Патент USA US2111899код для вставки
' _ingested 22, 193s l 2,111,899 r. ' untreu STATES.. vPA'raN'r-»or (ICE „2,111,899 l I .moonssron 'nm _ / t , E _ armena . a ' „ mNUFAc'rUnaor monton.. ~ 'rnedaorenggetnmxlmnmf Appumßnpeœmber 1s, 1935, serial N9. 55,011 ' ' ,-2 emma (cieco-1ro) . - while subjected to suitable pressure -and velocity method for producing ethylene, a hydrocarbon sc_that upon dashing the preheated oil into a gas (12H4 of the olefin seriesVfrom liquid hydro-v hotter reaction zone substantially fall of the oil carbon mixtures of the type round in petroleum.' is almost instantly heated and cracked to ethylene and hydrocarbons oi.' lessthan’four carbon atoms, 5 »5 „in which _new process the correlation of temper -' atures, reaction velocities and reaction periods of this hot 'gas being immediately shock chilled be ' The subject matter _of this invention is a new time produce yields of ethylene far in excess of . low the polymerization temperature zone toprac- ‘ the ~-yields by the current methods‘of, producing tically exclude polymerization before a substan tial amount of ethylene is polymerized. ethylene from hydrocarbons. io - In the oil industry ethylene is a by-product in converting heavy-oil to >gasoline by pyrolysis and 1 In the accompanying drawing I have illustrated 10 ’ diagrammatically embodiments of my invention: ` the -yieldvof ethylene, depending upon whether ' Fig. 1 illustrating v_an embodiment of the inven- g the liquid or the vapor phase method of crack tion wherein lthe reaction zone is externally s' ing is employed, varies in amounts up to approx heated; and . _ ‘ 15 imately 6% by weight of the charging stock. Fig. 2_ illustrating. an embodiment `oi" the inven- 'lo In the chemical industry, in the operation di- I tion _' wherein the reaction zone is' internally rected to the production of ethylene from liquid j heated. ‘ 1 ` ~ “.hydrocarbons,- a` variation of the vapor phase ~ As an example of the practice of my invention ’ method used in the _oil industry is employed. V Ñfor the production of ethylene from gas oil,` and ^ In the oil industry the yield-of liquids is in the- with reference ilrst of ,all tó Fig. 1:l Tlie oil to be order of 75% by weight of the charging stock and processed is taken from any suitable source of the ethylene yield as above indicated is only about ‘supply I and supplied to the pressure preheater 6%; in the chemical industry the yield of liquids 2 at a pressure in the order of, for example, 20 is in the order-oi.’ 40% by weightof the charging ,atmospheres or higher pressure, iiowing continu stock and the ethylene yield is in the 'order of , ously through the preheater to the reaction zone 10% by weight of 111e chargingstock. _ _3. The _oil -is preheated to a temperature in the As` distinguished kfrom these prior processes, order of 850° F. In the preheating step of my the present invention provides a method wherein process temperature and pressure conditionsare the ~yield of lliquids is reduced` to less than 10% by s ¿o weight of the charging stock and the _fyield of . 29 25 , i so controlled that the oil remains in the liquid phase. The preheated oil iscontinuously in- 30 ' 1 ethylene is increased to as high _as 45% by weight - iected into the hotter reaction zone 3, flashing of the charging stock. - ` into vapor, the temperature of the hotter reactlo'n ~ « .One of the `objects ofthis invention is the pro- ' zone being so controlled that substantially >all of' .. ' duction of ethylene as'the primary product oi' the ' the oil vapor'is’ converted to ethylene and hydro operation in converting substantially all of the carbons of less than four carbon atoms at a tem-. 35 . >charging stock to gases, the yield of >condensible perature of inthe order of 1400° F. _The' hot gases are immediately shock chilled to below '~ polymers being inhibited substantially .tol ex‘clu sion.“ This operation is notof necessity .an ad '1000°. F. in the cooler- 4 so as to practically- _exfA junct to .oil reñnery operations but can be con _clude polymerization before a substantial amount . 