CA1049433A - Carbonaceous material - Google Patents

Carbonaceous material

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Publication number
CA1049433A
CA1049433A CA231,705A CA231705A CA1049433A CA 1049433 A CA1049433 A CA 1049433A CA 231705 A CA231705 A CA 231705A CA 1049433 A CA1049433 A CA 1049433A
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CA
Canada
Prior art keywords
blend
weight
carbonaceous
coal
coking
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CA231,705A
Other languages
French (fr)
Inventor
Adriaan H. Stander
Leonard J. Dry
Andries Brink
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South African Coal Oil and Gas Corp Ltd
Original Assignee
South African Coal Oil and Gas Corp Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by South African Coal Oil and Gas Corp Ltd filed Critical South African Coal Oil and Gas Corp Ltd
Priority to CA231,705A priority Critical patent/CA1049433A/en
Application granted granted Critical
Publication of CA1049433A publication Critical patent/CA1049433A/en
Expired legal-status Critical Current

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  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

ABSTRACT

A novel carbonaceous material derived from solid carbonaceous fossil fuel, in particular low rank coal, such as brown coal, having a low ash and sulphur content, is prepared by deoxygenation and dewatering in the presence of hydrogen and a sol-vent having hydrogen carrier properties (e.g.
anthracene oil under conditions known per se for the solvent extraction of coal.) The entire lique-form reaction product is distilled down without prior filtration and recovered as the product which, besides the soluble components also includes the ash and carbonaceous insolubles. The material which has a ring and ball softening point above 30°C, pre-ferably above 100°C, is particularly useful for blending with coal having inferior coking properties in order to produce a coking blend useful for the production of metallurgical coke, applying conven-tional coking conditions.

Description

The present invention rela.tes to a carbona.ceous ~a.terial derived from solid ca.rbonaceous fossil ~uel, sub-jected to deoxygenation~ and where a.ppropriate dewatering, in -the presence of hydrogen ~nd a solvent ha.ving hydrogen carrier properties.
In the so-called solvent refining of co~.l, which process ca,n be applied to modera,tely hi.gh ra,nk through to low ra,nk coals, the coa.l, in a. pa.rticulate condition, is subjected to liquefaction in a high-boiling solvent7 (e.g, boiling between 200 and 450C), suita.ble as a hydrogen carrier (in a physica.l a.nd/or chemical sense), at a. tem-, perature a,bove 350C, say between 350 and 500C in the pre~ence of hydrogen, a,t a. pressure of about 30 to 250 bar.
After ha.ving been subjected to this treatment for about 15 to 120, ~ore pa,rticul~rly 50 to 90 minutes, the pressure is let down from the reaction product a~d the liqueform rea.ction mixture is subjected to a step of solids sepa.ra-tion, usua.lly filtra.tion, in order to remove therefrom all non-dissolved mattex, namely the char-like 301ids such as fusain and the ash. ~he clear liquid phase is then sub-jected to distilla.tion whereby the solvent is recovered ', and recycled, wherea~ the ~ubstantially non-volatile bot- :
: toms o~ the distillatio~ constitute the so-called solve~t ,~ refined coal (SRC) which can serve as a feed stock for ca.talytic hydro-cracking. ~he object of the solvent- :
refining o~ coal7 of which the solids removal step has always been an integral a.nd essential part, is the . '~
obtaining of a feed stock of low o~ygen and sulphur conte~t and substantially free of substances which can ~:
harm the catalyst physica.lly or chemically i~ the sub-.

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1~49433 sequent hydro-cra.cking step. Where SRC is advocated as a. fuel, its low ash and sulphur contents a.re in-varia.bly quoted a.s favourable chara.cteristics, which ca.n ma.ke a.n importa.nt con-tribution towards air pollu-tion a.ba.tement. ~he comparatively di~ficult solids remova.l step is thus a.n important a.nd e~sentia.l part of the known processes because the sepc~ration o~ ash ~.
a.nd carbonaceous insolubles harmful to the cata.lyst or for other purposes, i9 one of the prima.ry objec-ts of such processes. :~
Conventional solvent re~ined coa.l (a.n essen-tia.l characteristlc of which i9 the virtua.l a.bsence ; of ash) is known to have properties making it ~uit-a.ble for coking purposes. In pa.rticular, by blending . 15 a relatively small propor~ion of ~RC with a poorly coking coal, the coking properties of the coa.l a.re :~ substantially upgraded. However9 the comparativel~
:~ high cost o~ conventiona.l SRC ha.s mitigated again~t .
its production on a. commercial scale and hence its use for th~.t purpose.
.l It i9 an object of the pre~e~t invention to provide a novel product which ca.n be ma.nu~a.ctured by a. compara.-tively simple process and which nevertheless has some of the valuable properties of SR~. ~he invention i3 i.' 25 particula.rly applicable in a.ppropriate circum3ta.nces to , th0 provision o~ a ra.w material for upgrading coa.ls used .j in meta.llurgical coke production. ~-~ In accordance with the pre3ent i~vention a. ma.terial :~
; a.s de~ined in the introductory paragraph consists o~ or ~,: 30 comprises the combined, substantia.lly non-vola.tile, sub-. I ~

