DE2217869A1 - PROCESSING PROCESS FOR A GAS OR LIQUID HYDROCARBON RAW MATERIAL AND TUBE FURNACE TO PERFORM THIS PROCESS - Google Patents

Description

! • ATBNTANWALTB

DH. O. DlTTMANN K. U OCHIFF DR. A. τ. FÜNRR DlPU. IN O. P.

• MONCMKN βθ MAHIAKIt ^ Tt-ATX · * 8 Aftiliftpft

DA-8343

Description of the

Patent application

of

Vsesojusnyj Nautschno-Issledowatelskij i projektny;} Institut neftepererabaty-Yra _t 1uschtschej 1 neftechimitscheskoj promyr.chlcnnosti, USSR, Moscow, uliza Friedricha Engelsa, 32

concerning

VKßARBBITUlTGSVEllPAHliKti FOR KLMEM GASEOUS OR LIQUID ·; Κ KOHLENWASSISSROFP-EOHSTOPF AND ÜDHßENOFEil FOR PERFORMING THIS PROCEDURE

The present invention relates to methods for Performing chemical reactions and on devices to realize the same sonic more specifically to a processing method for gaseous or liquid hydrocarbon raw material imd to a tube furnace to realize this Procedure

The invention is most successful in the production of petroleum products of olefinic gases "which are largely used in the industry where organic compounds are only used by Eyrolyco"

There are already processing methods for gaseous and

309843/1126

known liquid hydrocarbon raw material in which the Hydrocarbon raw material flow under excess pressure in the convection zone is directed. The raw material is preheated in this zone. Then the preheated raw material becomes the radiation zone directed. In the latter it is at the same temperature warmed, at the Konlenwaeeer "tioff-RoliGtoff in Zielprodincte, e.g. ethylene, propylene, butylene, divixiyl etc. with simultaneous Coke formation is converted.

With such a preparatory work for coal carbon raw material, however, deposits of undesired products in the form of solid deposits, such as coke, arise. In this way the conditions are worse, among those dsr Wtirr · -..? Transferring process runs what niodrigore effectiveness Ooa Verarbeitung3verfahrens for hydrocarbon raw material, ie reduced yield of end products, with the result. It is necessary to remove the coke above, but this makes the process discontinuous.

A tube furnace for realizing the processing method for coal raw material is already known, in the body of which a tube coil is provided. A Abscfcnitt the coil is located in the Konvektioneaone of the furnace, the ^w to preheat the hydrocarbon Rohstoi fstroms serves * The other Robrschlangenabschnitt is the Radiations zone of the furnace, which is the hydrocarbon for ¹⁵ TWaTmGn st off current on the temperature determined, in which the raw material is converted into end products.

3 0 fJ 6 l> 3/1 1? B.

However, such furnaces operate discontinuously. The uninterrupted formation of significant coke cones on the inner surface of the coiled tubing makes it necessary to shut down the furnace often to burn out the anc ^e semm ^e l "t ^en coke. Coke formation also reduces the pipe cone cross section, which impairs the heat transfer through this wall and consequently the furnace throughput gorinner .

Changing the furnace charge Xteriatics while the furnace is in operation makes it much more difficult to optimally control the furnace.

In addition, the heat transfer coefficient in the tube furnace during the heat transfer from the inner tube wall to the stream of hydrocarbon raw materials and end products is relatively low, which makes the heat transfer process worse on the whole. The consequence of this is a very long pipe coil, whereby the tent, during which the raw material to be processed and the end products remain in the radiation zone, is lengthened.This increases the pressure in the pipe coil and consequently the yield of end products is reduced, but the expansion o in undesired by-products. Large abmoeguugea of the pipe coil result in significant external dimensions of the furnace.

It is the goal '.'. of the present invention, the above to reduce disadvantages

The invention is based on the object of such a processing method for gaseous or liquid hydrocarbon raw material to develop, to which the deposits

309843/1126

Desired products in the form of collected precipitates, e.g. of coke, lower nerdor \ ma dio productivity of the heat transfer in the RoJmtoifver & ^ processingazonsn is increased, as well as a tube »/> Acn to create the preliminary dleseo process.