40 veniently located wherever ethylene isfdesired for use either directly orfas a process material.V ( " `Another object of this invention is the produc tion of ethylene from liquid hydrocarbons. where in I obtain a yield of ethylene as high as 45% 45 by weight of the hydrocarbons charged, my meth# _ ’ od providingïor the ñash system cracking of pre, _heated liquid hydrocarbons, the ethylene thus -produced beingl prevented from polymerizing to of ethylene; is polymerized, thereby avoiding yields 40 of a substantial quantity of liquid, i. e., not in excess of '10% by weight of the charging stockí" ' " The cooled -gas ñows to a fractional distillation unit 5, which separates the ethylene> from the products of pyrolysis. . _ In the embodiment of my inventionlas illus ` trated in Fìg.'2 the procedure is the same as out- ' - lined above, the reaction zone being internally ’ heavier hydrocarbons'ythereby insuring the maxi- ` heated by hot products of combustion from source 50 mum yield of ethyleneand the liquids. \ ‘ yield of v 8. Chilling of the hot gas- is effected by water 5o injected into the/gas as indicated at 1. The ` Mynew process produces these novel results ~ ethylene is separated >from the products of py from liquid hydrocarbons in a continuous opera 'rolysis by chemical reactionas shown at 8. In e example given above ‘I have mentioned tion, the process comprising the operations ofpre 55' 4heating `the oil to a suillcientiy high temperature 'a tem raturein the order oi' 1400° Il'. with refer-' g55l F ence to the gas in the reaction chamber. This was in connection with the use of gas oil as' the charging stock. lIt is to be' understood that with diiierent charging stocks the temperature at which the reaction takes place and the time necessary to obtain the optimum yield oi ethylene _therefrom vary, but in any case the temperature should not be less thanv >approximately 1200? F. and the reaction time should not exceed approxi mately one and one-half seconds to avoid pro-v oil are instantly decomposed to ethylene and hy drocarbons of not more. thanfour carbon atoms, and immediately upon attaining this temperature shock cooling the gaseous mixture to below 1000“ F. tov exclude ,polymerizing reactions forming gasoline hydrocarbons and to retain the hydro carbons as ethylene and hydrocarbons of not more than four carbon atoms. 2. The process of producing ethylene from gas 'oil, which process comprises <preheating the oil 10 ducing condensates. Furthermore, the temper-' to a temperature in the order oi' 850° F. while ature should not exceed 1600° F, because at such ‘ subjected to superatmospheric' pressure, con temperature ethylene decreases. Preferably the temperature ranges between ~1300" F. and A1500° trollingtpressure and time conditions whilelpre heating so that the oil remains in the liquid phase, injecting all' of the preheated „oil into a temperature, preferably ranging from approxi flowing4 gaseous medium which contains sum mately one and one-halt seconds to less than » cientheat for heat exchange to the preheated one-half secondA in order to obtain the optimumv oil to ilash heat the preheated oil to within the yield 'o1 ethylene. ' temperature range of 1300° F. to 1600", F., at What I claim is: which temperature all of the hydrocarbons' of the 20 1. The process of producing ethylene from oil, oil are instantly decomposed to ethylene and hy which process comprises preheating the oil under- drocarbons .of not more than four carbon atoms, superatmospheric pressure while maintaining the and immediately upon attaining this vtempera oil slightly below its vaporizing temperature at ture shock cooling to below 1000° F. to exclude 25 25 that pressure, injecting al1 of the preheated liquid polymerizing reactions forming gasoline hydro 15 I". and the time varies in inverse relation to the oil into a ñowing gaseous medium which contains suiiicient heat for heat exchange to the preheated - carbons and to retain the - hydrocarbons as oil to flash heat the preheated oil to within the ethylene and hydrocarbons of not more than four temperature range of 1300”.F. to 1600” F., at 30 « . THEODORE NAGEL. , which temperature all of the hydrocarbons of the _ carbon atoms. ` . y « ` > .