US2015085A

US2015085A - Method of thermolizing carbonizable materials

Info

Publication number: US2015085A
Application number: US452482A
Authority: US
Inventors: Oberle Alfred
Original assignee: Individual
Current assignee: Individual
Priority date: 1930-05-14
Filing date: 1930-05-14
Publication date: 1935-09-24
Anticipated expiration: 1952-09-24

Description

Sepe; 24,1935.

A. oBl-:RLE

METHOD 0F THERMOLIZING `CARBONIZABLE -MATERIALS Filed may 1f,-19so '2 Sheets-Sheet 1 OBERLE uml-10D on THERMOLIZ'ING cARBoNIzABLE MATERIALS sept.l 24, 1935.

Patented -Sep-t. 24d,v 1935 UNI-TED STATESl PATENT OFFICE METHOD -OF THERMOLIZING CARBONIZ- ABLE MATERIALS Alfred oberle, washington, D. o. Application May 14, 1930, Serial No. 452,482 1o claims. (Cranz- 18) This invention relates to a method of y thermolizing solid and semi-solid carbonizable materials, such as coal, lignite, peat, petroleum carbon, mixtures of carbon and oil residues, or residues obtained from hydrogenation of oils or coal and oils, also'colloidal asphaltenes, carbenes and carboids resulting from cracking of liquid hydrocarbons, or other substances of similar-natures in l which the substance comes into intimate contact in such a manner and undersuch conditions as to cause the desired changes without danger of superheating, objectionable swelling and caking or other consequent excessive The novelty in the invention here disclosed lies in the use of heated mercury, amalgam, or

Y trolled,`in order to assure the maximum yields of gaseous or liquid hydrocarbons, as desired, without interruption of the process. dations can also be made through control of these `same factors for the treatment of charges of different natures.

Depending onthe character of the charging material, and the control, the process yields smokeless fuel such as is ordinarily produced by low temperature caibqnization or active carbon and gaseous and liquid hydrocarbons. In the process here disclosed the material to be treated is blown, or otherwise forced, into the thermolizing coil or tube to/come into intimate contact with mercury, which has already been heated in a separate coil and under pressure in the furnace, in such a manner as to insure intimate mixing and eiilcientheat transfer. The mixture passes through the thermolizing coil and into'the tower where the liquid metal and the residual carbonaceous material are separated from the volatile matter. The various products of the process are tional views of the apparatuses.

undesirable changes, the conditions of time, temperature and, `pressure being controlled.

Accommocollected in manners appropriate to their character.

It is distinctly understood that suitable -low melting alloys, such as, for example. lRose metal rconsistingof tin, lead, and bismuth or Woods 5 metal consisting of cadmium-tin, lead and bismuth, or amalgams may be used instead of mercury inthe practical application of-this invention.

In this specification, mercury has been chosen 10 as a typical example f the heat'conveying substance, although any of the above mentioned materials may be used instead of the mercury, with the various substances to be thermolized without alteration of the process.

The-details and advantages of the process will be best understood with the aid of the diagrams and the typical examples.

Figures 1 and 2 are diagrammatic side eleva- 20 Referring to Figure 1, l designates a pulverizer orl homogenizer for grinding the carbonaceous material or otherwise preparing it for passage through valve 2 and forcing by blower or atomizer 3 and line 4 into the thermolizing coil 5. l 25 is so constructed that pressuremay be malntained on it and/or heat applied to it if desired. As such features are Well known they are not indicated in the diagram.`

Line 4 contains valve 4a, and may also be pro- 30 vided with any conventional means for preheating the charge and with inlets for hydrogen and/or steam and/or catalyzing material if desired. Line 4 connects the blower or atomizer 3 A lwith the thermolizing coil. Coil 'l is for heating 35 the mercury to a high temperature under pressure up to 4000 pounds per square inch and is connected with'thermolizing coil 5 through pressure 'reducing valve .6. The inlets to coil 5 are so constructed and locatedthat they cause the 40 hot mercury and charging stock to enter-this coil tangentially and to cause intimate mixture and turbulence throughout the coil. Coils 5 and 'l are located in a furnace, not shown in the diagram. Coil 1, for heatingv the mercury is 45 placed in the hottest part of the furnace and the thermolizing coil 5 nearest where the fiue gases leave the funace.