The geatellto Autf & abo is solved by the fact that, in the known processing zone, for easy or flünnison Kohlennasßorstoff-Bokr, wQ; C £ by ZuI θ it η under overpressure of the preheated in the Eonvection zone to the zone for Emission to the Emission The temperature at which the appointed coal-fired raw material is converted into end products with simultaneous formation of coke, takes place in the coal-fired raw material inlet and melts without fuel and / or their oyydon and / or their salts can be drained from sol & / or salts , nolcho d «? a ßroü from atoff-Botetcff wbA .

because a® rolls; nus {^? br @ lt> otc and continuously oioh Zwiech © iiplirv? Ti3ilR © feo bot feohos Twcbiilean -der d # o Inteaoivoni Ablnisfa dienon Proaorrj'üfl-eateteiit ·

B®1 hote ^ n Gonchrjindigkeitoa uoa KohlennosnorotofffRohfltoffetro "* 3 dieß-5 FlüoolßhoitrncfeJLoht eterlt törnirbelt and is really ixx oincm state, yes that they are nlCi from the current surfaceQ loot ur», the sameB & 3. In this way, ebesXrlls dio Intewilvltät, who the Wörrxo

3O9ÜA3 / 1 12G

ίΐ

application process is running »increased

Simultaneously with the intensification of the heat transfer, the time increases during which the processing process of the gaseous or liquid coal wet rat off raw material runs continuously, since deposits of undesired products in the form of solid residues, e.g. coke, are avoided. Coca flipping through you? flleAcndci liquid θ layer; taken and ummt © rbroehe; & außs ^^ S ⁰¹ ^ ·

ZrrectaaäfilQorcslsQ nirö in d © n Kohlönnc ^ isoratoff-Rahstoffstrora except the river igke It forming melt aaohicht still molten mm Hotallen and / or your oxides and / or their Sal-sen in disporgiertMi state led, v the losses mentioned "Plüasighoitssohicht? Qtt75P "v ^ oh? Ii ·

Enpfohlen Ba nird, oF? R "5lK © eua metals and / or oxides ihron usd / odor their BcXz ^ n ₉ has the Sch in Kohlennasser- • toff Rotoatofffotroin SSOL ^ i ^ ot nJLrd a Siedetönp © temperature, the practice «dor ΤοηρονοΰϋΒ lirjjo, boi der dor ernSLtme raw material In. EndprsSw? rto ur-scnr ^ oXti n ^ fffl, r5hre®.4 your öafomolstexaperator nlc ^ jricjor rOLß öir« Tor ^^ ra ^ w? doo »it vorßerj appointed Ro.bitoffn lot.

üosm the fielmolBferripfffeCfiMP dor SSOB ~ 5lze above the temperature d © a moment (pü & rntcn KohlonnnSflarstoff-RohatoffotroiPa is, goes dlo ßohnolM toilr; Oino or fully beads in the solid phase and <s hrsJa dmsufolgo koine liquid aach layer of Schneiro _entntcbon.

üonn the sled temperature of the office below the temperature

91 ^ 3/1126

lies at which the mentioned raw material in end products is converted, a large amount of the melt becomes vaporous State discharged, i.e. the amount of melt used increases sharply.

Desirably the melt will be made up of metals and / or their oxides and / or their salts orryde of elements at least one of groups III, IV and V II of the Poriodensyatema of the chemical elements added in the solid phase. The melt of metals and / or their oxides and / or Their salts can be in the hydrocarbon Ro material flow to vr be routed to other points.

By adding oxides or salts in the solid phase, the viscosity is increased according to the resistance and sf ILLi rekelt of the cover layer, whereby the consumption of fuel is reduced. The mentioned oxides can Y have transactions vbalytische own.

In general, the melt is made up of all and / or Their oxides and / or their salts in the active Kokeblldungszone directed. This reduces the flow resistance when the raw material and the end product fly through the pipe coil decreased, resulting in increased effectiveness of the processing method for hydrocarbon raw material, i.e. the yield of end products is increased as the conditions for the flow of the heat transfer process improved and the coke deposits reduced The task at hand is achieved in that in the body do /

