DE2218764C3 - Process for the production of shaped coke - Google Patents

Description

The invention; relates to a process for the production of shaped coke inrt hardened surface, which during coking by splitting hydrocarbons and graphitizing the precipitated coals Layer of fabric is formed.

Conventionally, coke is made from coking coals as By-product or produced in so-called beehive coke ovens. The coke falls in t'orn- from irregularly shaped coke lumps. When handling. Break especially when shipping the Ivken and edges of these coke chunks as coke b / w. dust off. the / u difficulties in the Keeping the bellporosilate in the blast furnace and / u rapid clogging dir congestion samniei b / w. Separator systems drove !, in which the blast furnaces are equipped The aiii the wise one forms Coke b / w. dust isi but relative {.'roh and HiUk-I hardly any Staiibwol with normal handling ken The tendency of a coke, (ims oiler S'aub / u Wrapping can be done by suitable methods Be stiiiinil

From the US l'Sen SI K4. '·) !. JI 40 241 and il 40 242 Isi cm I ormcoke and its preparation process known by catalyzing coal particles, in dom iii.iii them in the presence of / iigcscl / len oxygen or Oxygen contained in the coal is about I2D (and under the lccrdeslillalioiislempcratiir temperature erhil / l. the kohlclcili hay afterwards abruptly .ml the I eerilcslillalionsleiiipcraliir erhil / l. by transferring them in a whirlwind hu hl, the .ml the desired. empty et / appending Irmper.iliir gehal th, the empty contained in the charcoal cake in one or more (arbomsicriingsstufcn essentially borrowed completely and then the 'particles an even higher lcmpcialiir to / η a (ichall, m Fliichligcn licsiaridlcilcn of niihl more than clvv.i i "/ o vcrkokl D.is so obtainable rc.iklivc V crkiikimgsprodiikl becomes el.inn mn a hiliiutmoscn Itiiidcmilli I hrikcl tu rl and then in Gegenw.itl from S.uicrslufl Ii Mi [> t ι.ihm η> ί hai let you to nmr diiiih Saucislofl

UIl (I Illl / C .IMS ₁ -I llISU M Kc.lkllou lllS! (Killt Mllltlls llllll

(l.illiil to iluiii desired. reactive coking is to stir, which iinehsidieinl and in the claims as "reactive i-orihkoks" is / eiclliu'f: if this I (fimkoks occurs ledoeli an ei Iu Mu Iu- slaiibbildiüig, ( lic by eiiif high con / oii (raiioii au iillraleiiicii koiiichi'it in eilieifi KofngidKciiln-icu h from Ί to 2 (1 | in the vcmis.iihi I ine lldk-isiichiiiig iuiu-r your microscope is hot! recognize that the obcrllächc von mikliveni molded coke contains many pores smaller than 5 μm, so that ultrafine granules are formed when it is abraded. An examination under the microscope showed that the cell walls of Jes coke are much thinner in reactive molded coke than in conventional coke there is a cell-like or honeycomb-like structure with very fine pores, in which the wall thickness is of the order of magnitude of 1 to 5 μm and also the size of the pores themselves in this area

ίο lies. Also, there are deeper pores with thicker ones Walls in place. During abrasion, these thin walls collapse and form the ultra-fine abrasion dust.

A solution to the safety problem is thereby complicated and difficult for its use in blast furnaces and other fields of application essential properties of the molded coke must not be changed and the production costs must be kept low.

From the DF-PS 7 17 721 is a process / ur production of hard, lumpy coke from lignite known, in which the solidification of the coke is promoted by the fact that one during the final coking Hydrocarbons are passed through the molded coke

2-i are split and a graphitized solid protective layer form.

The invention is based on the object a Process / ur production of molded coke. in particular to create reactive I ormcoke, which is at best one

in slight inclination / ur formation of l'lugslaubabricb has, the production costs of the coke are at most negligibly increased.

According to the invention, this problem is solved by that the I leißgase / um coking by adding Weilerer

il carbon water vapor of which at least 10 vol menpro / cnl included. The hydrocarbons are gecr.ickl in the presence of the hot ί ormkokses and thereby form on the gaii / en surface of the I ormkokses a thin layer of (ilan / carbon.