:~ :

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1~9433 sta.ntia.lly solid product a.nd residues o~ sa.id deoxygena-tion (and where a.ppropriate dewatering), including ash and carbona.ceous insolubles, the materia.l having a.n R
a.nd ~ (ring and ball) softening point above 30C. In practice this value is preferably above 100C. Prefer-ably the total char content (i.e. a.sh plus carbonaceous insolubles) i5 less than 12%, more preferably less than 8%. Pre~erably the actual ash content is not more tha.n 10%, preferably not more tha.n 7%, a.ll by weight of dry solid matter. .:
Also pre~erably the product contains at the most
2% sulphur, preferably less than 0,5% sulphur. (By weight) ~he scope of the invention includes coking coa.l blends incorporating such product as above defined.
~he scope of the invention is also intended to embrace coke ~anufactured from a material or blend in a.ccordance with the in~ention as defined a.bove, and the use o~ such coke for metallurgical purpose3, e.g~ for use in blast furnaces.
Also in a.¢cordance with the invention there is provided a proces~ for the manufacture o~ a materia.l as defined above, preferably ~-~ a cokLng coa.1 ble~d starting :.
material suitable for use in the production of metallur-l.~ gical coal, which comprises subjecting a solia ca.rbona- ~ :
1 ~ 25 ceous ~ossil fuel material containing preferably not more than 7%, more preferably not more tha.n 4% by weight of ash, a.nd preferably not more than 4%, more prefera.bly .~ not more than 2% by weLght of sulphur, both based on .~ solid dry matter, but of which the oxygen content is un~
.: ~0 aesirably high, more particularly too high for sa.tis-. ~
~, j .
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-1~49~33 factory coking properties, to a step of deoxygena.tion and removal of such water as ~ay be presen-t, which step com-prises heating the ca.rbonaceous material in in-timate conta.ct with a liquid solvent and a hydrogen carrier and hydrogen under pressure to e~fect the deoxygena.tion, followed by distilling the solvent a.nd such volatiles a.s a.re for~ed off the combined product of sa.id hea.ting, a.nd recovering the combined residue of such distilling a.s a product.
More preferably the sa.id solid fuel ~ateria.l used a.~ a. starting material contains less tha.n 2% of ash a.nd preferably also less tha.n l~o of sulphur, both ba.sed on solid dry ma.tter. However, higher ash and sulphur con-tents ma.y be accepta.ble, provided the final product meets the required specifications.
In order to guide the process towards the formatio~
of solid products as defined in the aforegoing, principles are adopted which a.re known as such to those ~killecl in coa.l liquefaction, a~oidance of very high pres~ures a.nd :.
temperatures a.nd the a~oidance of catalysts which a.re known to favour the formation of liquids.
~he hydrogen carrier m~.y be and preferably is pro-vided by the solvent itself, more particula.rly by such solvent comprising hydroaromatic compounds.
~` 25 It is also possible for the hydrogen carrier to be ~i~ supplied wholly or in part by a non-vola.tile hydrogena.- :
tion catalyst, which may be added to the syste~ for that purpose, or may be present in the ash of the coa.l.
However, the presence of a catalyst is not an .
es~ential prerequisite.