3098/4 3/1126

Tubular furnace for the process according to the invention is provided with a pipe coil, one section of which is located in the convection zone of the furnace, which is used to preheat the hydrocarbon raw material stream, and the other section of which is in the radiation zone for the oxygen raw material, which is used to heat the carbon fiber raw material flows to the temperature at which he? is arranged, in the pipe coil wall at least one opening is provided for the flow of the molten metal and / or their oxides and / or their salts fed to the injection nozzle into the pipe coil space, in which there is a flow of coal-fired raw material and / or end product ·

Sine such execution de. Tubular furnace significantly increases the time during which it is continuously in operation, since the carbon deposits on the tube surface are significantly reduced and coke is reduced by the flowing liquid. E layer of melt is continuously discharged · This design also increases furnace throughput as the yield of end products increases and the yield & a. unwanted by-products smaller nird. The reason for this is the intensification of the heat transfer process, which enables the length of the pipe to be reduced significantly and, at the same time, to maintain smaller outer dimensions of the furnace «

■ 3098 A3 / Π 26

rcordrt *. in the Rndiatio & snono In Rohr-

schlengenrptwi 8cbXftwtasy & £ 8xT \ i.fso iSa & aixColn ^ goortosti

The ßchr & ufoeaTÖrmisra shovels AIfMNi swi uniform share dor nüaeißhoitsßchicht & ub 8ebr.9l & 9 u & d to nt, nb 11 on Flleßea dlorsr Flttnolß? ToItsschicht entires dor Rotß © Wtßagenixmentläcbo ·

Ee τιΧτύ Γ- »ρίΡφΕΛ © 3», dl © rßlM »attbcsiföml5 © a Sohnnfola hattpteächllch rn don ßüollrn γ ^ γ, ιλοτγ ^ γώ, ca demon die Roferschlenee uia-Int«

Ztelo ewd VosrtolLo dor iftefiaduas Bind nwvo dor

^ ülXlc ^? x P ^ nciircilbiHOs von AucTtlhrimssH belepielen umä awn äon Z ^ Xohurm ^ en can be seen; ea so igt

Jig 1 dim ecfer ^^ tilecher structure don Eöhrenofona,

Fig. 2 the RiPsTürmißo Binspritzdüee for guiding Melt in don Roarcchlcoasenrcxwrx and a ring-shaped show » fine,

Eiß · 3 den VorojrbQifci ^ snproBcS by ßeusförnigri odor

iron KoML © ar7ffiffli2 '*) 3!? oti © £
© aofSmiisor <r? »Or

often arrives la ßcnin ^ h nit ünnordpr ^ f cwofeer © inrra Brttoii from 3 ·. · 1-5 e & ewa Vorcflrriift r "S oiiao Tcr ^ esspisiir vea Γ <ϊΟ. #. TQO ⁰ C in the Ko3S90lctloiiacone. B ^ r rafter9 E ^^ tioff tsJjpö ßpan In the Re ^ iationQseso cun ί ^ χ. '^ Λ' »wrf eino £ ογ $ * μ? ΓΛ?« From 700 ... HOO ⁰ C ßQleltot, boi dos or in Endprodiairto, β · Β · Eutjlen, propylene, divinyl urane, under

309843/1126

education nnjjrrjeiaiÄKLt! trirfl. Ia ϋπη Kohl emnnonarot off -Rohst off-

■ *

atrora, dor nit h®hrv (fanchrtirfliGftolt fXIeBt »nwill eiivs melt from MetrvLlon uwVoilcr your ÜT ^ dra iraä / odor your sflzen so ßoloitcri;» Är \ Q nino fluxoado nüesis ^ eitnschicht au? rürßfeoa stron from Kohlenrf & niMMtoff-Rohetoff uü4 / ODNR Endprodu.M;. ojx · driving under Dierson Bodingungen atrunt dio riüoni ^ ^ oitn ohicht in deraelbra direction as the raw material PIb Biedotr-dor Tsoratwx introduced melt is above represents Ecrpornttsi roa 700 ....? 1100 ⁰ C, bsi dor dor raw material in

nirfl, nourishing the ßchaelatoraporatur

untor Aas Eohot; oif-VorT-torau3i> sntc? «poratur of 300 ... 70O ⁰ C. KoKn (in F © 3m from Έ.Φ) nird fli ^ roh dl © flowing liquid aachioht ftw.a Behsiolr ^ nitsan © '- ¹ ·· * ^? * And ununtorbroohcn discharged