4Ii the the. In the (Jbcrllai he des I onukokses Peeking b / w l'nren. the smaller al «· about ~> um are, aiisfulli and the KcM closer to the surface / iehi. At your iilan / kohlctisiolf haiidell it is a silvery glaii / end of urine from Kohlcnsloll. du- yourself when (painting

■ ι, hydrocarbons deposited on a surface. Such (ilaii / kohlcustollsihichlcn .ruf loiinkoks are from the I) I AS IO 78 OM per se hek.ninl I one isl es from the Dl I ¹ S 4S "> b7 known the () surface poices of 1 ormkoks d. iiluri Ii / il close off that one

in the past SehliilUerkoken with l'iopanbihmien liaiikt and a S.iiicrstollhehandliing iinierwiili der erhalleiie molded coke has a low reactivity

The titich your inventions-gi-Maßcn process hcrgi MeIIu- I ormkoks isl in the htsl.nihend and ergibl germ

Vi Kußileeken / war can also lu-i a Kiihlciivv.is serslolfd.impfkon / eiilr.ilion of less than Kl VoIu menpid / enl ein (il.iii / kohleuslollsi hu Iu form μ lloi Ii sees d.ilu-i ilei ( i! .iM / kiihliMslo ([in so> · ι ι iiigeli MrM) ¹ I Il dall du nlli.ili Uli η l'oieli <lts tieh.iiidi III -Ii

I ₁ Il I Ol lllkoksi S Ml. Ill VoIKl, null} '.IIISJ'I llllll VVtI (UlI IMIlI

aiii the KtiksnIu'iilacliL-n no fully slithering. ti ii diüsc im weseli ι borrowed completely coverkender, < iliiu / kiihleiisloffilm hilden / in-1 i / ieliing i'ilier ililsieiclu'lHli-ii kohlcuwassi'istiiird.iiiipfktiii / eiilriiliOM by uiiiidi> kn-, ι ,, Kr Voliimeltpiu / efit uiiisseii therefore i'iluuluUgsgelii.iH dcll f li'iMgiisen /us.ii/lii he kolllenwassersloffdaiiiple in hen from all coke links aii.stieleiideii coals w.lsseislolleil / ii) / cliilill be.

The method according to the invention can also be applied to other types of shaped coke, d. H. even on reactive molded coke, in which case it is preferred. that the reactive form coke in itself is cured in a known manner before coking in the presence of oxygen.

According to a preferred embodiment of the method according to the invention, the in the hot coking gases contained hydrocarbon vapors by introducing raw or partial Carbonized or coked coal in the for the production of the used for the coking of the molded coke Combustion gases, whereby the gases are cooled to the desired operating temperature and at the same time a reduction in the reaction taking place between these gases and the molded coke is achieved, which leads to an improvement in the quality of the end product.

The hydrocarbon vapors can be added in any suitable manner, preferably by using coal or partially coked b / w. Smoldered coal in / around coking the Srikct.s used combustion gases on entry into the Oven egg ^ splashes. This type of supply of hydrocarbons is wake-up in various ways, and nmr / ur temperature control of the hot gases and / ur Setting the flame temperature. because the Reaction of the coal with the combustion gases is endothermic. Typically drove! the burn vein propane or a similar gas under exactly or almost neutral to reducing conditions in order to avoid an excessively strong reaction with the Briquettes are required / ti a lammentemperalur of about 1540 C. during optimal Vcrkokiingslempe ratiir about in a kingdom of St. "> up to 425 C. Through I iiifiihreii the hollow in the healed R.iuchgas becomes the temperature of which is considerably reduced, sn that a lower I Imualzgeschumdigku in the cooling gas ei lordei in h is.

Furthermore, the colic cagicrts the tired Verbieitiiiiiigsprodiiklcu Ivw cam ligases forehands new carbon dioxide and W.isseidanipl under! separation min carbon monoxide and W.isscrstoll thereby and the Rcaktionslahigkeil des Ram ligases mn den liiikells ν ei Hilpert, whereby uicdciimi the (Jiialil.il des I mlpm iliikls vcibcs'ei t will

I then have a further advantage, d.ili /iis.il/liilie Coals », issersliiNdiiniplc formed pastures, the .ms ilen Exhaust gases .ins der (jlt mn iiingsvoi ι u lining won can graze Is wii 'assumed. d.iLl this Improving the howling by / by I eil .ml der / uliihi the coal is contained in the coal of house i'is scrsloffe is based, and so see also Kohlcnw.isser should im (iasslrom diiich Re.iklion / wischen in Presence of the heat ι ak inierlen coke formed lit i R.iilik.ilen arise

Si hlit'IUn Ii becomes the coal or the Vt ikohliingspio diikl of nonsense components bright and k.inii. Ut im in.in them Ui the Sl.iuhs.imiiiclsvsiciii aullaiigt and (■ ι uiitiii. In quantities his / H Id "., Di s entire please use granular M, ilen.ils! will, whereby the howl are further improved

The Kohienwasscrstoiklämpic. the home procedure dci! '. rlilulimg * in the coking gases voi h.indeli scm must be / was preferably the hot topic. iiiihl icuipcnerleri flue gas /iij.'esei/i. iedo (h you can iitii'h in a different but more expensive way /iisct/.uti and still receives complete glaii / cabbage fabric films.