Dampers are arranged in the furnace, yso that the heating of thermolizing coil can be controlled. 50 Line 9 in which is a pressure release valve 8 con-1 nects the thermolizing coil 'l with tower I0 in which the hot liquid mercury and the treated carl bonaceous material are-separated from volatile matter. 55

The hot liquid mercury settles to the bottom of tower I8 where it forms a pool I I on' top of which an endless screw I2 is so operated that the carbonaceous residue collecting on top of the mercury pool is continuously discharged through passage I3 which connects tower I8 with tank I4, one of several like carbon collecting tanks which has a manhole I5 for the removal of carbon, a vapor line I6 with a pressure regulating valve I1 for the removal of volatile matter, and a line I8 and a valve I9 through which any mercury which may collect in the bottom of tank I4 is returned to the system by line 20 and pump 2l. Tower I0 and tank I4 may be provided with connections (not shown here, but such as are shown in my co-pending application Serial No. 448,704 led April 30, 1930) for admitting steam at their bottoms. Tank I4 is providedwith conventional shut-ois (not shown) so that it may be used al- 'for the withdrawal'of all volatile material and lead to any conventional condenser system (not shown here) for the separation of the liquid and gaseous hydrocarbons.

The inlet pipe 32 serves for introducing liquid materials for treating the volatile products in tower I0. For this purpose, the irlet pipe 32 is provided with

branch pipes

33, 33 having valves 33a, 33h and 33c controlling the passage of such introduced materials into the pipes 34a, 34h and 34o from whichthey are introduced into the tower I 0. Desirably plates 35 are provided between the pipes 34a, 34h and 34e, so that liquids are thus caused to contact with the materials in tower I0. The liquids drop from one plate 35 to v the next lower one, until the plate 36 is reached where they accumulate to be Withdrawn either wholly or in part through the pipe 39 provided with valve 38, or pass through the bubble plate risers 81 down onto the pool of liquid metal. The volatile materials generated in the lower part of tower l0 pass up through the openings or risers 31 in plate 36 and into contact with the liquid descending from plates 35.

Figure'2v represents a modification of apparatus especially adapted for thermolizing petroleum carbon or residues although it may be used successfully for treatment of other carbonaceous material.

Referring to Figure 2, I is a hopper into which the petroleum coke or residue `is fed, 2' is a crushe'r and 3' is a pulverizer for the reduction of the coke to a relatively ne condition preferably small enough to'pass through a 300 mesh screen. A screw conveyor 4' driven by a motor, not shown, attached to pulley 6', delivers the finely divided particles to an atomizing chamber 1 into which superheated steam is introduced by means of pipe 8', controlled by valve 9', and heated mercury by pipe 48" controlled by valve 48' and supplied from heat coil 44'. A trap I Il is for collecting the relatively heavier particles or impurities, I I is an insulated mixing and thermolizing tube in which are located bailles I2' and turbulators I3' which serve to intermix the contents of the tube more intimately. Tube II opens into an expansion chamber I4 equipped with a peephole I5', the manhole plate I6', and a perforated steam pipe I1', the latter being placed near the bottom of the chamber. 5

The expansion chamber I4' is heavily insulated as shown at I8' and is mounted above the furnace I9' by means of which the temperature in the chamber may be accurately controlled. Mercury falls to the bottom of chamber I4' and forms a 10 pool, the depth of which is controlled by withdrawal of .excess of mercury through lines 38', 31', and valve 40'. Chamber I4 is also fitted with a gauge I6"-. .The mercury thus withdrawn is returned to the mercury feed line. The rel5 turned .mercury 2is supplemented by mercury which enters the system through line 4I' and valve 42 and passes through pump 43' after which it is yagain supplemented by mercury which collected in trap I0 and is returned 20 through line 45 and valve 41' and is then heated in coil 44 in the furnace 45'. Vapor line 20' leads from the top of chamber I4 and contains baiiles 24' and trap 2|. Trap 2|' serves to collect mercury and any solid material which is carried over mechanically. Line 31' has an opening of a conventional type which permits entry of the mercury, but not of the carbonaceous product. The mercury is returned to the feed line through line 31', valves 38' and 40. 2|" is-a manhole for 30 the removal of the carbonaceous product which may" be activated carbon, coke,- or other carbonized residue.