The forehand ones in the öor flicScaden layer of liquid guarantee dead ( ¹ I (JXO ^ Zßsfocfö intchnSZctulncA üarnenantaunch, d © r by Ale Jtefli ^ stnsen ^ οπί52 / - ~ Λ öJUsröj v ^ tor dcl toonacn dio ü5xindosso tochLncerticrtic rtochfcirden from the Htteal döf3 Ee ^k ^ e ^ T7Qqc0ffn15®iiS-Rotefrö © S £ ntror.r »icft dio ßloKo der Flüesic-

c ^ ffiß ^, oio nir ^ nöwplc vorirbolt and is located in © in the F ^ M ^ r ^ i * λ fin nio αλοίι vei »dos? £% ronoborfläche us "3 ^ Jioioivi-sltlg .pnrsioirte Eofer ^ lß ^ erfeSt» On this will oinn ro it ntt ^ cob3? OiuOti5 waA continuously oich erefe ^ wpiwaonfl ^ oho bc <i high tarbul <ma - the main dinßU03 doa intonaiven dos Vämeübertrasungoprozunggebildot ·

309843/1126

> 217869 - ίο -

The Jladexung the hydrodynamic conditions and zn ar of the raw material off ν oil uaens by heating and converting and the linear

"- * ·" speed leads to the rupture of the liquid

; uo · To make up for the loss of liquid layer, Melt from metals and / or their oxides and / or in the dispersed state

ale

the chemical

aar druppeu III.CT ^ dVtH ae ₃ EL ^ ute in solid ^ '^ have catalytic properties.

The melt "earth at" Ehreron points of the Raw material drops. e.g. ** first PunW In h. one sohicht and at the point to the sealed state but apply . that »elferhln a liquid layer forms,

fed

The melt is going to. the flow resistance when flowing

of the hydrocarbons in the active coca formation

zone directed

The process is carried out under a pressure of, for example, 40 atm. At the outlet, the end products are separated from the liquid as aschich ⁴ '. The latter is fed back into the cycle for regeneration and then

Example # 1 In the convection zone, butane is mixed with 2%

:, which makes up 23% of the butane weight. The Bc

309RA 3/1 1 26

'• ν

Ze ana lithium chloride is fed into the radiation zone with a temperature of 625 ° C in the form of a liquid layer. The process is at a pressure of 15, and carried out at a Tenperatur of 780 · ⁰ ..820 C at the outlet, wherein the butane 0.7 ... 1.0 s remains in the Badiationszone.

The uranium degree of butane is at least 90 pounds. The yield of the most important end products is as follows ©. ' Ethylene ^C 2 ^H 4 ~ 2 ⁸ ··· ^ ^{2 wt} «#» propylene CJI _6-16 ... 20 GewoJS, Diviryl C ₄ H ₆ -. 1.8 ... 2.5 weight%.

Example Kr.2

^{Gasoline ratet ion gexoitot preheated to 500 0} C and diluted up to 40 / i by water vapor in the tubular hoactor with external ^{heating, which starts to boil at a temperature of JO 0} C and stops boiling at a temperature of 160 ⁰ C and ends is composed of the following components: n-paraffins - J6% by weight, i-paraffins - y * % by weight, naphthenes - 22% by weight, aromatics - 8% by weight. In the Roaktor will also lead melt with the addition of a mixture ⁷⁰⁾ ^ ⁰ "which is promoted by Kaliiunvanadat advantage, SiO _2, NiO * passed. This mixture is taken in an amount equal to 20% by volume of the melt. Last gate is fed in such a way that a flowing liquid layer is created which surrounds the gasoline fraction stream. The gasoline fraction remains in the reactor for 0.4 ... 0.6 s. When leaving the reactor, the products have a temperature of 670 ... 76O ⁰ C and a pressure of 0.1 ... 0.2 at. The yield of the most important end products is as follows: Ethylene C ₂ H ^ - 24 ... 28 wt ^. Propylene

309843/1126

C ₇ H ₆ - .13 ..ί »6% _{by weight, butylene C 4} H _8-3 ··· ^% by weight, divinyl C ^ H ^ - 'U.« 2% by weight, benzene C ₆ IT ₆ -2 3% by weight.