Such a metiode consists, for example, in the hydrocarbons directly into the hot zone of the Furnace in a concentration of at least 10%, based on the total gas volume, resulting Introduce crowd.

In the laboratory, the desired hydrocarbon concentration can be achieved by using the Container in which the briquettes are placed in a laboratory muffle furnace

to be coked, charged with raw pulverized coal, so that in the surrounding the briquettes Gas atmosphere sets the desired hydrocarbon concentration. However, this technique can be used in a Production line using a moving bed of briquettes cannot be used as the Coal would melt and clog the furnace.

The invention is described below with reference to the drawing of an apparatus for carrying out the method according to the invention, explained in more detail. The device has a vertical furnace 10. the off a loading section 12. a « section 14 and a cooling section 16 best.ht.

The charging section 12 is charged with hardened briquettes by means of a belt 18, which then

.'-, under the effect of gravity in units by a Lock ™ .fiter 20 get into the relief section 14.

The locking bar 20 has slides 204 and 20ö.

which are operated alternately, so that the im Sperrtriehter 20 located material in uniting the

κι heating section 14 is supplied.

Der f rhitztingsabsehnitt 14 is burned by 22 from a burner in the propane or other gas generated · Vei burning heated ingsgase The \ lammen of the burner 22 to beat in a vertical

ι, chamber 24 at the testicles coal or partially coked coal through a line 26 together mn temperature gas is supplied. The mixture of coal ll.immcng.is and lempcriergasen flows through a elongated mixed and rcakiuwsk.always 28th from the -.ic in

in the help section 14 near this Enters soil to calcine the bouquet. The hot ones h / w behei / th section <- ■ 14, 24 and 28 are all mn Refractory material 50 lined and covered with an insulation 51.

ι. The briquettes come out of your I rhitziuigsjbsi hnitl 14 under Schwerkr.illwiikimg in the Kiihljhsehnill 16. der The Kuhlab section 16 has an Australia funnel 32 groove 'vbsperrelcmenlen S2 I and 52 / f on. the mn dem

, H shut-off valve 20 synchronized, isi to ensure dall fed to the furnace 10 and discharged therefrom Material are in a balanced proportion. Of the Auslragsperrtrichtei 52 iiwindet aiii a tape 34. that the fcr'igc.i c.ilcinicrlen unil cooled briquettes for

,, Storage or for Verfr.ic 'bloody hclordeil

The gases in the (.ikinicriHU "> ahsi hunt go through a / vkloiisvslem 56. that, ms a single / yklone or several AkIo connected in series huller ciii.iiidci new heslehen can uiul to June, dragged along

mi I isisiollc to separate V to get / vkloiisvslem 36 the exhaust gases through a position! 8 / to a washer, in the the tar products dar.nis are taught. These Leerprodilktc usually contain about 6 his If) l'iozciil from the / yklorisystcui 56 into the washer

'., milgesihleppte (n) K.-hlc or coke Both the alcohol and the empty: let us use two kinallig, part of the basic material for ώι Bnkellherslelliiri) ·.

In order to enable a corresponding temperature control in the method of the invention, several termocouples Ti to 7 * 6 are provided. The thermocouple 7 * 1 measures the flame temperature of the burner 22, the thermocouple TZ the temperature of the gas entering the calcining device, the thermocouples 7 * 3 or T4 the temperature in the middle or at the top of the furnace, the thermocouple 7 * 5 the Exhaust gas temperature and the thermocouple T6 the temperature of the cooled briquettes.

Typischerweisc the temperature at the measuring point 7 * 1 around 1540 ⁰ C. at the measuring point Tl about 870-925 "C. At the measuring point Tl about 815-870 ⁰ C. at the measuring point 7 * 4 about 480 ° C and at the The measuring point monitored by the thermocouple 7 * 5 is about 260 to 315 ° C. The temperatures can, however, fluctuate within any desired limit values that are required for calcining the currently heated molded coke.