The uncondensed gases and steam pass through valve 22 and valve 25' through nozzle or jet 26'.A 35 intocarbon chamber 21', or after passing through valve 22 may be diverted through line 33' which contains valve 33". Line 34', containing valve 34"', is an auxiliary fuel line and 36' is a pilot light fed by line 35' and controlled by valve 35". 40 Within the chamber 21 are baiiles 28' and screw 29 driven by pulley P, for conveying the carbon black into carbon collector 38 provided with a manhole 3|' for removal of carbon, and a line 32' for escape of gases. Chamber 21 is also pro- 45 vided with a gas escape line 32".

All drawings are only diagrammatic and the Idimensions of the variousparts may be altered, especially those of the heating and thermolizing tubes or coils. Pyrometers, pressure gauges, and 50 various devices for control and safety may be introduced as and wherever desired.

The underlying principles of the invention are further explained by means of examples illustrating two practical embodiments of the process and of apparatus suitable for carrying it into ell'ect.

Referring to Figure 1, in a typical operation, carbonaceous material, as coal, to be thermolized,

'is charged into the pulveriz'er in which it is ground to the size necessary, passes through valve 2 and 60 is forced by blower 3 through line 4 and valve 4a into the thermolizing coil 5 tangentially in such y. a manner that it is intimately mixed` with the 2,015,085 i the volatile matter is withdrawn through valve 4I) in line 4I as fast as formed into any conventional condensing system, before undergoingthe unde-4 .churns the coked residue and the surface of the hot mercury thus aiding in the removal of volatile constituents and continuously discharges the coked residue through passage I3 into a carbon collecting tank I4. It is an advantage tohave two or more collecting tanks so connected with the tower I0. and return line I8 that each one may be operated independently in order that .one can be emptied while another one 'is being filled. The coke .or char is removed from collecting tank I4 through manhole I5, the vapor through line I6 which isv fitted with pressure regulating valve II -and any mercury which may have collected in the bottom of tank I4 is returned to the system by line 20and pump 2|.- The excess of hotlmercury which collects in the bottom of tower I0 is continuously withdrawn through pipe 29, valve 30, line 25, and valve 26, and again pumped into the system by pressure pump 2'I and line 28, if

necessary, together with added mercury from line 22; valve 23, pump 2|, valve 24, connection 2,5 and valve 26.

crushed by vcrusher 2', and pulverized small` enough to pass through a 300 mesh screen by the pulverizerl in chamber 3. The screw conveyor 4', driven by. pulley 6', conveys the nely divided particles to the atomizlng chamber 'I' in -which it is mixed with superheated steam from pipe 8',

controlled by valve 9', and atomized, heated merv cury from pipe', controlled by valve 49', and supplied from heating coil 44.

A trap I0 collects the relatively heavier Aparticles and impurities. Any mercury which collects in this trap is returned through line 46' and valve 4'I' and supplements the m'ercury to be heated'. The mixture of steam, petroleum coke Iparticles, and atomized mercury then passes'into the' insulated mixing tube I I in which are located baflies I2' and turbulators I3' which serve to further intermix and prevent separation of the mixture and thus aid in the transfer of heat carried bythe mercury and steam to the petroleum carbon.

K The use of steam aids materially in removing vapors and gases from carbonaceous material and from tube and chamber, activating influence helps turbulence in tuber and keeps carbon over the mercury pool in motion. From tube I I', the mixture goes into expansio chamber I4', in which the hot mercury and the heavier carbonaceous product settle to the bottom, the mercury forming a pool in the bottom. The gases and uncondensed vapors andlght,

very fine, dust like carbonaceous material Aleave this chamber by line 20'.

The temperature of the mercury pool in chamber I4 may be elevated by means of furnace I9' over which chamber I4' is mounted and also steam .may be injected into the chamber through the fperforated'steam pipe I'I' which is submerged in the mercury. The carbonaceous product which may be activated carbon, coke, or other carbonized residue 'is removed through manhole I 6 and excess of mercury withdrawn through lines 31', 33' and valve 40. The hot mercury withdrawn is returned to the mercury feed line, where, supplemented by mercury which enters the systeml through line 4I and valve 42', it passes through pump 43A and to it is added also any mercury from trap I0', after which it passes into the mercury heating coil 44' in furnace 45.