.~
3 3 ~he proce~s may be carried out with technical hydrogen or with hydrogen-containing gas mixture~, such as industrial mixtures comprising hydrogen and carbon ~onoxide a.nd steam, or mixtures which ca.n genera.te hydrogen in situ, e.g. C0 and water. When employing wa.ter ga.s or pressure generator gas, it is possible to but not necessa.ry to remove C02 by scrubbi~g.It is also possi-ble but not necessary to upgra,de the hydrogen content by the shift rea.ction or purifica,tion.
~y thus evapora.ting down the combined residual product, including carbonaceous insolubles and a.sh and, where appropriate 9 by selecti~g a. starting material meeting the defi~ed requirements, it becomes possible to bypass the difficult and expensive solids removal sta.ge of SRC manufacture a.nd produce a valua.'ble product at reduced cost.
' ~hs preferred carbonaceous fossil fuel material for use in the process and material in accordance with the ~.
invention i~ a low rank coal having the defined cha.racteris- '.
~,20 tics, in particular a. brown coal, Brown c03.1 often ha.s a.
very low ash and sulphur content, rendering it particularly suitable for the present purposes. ~he invention a.lso ! envisages the u~e of suitable peat for the process~
~he conditions of the deoxygenation sta.ge ma.y be ,,25 substantially as employed in the manufacture of SRC. lhus, the liquid sol~ent and hydroge~ carrier ma.y be one of the high-boili~g solvents used in the manufacture of SRC, more particularly .a hydro-aroma.tic liquid boiling between 200 and 450C. Creosote fractio~ necessary suitably . 30 processed for the purpose, ma,y be used~ Appropriate coke .

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~61 49~3;~
oven or coal pyrolysis tar fraction~ or coal gasifica.tion fra.ctions such a.s the a.nthracene oil fraction or simila.r fra.ctions may be employed. ~he aroma.tic extract from lubrica.tion oil refining may al~o be employed after suitable pre-treatment, in particular partia.l hydroge-nation.
As in the manufacture of SRC the solvent is employed ~ in an a.mount sufficicnt to form a slurry. Solvent/coal : ratios can vary from less tha~ 0,5 to more tha.n 5,0 but fall preferably in the range betwee~ 1 and 3. ~he pre-ferred temperature during the deoxygenation stage is above 350C a.nd below 500C, preferably between 400 and 450C, ~ay 430C. ~he h~drogen pressure can be between 30 and 250 bar, prefera.bly between 70 and 200, say 140 bar. It will be apprecia.ted that higher temperatures can be employed if the pressures are higher, provided the formation of liquid products is sufficiently suppressed.
~he process for making the said ca.rbonaceous ma.terial may be carried out batch-wise or on a continuous basis.
Also in accordance with the invention there is pro-vided a process ~or making coke, suitable for metallur-gical purposes, wherein the carbona.ceous material in acoordance with the invention, more pa.rticularly the . product of the aforesaid proces3 in accorda.nce with the :l 25 invention, i~ subjected in the form of a blend to coking, ~ore parti~ularly u~der commonly k~own coking conditions.
urthermore there is provided, in accordance with the lnvention, a proce~s for the making of a coki~g coal blena, wherein the ca.rbonaceous material in accordance ~ 30 ~ith the in~ention9 more particularly produced as de-~! -7-.. . ,. ... . .. . . ~ . . .

l~g~33 scribed above, is blended with other sui-table carbana-ceous matter having comparatively inferior coking proper-tieg 9 in order to for~ a blend having comparatively im-proved and adequate coking properties.
The material in accordance with the invention can also be used as a fuel per se or in blends, being sub-~tantially upgraded as compared with the starting material.
I~ appropriate circumstances it can also be u~ed as a ~eed stock for processing to fuels or petrochemicals and their precursors.
E~am~le 1 A brown coal was used having the following analysis (all figures in mass perce~t).
~sh 1,0 Moisture 10,1 Carbo~ 60,3 Hydrogen 4,0 ; ~itrogen 0,5 Sulphur 0,25 O~ygen 2~,9 500 g of this material was ground to a particle 9i2e les~
tha~ 100 ~esh and slurriea with 1000 g of tetralin.
This slurry was heated in an autoclave with agitation for 75 ~inutes at 420C, hydrogeu bei~g introduced at a pressure of 90 bars~ (i~itial pressure~. ~o catalyst was employed.
At the e~d of that period the pressure was let down ~d the ~lurry was fed directly into a distillation apparatus a~d ubjected to distillatio~ under partLal vacuum to a cut point of 420C a~ 760 ~m ~g.
l ~

, ~ ,~ ~ .-' ' ' " ' . , . . ' ' ' ' ' ~4g9L33 The residue was a brittle, shiny black, ~olid material having the following composition (in ma~ percent):
A8h 2,0 Moisture 0 C~rbo~ 86,2 Hydrogen5,9 ~itrogen0,5 Sulphur0,07 O~ygen 5,4 10 ~he yield was about 50 ~a~ percent based on the original ¢oal.