"As already mentioned above, the invention is particularly valuable in the case of reactive molded coke, since the reactive molded coke according to the invention coated with lustrous carbon not coated in the manner according to the invention Form coke is considerable in terms of abrasion resistance and other handleability properties superior, but at the same time still quick and responsive.

The method of the invention can also be applied to other coke briquettes made by briquetting non-reactive coal particles with bituminous binders and subsequent coking at high Temperatures can be produced with or without prior curing in the presence of oxygen. Included Charcoal coatings are produced on these briquettes to prevent abrasion through mechanical handling or help to reduce stress. However, these coatings eliminate the chipping problem not that is one of the major difficulties encountered in burning such other shaped cokes.

The examples illustrate the invention. All quantities or ratios relate, if not

10

15th

20th

25th

30th

35 black and streaky and have the typical fine surface portions of shaped coke bricks according to the state of the art. The briquettes coked in the presence of the coal have a uniform film of lustrous coal over the entire surface, which fills the pores that are smaller than 5 micrometers. These inventive briquettes do not give any black lines.

Example 2

Like the briquettes produced with the dimensions 3.81 χ 3.81 χ 2.54 cm used in Example 1 are placed in the locking funnel of the device shown in the drawing and caicinated at a temperature of about 982 "C (T2 in the drawing), the briquettes are passed through the device at a rate of 13.61 kg / minute until a total of about 227.2 kg of hardened briquettes have been processed.Through line 26, raw Elkol-Adavillc coal from Kemmerer Wyoming is crushed to a grain size of 1.19 m (a bog coal "B") is fed in at a rate of 0.091 kg / minute. It flows through between the briquettes located in the heating section 14 and is recovered in the cyclone system 36 as a powder with a volatile content of only 4 percent Briquettes discharged from the bottom of the furnace 10 have a uniform coating of deposited glossy carbon, which can be seen under the microscope Briquettes the surface pores up to 5 micrometers in size are filled and the glossy carbon film covers the larger pores. Comparative abrasion tests between these molded coke briquettes produced according to the invention and briquettes produced in an analogous manner from the same batch of hardened briquettes but coked without the addition of coal show that the abrasion passing through a sieve with a mesh of 44 micrometers in the comparison briquettes produced according to the known method was 0.58 percent , with the inventive

Example II
(Laboratory test) ₄ -

Hardened. Briquettes made from Illinois No. 6 coal by the methods described in US Pat. No. 3,140,241 up to and including hardening are used in this test. Two identical batches of 40 g of pillow-shaped briquettes each with the dimensions 3.18 χ 2.54 χ 2.22 cm (or the number of whole briquettes closest to this weight) are each placed in a 250 ml beaker made of corrosion-resistant steel, whereupon the beakers for the purpose of coking the Briquettes are each placed in a 954.4 ° C muffle furnace for 20 minutes. In one of the beakers 1 g of raw Illionois No. 6 coal is also placed, while the other is not treated in this way. After coking and cooling, the briquettes obtained in each case are compared with one another. The briquettes not coked in the presence of added coal are 'tnr * nr ~ nn ** .. ·· ~ .a ** UA

the reduction in the amount of abrasion achieved according to the invention in the very fine-grained portion of the Abrasion dust with a grain size of less than 5 micrometers is even more pronounced.

Example 3

Example 2 is repeated, but with the exception of hardened briquettes. i'm worse Quality can be used as the starting material from the raw Elkol-Adaville coal used in Example 2 are made. The dust index of these briquettes is quite high at the beginning. (0.75 percent abrasion dust which passes through a sieve with a mesh size of 44 micrometers), and the briquettes are badly dusted. However, if the briquettes are in the presence of raw coal tar fumes in the process described in Example 2 are coked in the manner described, the dust index is only 0.4 percent, with the proportion of ultra-fine abrasion dust is low enough. that the product no longer develops any airborne dust.

For this purpose 2 sheets of drawings

Claims (2)

99 1R claims: 1. Process for the production of molded coke with hardened surface that occurs during coking by splitting hydrocarbons and Grouping the deposited carbon layer is formed, characterized in that that the hot gases for coking by adding further hydrocarbon vapors therefrom contain at least 10 percent by volume. 2. The method according to claim 1, characterized in that that in the production of reactive form coke this before coking in the presence is hardened by oxygen.