hydrogen -2.1 -2. 5 -2 ~ 3 -2 . 0 Unaccounted f'or -2.7 0.O -2.8 0.0 100 o O 100 . O 100 . O 100. 0 * An un~nown amount o~ feed was left in hopper, yields are :
normalized to 100 *~ Ga~ by di~feren~e '~ ~
', 65~

. .

3~6~

TABLE X
HYDROCARBONIZATION_O~ LIGNIT~S AND I~YODAK COAL
GAS YIE~LDS AND~ COMPOSITION

Coal or ~a~e de SmetTexas N. D. Lignlte Wyodak Lignlte Lignlte Wei~t Ga, 370 37 294 306 Yolume Gas, SCF/TonMAF 5300 5820 4570 4830 ~b~e Per Cent Methane35 . 7 45 . 6 44 . 0 48 . 9 Ethane11.4 12.7 11.6 11.3 Propa ne 2 . 1 3 ~ 7 3 . 6 7 . 6 Carbon - Manoxide 29.0 28.3 32.0 26.5 Carbon Di~ide 21. 8 9 . 7 8 . 8 5 . 7 Molecular We lght o~ ma ke Ga s 27 . 724 0 9 24 . 9 24 . 5 ; ~ ' ' ' - -"' -- ' ` -' ' ':

~66-.

, .. . . . . ..

IL~83~6~
TABLE_XI
HYDROCARBONIZATION OF LIGNITES AND WYOD.AK COAL
SOME PHYSICAL PROPERTIES _F THE TAR
Coal or La~e de Smet Texas N.D. Wyoda~
Lignlte Llgnite Lignlte Cyclohexane Insoluble Asphalt Per Cent Tar 21.0 21.7 26.8 17.6 Per Cent MAF
Coal 5.8 6.8 7.2 4.6 Tar Dl~tillation, Welght Per Cent IBP - 1109.3~ 1.8**3.5**
110 - 26029.8 21.529.2 260 - 32010.9 -~
260 - 3~0 ---- 17.816.0 Re~ldue 50.0 55.851.3 Oil Yields. Per Cent MAF Coal IBP - 110 2.6 o.6 1.0 110 - 260 8.2 6.7 7-9 260 - 340 ~-- 5.6 4.3 To~al IBP
320 13.8 -_______ .
Total BP -3 ~~~ 12.~13.2 _67-3L~83~ 76~

Phenol s _a nd Ne ut ra l Oil Yle~ ~6 MAF Coa 1 _I 1 n/~ :W r~

Phenols 5 . 8 3 5 5 7 Neutra 1 011 2 . 5 3 2 2 2 ~60 - 320 Phenols 1. 6 -~
Neutral Oil 1. 5 Phenols ---- 2. 4 2 5 Neutral 011 ~ 3. 2 1 9 Total Phenols, 1 10 -3 20 7 . 4 - _ _ _ ~ _ _ _ ~otal Phenols 110-340 ~ 5 . 9 8 . 2 _68-, , . . ; . : .
. ~ . . , . . :

76~6-1 ~ ~ ~ 3~3~

* Dlqtillatlon ln a pac~ed column with re~lux ** Vlgreaux dlstlllatlon on llgnlte tars.
The hydrocarbonlzaklon of a sample o~ Texas llgnite in a hydrogen atmosphere at 1000 p91g and 510 C. gave a yield of 625 pounds o~ tar per ton of moisture and ash ~ree lignite. This may be compared to a tar yield Or 55 pounds per ton when La~e de Smet coal ls hydrocarbonized at the ~ame opera~ing condit,ions. A North Dakota lignite and Wyodak coal gave about the same tar yield as the La~e de Smet coal.
The light oil phenol yield i9 115 pounds per ton of MAF ~eed ~or the North Dakota llgnite and the La~e de Smet coal. The light oll phenol yleld for the Texas lignite is 70 pounds per ton o~ MAF lignlte.
- :

--~9_ ., .. . . .