The tube furnace to realize the above Owns processing procedure for foal water raw material a body 1 (Fig.!), in which a raw snake 2 is housed let. '

One section of the pipe coil 2 is located in the convection zone 5 of the furnace, which is used to preheat the hydrocarbon raw material stream to a temperature of JOO.600 C * On the other hand, the powder section is located in the radiation zone 4 of the furnace, which is used to heat the carbon hydrogen raw material stream to a temperature of 700 ... 1100 ⁰ C, at which it is converted into end products, such as ethylene, propylene, butylone, Diviayl, etc. with simultaneous coke formation.

The walls of the radiation zone 4 of the furnace are formed from several rows with burners 5 in which the fuel, which is fed in via a pipe 6, is prebaked. The gas v? Vore! On obtained in this way is removed from the furnace via a smoke vent 7. The section of the Rohrschlp & so 2, which is in the Radiationazono 4 ü®b ΟΓβηιι, plumb bob with a ring-shaped Einspritsaüao Ö (Fic »2), ura dlo melt uue MotaJ.lon and / odor their Oa ^ dea and / odor their Solzsn to lead. At the tunnel, in which the Einaprltzdüoo 8 is cngebrc.cht, there are in the wall of the pipe coil 2 openings 9t through which the melt in the space of the pipe coil 2 ports,

. ' 1 1

in which the carbon raw material stream flows.

Helical blades 10, which are used to increase the Resistance of the liquid layer from melt serve. are mainly in the space of the pipe coil 2 to the Places where it is bent, inserted

The processing process of gaseous or liquid hydrocarbons -Rohst off ο in the tube furnace is based on the in illustrated process, <3 © r from the I ^ rrolysis of the 8toff raw material advises, considers

Gaseous or liquid carbon raw material in a mixture with water vapor is passed under a pressure of 3 ·· .45 atm for preheating to a temperature of 300 .., 70O ⁰ C in the section of the pipe coil 2, which is in the ready-to-use 3 of the tube furnace is · Thereafter, the hydrocarbon raw material is placed in the portion of the pipe coil 2, the ε-I is of the tube furnace in the Radiationszono 4-, and mixture ^ with dor melt aua metals and / or their oxides and / or their salts dia The ring-shaped injection nozzle 8 (FIG. 2) can be fed to the north, so that a flowing layer of liquid is created. The coil 2 is heated in the radiation zone by radiation from the rows with burner mandrels 5, into which fuel, which is fed in via pipe 6, is burned The help RpAich & aso flow out of the Radiationazono 4 of the furnace Into the Konvoktionazono den OSorm, no they give their Warmo to preheat the hydrocarbon raw material On the Rauchgaoo the stove over the Raucli extractor 7 (Fig.l). The coal ^ .va-

Hydrogen raw material is heated in the radiative zone r of the Ofono of the pipe coil 2 to a temperature of y (J ... 1100 C and subjected to pyrolysis, in which the end products, e.g. ethylene, butylene, divinyl and propylene Since the pipe coil 2 pyrolysis products and di «i'iüsaigkei.tsachich ■ from Schmelso move around in the room, the pyrolysis process is highly effective heat transfer and without coke deposits on the pipe slaugon walls ^ on the pyrolysis product and the PlüssiükoitRschicht with ueü captured coke particles for cooling in a heat exchanger 11. Here the pyrolysis products are cooled down quickly to 500 ... 650 ⁰ C, whereby the occurrence of undesired reactions, i.e. the formation of undesirable by-products, is prevented The flow of the pyrolysis products leaving the heat exchanger 11 with the liquid layer made of melt with the stones contained in it The small portion reaches a separator 12, in the dome the coke pulp in the liquid phase is separated from the pyrolysis products. The latter?; Earth for further cooling and processing. The melt with the coke suspended in it passes into an apparatus IJ for separating out the coke 11 chezi. From this apparatus IJ, the melt *, which has been cleaned of coke particles, flows back into the system, while part of the melt with a high coke content is passed into an apparatus IA-for removing the coke. In JU> parat 14 you can

309 8 43/1126

Coke to be burned. For this purpose, fuel gas and air are used Passed into the apparatus 14. Flue gases escape from the latter and the melt, which has been cleaned of coke, passes through the annular injection nozzle 8 in the radiation zone 4 of the furnace the pipe coil 2.