The vapors from the topof chamber I 4 pass through line 20', which contains baffles 24' and l0 v trap 2l'. The mercury, and any solid material which is carried over mechanically, collect inthis trap, the mercury being returned to the mercury feed line through valve 39', line 31' and valve 4D', and the carbonaceous product removed through 15 manhole 2I The uncondensed gases pass through valve 22' and valve 25' through nozzle or jet 26' into carbon chamber 2I', or may be diverted through line 33' which contains valve 33, after passing through valve 22'. The gases 2o arc burned to lamp black in chamber 21'. Auxiliary fuel may be introduced through line 34 containing valve 34". Pilot light 36' is fed by line 35', or from any other conventional source, and is controlled by valve. 35". The carbon thus formed, 25 in 21', is collected by baies 28 and conveyed into carbon collector 30 by screw 29 driven by pulley P. The carbon black which collects in carbon collector 30' is removed through manhole 3|', and the gases escape from the collector through 30 line 32'. Gases may also escape from chamber 21 by the line 32 there provided. Alterations in temperature, pressure and other controllable factorsdetermine the character of the products and accommodate the process to 35 charges of highly dilferent'character.

Temperatures in the thermolizing tube 5 range preferably between 250 and 1000 C.

Hydrogen or steam; and/or any desired catalyst, such as pumice, iireclay, metal-oxides, silicon' 40 compounds, iron, cobalt, molybdenum, vanadium,y active carbon, mercury, and other suitable catalysts separately or together, may be introduced into the thermolizing coil at its inlet through any added suitable connections not shown in the dia- 45 gram but such as shown in my co-pending application Serial No. 448,704.

Steam may also be introduced into either or both tower I0 and tank I4 by connections already mentioned but not shown/in Fig. l. Also, intro- 50 duction of steam into tube I.I and chamber I4 of Fig. 2 may beomitted if desired.

vIl? petroleum carbon is used as charging material, a high grade of active carbon will result.

The charge may advantageously be heated to as 55 high. a temperature as technically practical bel* fore entering the thermolizing coil.

'I'he chief features of the process are the following: The charge is brought into intimate contact with Yatomized, highly heated, mercury in such a 60 to supplement that from the mercury but insuiiicient to cause superheating of the contents of the tube on its inner surface; the mercury `prevents the clogging of the tubes and the caking ofthe residue in the system. j 1

, The return of the-hot mercury to the system from the bottom of tower 'I0 is an economy in heat.

The relatively short .period of carbonization and the withdrawal of the volatile products as fast as 5 formed as well as the good control of the temperature throughout the process avoids the undesirable changes which take place when this volatile matter is heated too long and/or to too high a temperature.

Dilution of the uncondensable gases by air, thus lowering their caloriiic value is avoided, as is also the loss of these gases into the air.

Due to the fact that the mercury is non-infiammable and non-combustible, there is a great re duction of fire and explosion hazard.

The use of steam aids materially in the carrying of the mixture, in maintaining turbulence in the thermolizing tube and in separation of volatile matter in the tower.or chamber.

The pump in the mercury feed line and the pressure release valve in the entrance to the.'

thermolizing coil make it possible to maintain as high a pressure on the mercury in the heating coil as desired, within reasonable limits.

This feature of regulating the temperature at which the thermolizing coil is kept somewhat independently of the temperature of the mixture of charging material and mercury entering therein, is important.

The pressure in coil 5 is also controllable by means of the outlet valve 40 connected to tower I 0.

Due to the high velocity with which the intimate mixture is passed through the thermolizing tube it is possible to use mercury heated to a very high temperature before it enters the thermolizing tube, thus insuring very effective, although brief, contact of the highly heated mercury particles with the material to be treated before they are expanded in the vaporizing chamber.

There is iiexibility in the operation, due to the fact that the heat stored in the mercury is made available in both the thermolizing coil and the tower and also due to the fact that the temperatures of both can be increased as desired by control of the two furnaces respectively.

The use of mercury in this process and apparatus has many advantages, among which are:

-the intimate contact it can make with the material being treated, without,'however, being soluble therein; the amount of mercury and the temperature to which it must be raised are readily determined and controlled; also, because of its liquid state and its high specific gravity, it can be readily fed and transported with the aid of appropriate reservoirs and pumps; it aids in vaporizing any volatile matter held in the residue; its use is economical becauseit can so conveniently be raised to the temperatures desired in the treatment' of carbonaceous material, its recovery is practically complete, and it can be returned to the system at a relatively high temperature; it aids in causing turbulencev and prevents clogging and sticking.