Claims (20)

WHAT IS CLAIMED IS:

1. A process for the hydrocarbonization of coal particles employing a fluid-bed zone of hydrocarbonization consisting essentially of:
a. fluidizing said particles with a non-oxidizing gas to form a dense phase;
b. pressurizing said particles with a hydrogen-rich gas;
c. preheating said coal particles in said dense phase in an essentially oxygen-free environment to a predetermined temperature below a temperature at which said coal particles undergo plastic transformation;
d. providing a fluid-bed within said zone for hydrocarbonization at a reaction temperature of between about 480°C and about 600°C, said fluid-bed comprising a matrix of non-agglomerating particles at said reaction temperature fluidized by a hydrogen-rich, oxygen-free gas;
e. continuously introducing said coal particles and a hydrogen-rich, oxygen-free conveying gas into the lower portion of said zone in an essentially vertically upwards direction, said coal particles having a velocity greater than about 200 feet per second and sufficient to rapidly and uniformly disperse at said predetermined temperature, within said matrix.
f. continuously reacting said coal particles in said zone with hydrogen in said zone at said reaction temperature to produce a product comprising a condensable vapor and solid char.

g. maintaining the solids in said zone for an average residence time of about 5 to about 60 minutes and said vapor for about 10 to about 250 seconds;
h. maintaining the average hydrogen partial pressure in said zone at about 100 p.s.i. to about 1200 p.s.i.; and i. continuously withdrawing from said zone said product vapor and solids.

2. A process as defined in claim 1 wherein in step e, said coal particles and said conveying gas are introduced through the substantially axially central portion of the bottom of said zone.

3. A process as defined in claim 2 wherein said coal particles and said conveying gas are introduced into the lower portion of said zone through at least one inlet having a constricted cross-sectional area designed to accelerate said coal particles and said conveying gas to said velocity.

4. A process as defined in claim 3 wherein said coal particles and said conveying gas are introduced into said lower portion of said zone through a multiplicity of inlets.

5. A process as defined in claim 3 wherein the surface of said inlet through which said coal particles flow comprises a wear-resistant material.

6. A process as defined in claim 5 wherein said wear-resistant material is tungsten carbide.

7. A process as defined in claim 1 wherein in step g, said average solids residence time is about 8 to about 30 minutes.

8. A process as defined in claim 1 wherein in step d, said non-agglomerating particles comprise partially reacted coal and char particles, and in step h, said hydrogen partial pressure in said zone is between about 200 p.s.i. and about 800 p.s.i.

9. A process as defined in claim 1 wherein said coal particles comprise non-agglomerating sub-bituminous or lignitic coals.

10. A process as defined in claim 9 wherein said coal particles have at no time been exposed to oxidizing conditions prior to hydrocarbonization.

11. A process as defined in claim 1 wherein said coal particles are finer than about 8 Tyler mesh.

12. A process as defined in claim 1 wherein said coal particles comprise agglomerating bituminous coals.

13. A process as defined in claim 1 wherein said coal particle velocity is greater than about 400 feet per second a

14. A process as defined in claim 1 further including in step e introducing a stream of recycle oil into the lower portion of said zone in an essentially vertically upwards direction at a velocity greater than about 400 feet per second.

15. A process as defined in claim 14 wherein said recycle oil velocity is greater than about 400 feet per second.

16. A process as defined in claim 1 wherein said predetermined preheat temperature is between about 200°C and about 375°C.

17. A process as defined in claim 16 wherein said predetermined preheat temperature is between about 325°C and about 375°C.

18. A process as defined in claim 1 further including after step i, j. lowering the temperature of said solid char product to a temperature between about 300°C
and about 375°C.

19. A process as defined in claim 1 wherein the reaction temperature, hydrogen partial pressure and solids residence time conform to the equation:
SH = T(P)0.067 (t)0.067 wherein SH is a hydrocarbonization severity factor having a value of from 550 to 700; T is the hydro-carbonization temperature in °C; P is the log mean average hydrogen partial pressure in said hydrocarbonization zone in p.s.i. divided by 1000;
and t is the solids residence time in minutes.

20. A process as defined in claim 19 where in order to maximize total liquid product and minimize hydrogen consumption, the temperature and vapor residence time conform to the equation:
Sc = T(.theta.)0.048 wherein Sc is a vapor cracking severity factor having a value of from 600 to 690; T is the temperature in °C;
and .theta. is the average vapor residence time in seconds.