By preventing coke from depositing on the walls of the coil 2, continuous tube furnace operation without shutdown is started for coke burnout, ensured. As a result, will the automatic control system of the process is significantly simplified.

DlO pyrolysis is carried out with a significantly lower dilution of the gaseous or liquid hydrocarbon raw material Steam is carried out than is the case with the usual heat treatment.

As a result of the highly effective heat exchange, the pipe coil length l _t 5 ... 2m & l becomes shorter without changing the performance during raw material processing. As a result, the outer dimensions of the furnace are significantly smaller, the pressure in the system is reduced, the time during which the raw material to be processed and the end products remain in the system, significantly shorter because the average total temperature of the process can be increased, which in turn results in a higher yield of end products has the consequence.

3 O 9 B 4 3/1 1 2 6

Claims (1)

PAIEKT CLAIMS: {1. J Preliminary work on the longitudinal process for gaseous or liquid hydrocarbon raw materials through the supply of ei * under excess pressure of the hydrocarbon raw material flow pre-heated in the convection zone into the radiation zone for heating to the temperature at which the extracted © hydrocarbon raw material in the end product © with simultaneous coca formation is urose-treated, characterized in that melts made of metals and / or their oxides and / or their salts are fed into the hydrocarbon raw material flow in such a way that a flowing liquid layer is created from the melt, which surrounds the flow of carbon dioxide raw material and / or end products. Processing method according to claim 1, characterized in that in the coal-dyestuff raw material stream but the so-called liquid layer forming the so-called "still aisles" or their oxides, cM / odorous their sweetness and odor are diverted into the dio loss ο cn erräfeato »nünalgkeitacofeicht nettsumofeoa · 3. Processing method Dn $ h claim 1 and 2, d β -by gok © r \ nr, ο ichnet, drß dio ⁰ O ^, oil so made of metals, ussa / odo :? IJbcrc ^ Oryör- ^ and / or their ßsls ^ i, which nlrJ in the coals & an ^ r & tiofJC-Eol ^ toffotroai, has a ßledetemporatur, dio ^ bQJ? dor tenporatur · lies at which the mentioned raw material in end product ο umgevroAdelt nlrd, nourishing Your Schaelztenpercvtur imtor dor door temperature dos preheated 30A3 / 1 12 « mentioned raw material lies. 4 · Processing method according to address 1 ... 5, as it is indicated that the visor made of metals and / or their oxides and / or their salts of elements is at least one of the groups IH ₁ IV and VI I of the periodical system • * ■ * * ■ of the chemical elements in the solid Ph? g . 5 · Processing method according to Anapx .ch 1 ... 4, d ad u r c characterized in that the melts of metals and / or their oxides and / or their SaI: η in the flow of Carbon dioxide raw materials and / or end products at various Points is forwarded, 6 · bequeath it to ungsverjtahr by steps things I 5 "in the fact gekennze iohnet _t that the Sch; > Salts made from metals and / or their oxides and / or their. BaIren in the Kohlenwaaseratoff-Rohstoffatr-om in the active coke formation zone it becomes yellow. 7 · tube furnace for Vernirklichen of Vererbeitungsverf ch rejQS according to claim 1 ···. 6 a coil is provided in its body; one section of which is in the vection zone of the furnace, which is used to preheat the hydrocarbon raw material Stroms serves, and the other section is in the Rßdlationszone dea furnace, which is used for heating of the hydrocarbon raw material flow on the temperature, in which he la end products with simultaneous coke formation is converted, characterized in that that the pipe coil (2) at least with an annular 3 0 9! Sa 3/1126 - 18 - Injection nozzle (8) is provided in any furnace zone is attached, and that at the point where the aforementioned injection nozzle (8) is attached, in the wall of the pipe coil (2) at least one opening (9) for the throughflow of the molten metal and / or melt fed in via the injection nozzle (8) their oxides and / or their salts in the room, the pipe coil (2), in which the stream from hydrocarbon raw material and / odsi Target products flows, is provided 8. Tube furnace according to claim 7 »dad ure h | g e k e η nzelATED, that helical blades (10) are arranged in the space of the pipe coil (2) 9 · Tube furnace according to claim C, characterized. marked, desß the helical blades (10) mainly, are arranged at the points where the pipe coil (2) bent 1st 3098A3 / 1126