From the residue obtained in Example 1 a blend is prepared a~ follow~:
The brown coal extract wa~ crushed and added in amounts of 5~ ~nd 10~ to two coals, one of them with no coking properties and the other a good coking coal. The coking propensities of the mixtures were then oharacterised by means of Roga Index and Dilatometer determinations.
Ro~ Index ~c Dilatation Coal ~ 24 ~ 15 ~ 5% ~CE 29 - 12 - : ~ + 1~% ~C~* 35 - 5 Coal B 55 50 + 5%~CE 56 ~ 90 10~ ~CE 61 139 * ~CE = ~row~ Coal E2tract It is clear that the additio~ of the brown co~l extract : hss a beneficial e~fect on the coking properties of a coal -, ~
and th~t ~he coke produced from the appropriate blends will :,~ be suitable for metallurglcal purpo~es~
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r~ ~ .

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Claims (20)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A coking blend, which when subjected to conventional coking conditions is converted to a coke useful for metallurgical purposes, said blend consisting essentially of:
i. up to about 10% by weight of a carbonaceous material derived from solid carbonaceous fossil fuel subjected to deoxygenation and dewatering in the presence of hydrogen and a solvent having hydrogen carrier properties which consists essentially of the combined, substantially non-volatile, sub-stantially solid product and residues of said deoxygenation, including ash and carbonaceous insolubles, the material having a ring and ball softening point about 30°C, and ii. the balance of said blend consisting of coal having coking properties inadequate for metallurgical purposes.
2. A blend as claimed in claim 1 wherein from 5 to 10%
by weight of said carbonaceous material is employed in said blend.
3. A blend as claimed in claim 1 wherein the total char content of said carbonaceous material is less than 12% by weight of dry solid matter.
4. A blend according to claim 3 wherein said total char content is less than 3% by weight of dry solid matter.
5. A blend according to claim 1 wherein the actual ash content of the said carbonaceous material is not more than 10%
by weight of the dry solid matter of the carbonaceous material.
6. A blend according to claim 5 wherein said actual ash content is not more than 7% by weight of said dry solid matter.
7. A blend according to claim 1 wherein the carbonaceous material is derived from brown coal.
8. A blend according to claim 1 wherein said carbon-aceous material contains at the most 2% sulphur by weight of dry solid matter.
9. A blend according to claim 8 wherein said carbon-aceous material contains less than 0.5% sulphur by weight of dry solid matter.
10. A blend according to claim 1 wherein said carbonaceous material has a ring and ball softening point about 100 C.
11. A process for the manufacture of coke useful for metallurgical purposes, which consists essentially of:
i. preparing a carbonaceous residue by subjecting a solid carbonaceous fossil fuel material of which the oxygen content is undesirably high for satisfactory coking properties to a step of deoxygenation and removal of such water as may be present, which step comprises heating the carbonaceous material in intimate contact with a liquid solvent and a hydrogen carrier-and hydrogen under pressure to effect the deoxygenation, followed by distilling the solvent and such volatiles as are formed off the combined product of said heating, and recovering the combined residue, ii. blending up to about 10% by weight of the carbon-aceous material produced by step (i) with ordinary coal having coking properties unsatisfactory for metallurgical purposes, and iii. subjecting the blend of step (ii) to conventional coking conditions and recovering the resulting coke as a product.
12. The process according to claim 11 wherein about 5 to 10% by weight of the said carbonaceous material is employed in step (ii).
13. The process according to claim 11 wherein said solid carbonaceous fossil fuel material contains not more than 7% by weight of ash and not more than 4% by weight of sulphur.
14. The process according to claim 13 wherein said fuel material is selected with an ash content of not more than 4% by weight.
15. The process according to claim 11 wherein step (i) is carried out with a technical gas mixture containing hydrogen.
16. The process according to claim 15 wherein said gas mixture is water gas or pressure generator gas.
17. The process according to claim 11 wherein said fuel material is selected with an ash content of less than 2% of ash and less than 1% of sulphur, both based on solid dry matter.
18. The process according to claim 11 wherein a low rank coal is used as the fossil fuel material.
19. The process according to claim 18 wherein the low rank coal is a brown coal.
20. The process according to claim 11 wherein the conditions of the deoxygenation stage are substantially as employed in the manufacture of solvent refined coal.
CA231,705A 1975-07-17 1975-07-17 Carbonaceous material Expired CA1049433A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CA231,705A CA1049433A (en) 1975-07-17 1975-07-17 Carbonaceous material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CA231,705A CA1049433A (en) 1975-07-17 1975-07-17 Carbonaceous material

Publications (1)

Publication Number Publication Date
CA1049433A true CA1049433A (en) 1979-02-27

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Family Applications (1)

Application Number Title Priority Date Filing Date
CA231,705A Expired CA1049433A (en) 1975-07-17 1975-07-17 Carbonaceous material

Country Status (1)

Country Link
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