It is readily apparent that the process, described above, with various disclosed modifications may be applied to carbonaceous materials of widely varying nature through control of temperature, pressure, and other controllable factors and that the productsof the process can also be appreciably varied as desired by control of these same factors.

I claim:

1. A method: of thermolizing solici carbonizable material which comprises passing a stream of intimately admixed solid carbonizable material and hot 'liquid metal through a thermolizing zone,

zone, and recovering coke and volatile by-prodl ucts.

2. A method of thermolizing solid carbonizable material which comprises continuously passing a stream of intimately admixed solid carbonizable material and hot liquid metal through -a thermol0 I lizing zone, continuously withdrawing said stream of intimately admixed material and hot liquid metal fromI the thermolizing zone, and continuously introducing said admixed stream of material and hot liquid metal into an enlarged zone, 15 and recovering coke and volatile by-products.

3. A method of thermolizingsolid carbonizable material which comprises passing a stream of intimately admixed solid carbonizable material and hot liquid metal through a thermolizing zone, 20 withdrawing said stream of intimately admixed material and hot liquid metal from the thermolizing zone and introducing said admixed stream of material and hot liquid metal into an enlarged zone, at least one of the treatments being carried 25 out under superatmospheric'pressure, and recovering coke and volatile by-products.

4. A method of thermolizing solid carbonizable material which comprises passing a stream of intimately admixed solid carbonizable material 30 and hot liquid metal through a thermolizing zone under superatmospheric pressure, withdrawing said stream of intimately admixed material and hot liquid metal from the thermolizing zone and introducing said admixed stream of material and 35 hot liquid metal into an enlarged zone, the pressure in the enlarged zone being less than that in the thermolizing zone, and recovering coke and volatile by-products.

5. A process of thermolizing solid carbonizable 40 material as described in a continuously advancing closed stream of hot liquid metal, including intimately mixing the 'solid carbonizable material and hot liquid metal and conveying the mixture Vin a confined stream to an enlarged zone, and remov- 45 ing residual solid, liquid, volatile and gaseous material, wherein the mixture of hot liquid metal and the material to be treated is further heated while advancing through a thermolizing coil.

6. A process for carbonizing pulverized semi- 50 solid or solid carbonizable material or fuel yielding material in a continuously advancing stream of hot mercury, consisting in intimately mixing the fuel and hot mercury and conveying the mixture ina turbulent confined stream into an expansion chamber containing a heated mercury bath, distilling and carbonizing the fuel in the expansion chamber, separately withdrawing the vapors and gases from the chamber, collecting the carbonized residue over the mercury bath, 60 and withdrawing the carbonized residue' from the chamber.

7. A process forthermolizing solid carbonaceous material, as described,V in a continuously advancing stream of hot mercury, in the presence 65 of hydrogen introduced into the system, consisting in intimately mixing the solid carbonizable material and hydrogen with the hot mercury and conveying the mixture in a turbulent confined stream into an expansion chamber, wherein the volatile products are distilled of! and the liquid and solid products -collected in the base of the chamber over a pool of hot mercury.

8. A process for thermolizing solid or semi-solid carbonizable or fuel-yielding material in a con- 75 tinuously advancing stream of hot mercury, consisting in intimately mixing the carbonizable material and hot mercury with hydrogen and steam and conveying the mixture in a turbulent confined stream into an expansion chamber containing a heated mercury bath, distilling and carbonizing the material in the expansion chamber, separately withdrawing the vapors and gases from the chamber, collecting the carbonized residue over the mercury bath, and withdrawing the carbonized residue. from the chamber.

9. A process for thermolizing solid or semisolid carbonizable or fuel-yielding material in a; continuously advancing stream of hot mercury, consisting in intimatelyrmixing the carbonizable material and hot mercury and introducing hydrogen, steam and a catalyst into the mixture of hot mercury and carbonizable material and conveying the mixture in a turbulent conlned stream into an expansion chamber containing a heated mercury bath, distilling and carbonizing timately mixing the material to be treated and the y hot mercury and conveying the mixture in a turbulent conned stream into an expansion chamber containing a heated pool of mercury, distilling and carbonizing the material in the expansion chamber and introducing steam into the pool of mercury, separately withdrawing the vapors and gases from the chamber, collectingl the carbonized residue over the,mercury bath, and with-L'v drawing the carbonized residwr from the chamber.

ALFRED OBERLE. 20