Process and installation for recovery and purification of ethylene produced by pyrolysis of hydrocarbons, and gases obtained by this process

Abstract

A process for the high-yield recovery of ethylene and heavier hydrocarbons from the gas produced by pyrolysis of hydrocarbons in which the liquid products resulting from the fractionated condensation of a cracking gas for the recovery of almost all the ethylene, are supplied to a distillation column, called a de-ethanizer, at different intermediate levels. At the top of the de-ethanizer the vapor of the column distillate is treated directly in an acetylene hydrogenation reactor, the effluent containing virtually no acetylene being separated by a distillation column called a de-methanizer, into an ethylene- and ethane-enriched tail product, while the head product is recycled by compression or treated for subsequent recovery of ethylene.

1. A process for fractionation of a substantially anhydrous gas resulting from pyrolysis of hydrocarbons, containing hydrogen and hydrocarbons, particularly hydrocarbons from C 1  to C 3 , including ethylene, propylene, and acetylene, in at least one of a hydrogen and a methane-enriched current, at least one of an ethylene-enriched and an acetylene-poor current, and at least one propylene-enriched current, the process comprising, in stages:
 a) cooling and liquefying a gas resulting from pyrolysis of hydrocarbons, progressively, under pressure by passage through a series of increasingly cold successive heat-exchange zones, separating at least one condensate after passage into each heat-exchange zone, at least a first of the condensates being propylene-enriched, and at least a second of the condensates being ethylene- and ethane-enriched, and containing, in solution, a smaller proportion of hydrogen, methane, and acetylene; and collecting a residual hydrogen-rich gas;  
 b) at least partially evaporating, by a reduction in pressure, the second, ethylene- and ethane-enriched condensate and the first, propylene-enriched, condensate, and heating, in at least one of said successive heat-exchange zones, by thermal exchange with fluids to be cooled, including at least the gas resulting from pyrolysis, to provide, respectively, a first fraction at least partly evaporated due to the reduction in pressure and the heating of the ethylene- and ethane-enriched condensate, and a second fraction at least partly evaporated due to the reduction of pressure and the heating of the propylene-enriched condensate, to provide at least part of the cooling necessary for the cooling and liquefying of the gas resulting from hydrocarbon pyrolysis upon passage into the successive heat-exchange zones successively;  
 c) introducing the at least partly evaporated first and second fractions resulting from stage (b) into a part of a distillation column called a de-ethanizer, the ethylene- and ethane-rich first fraction which is at least partly evaporated, at a point of said distillation column higher than a point of introduction of the partly evaporated propylene-rich fraction after the partial evaporation, the part of the distillation column operating under conditions of temperature and pressure for separation, in an upper part, of a first head gas current rich in ethylene and ethane and containing, in a smaller proportion, acetylene, hydrogen, and methane, and in a lower part, a first bottom liquid current enriched with propylene, and collecting the first bottom liquid current;  
 d) sending the first head gas current from stage (c) into an acetylene elimination zone eliminating acetylene by one of extraction with a solvent and selective hydrogenation of acetylene with the hydrogen contained in the first head gas current to provide a current essentially free of acetylene, and  
 e) cooling and fractionating, in a part of a distillation column called the de-methanizer, the current essentially free of acetylene to produce a second head gas fraction enriched with one of hydrogen and methane, collecting the second head gas fraction, and a second bottom liquid fraction, enriched with ethylene and ethane, and essentially free of acetylene, and collecting the second bottom liquid fraction.  
 
     
     
       2. The process according to  claim 1 , wherein the gas from hydrocarbon pyrolysis is at a pressure of 15-50 bar, and the distillation column is at a pressure of 10-30 bar and, lower than the pressure of the pyrolysis gas. 
     
     
       3. The process according to  claim 1 , wherein the evaporated fractions introduced into the de-ethanizer contain dissolved hydrogen in a proportion so that the first head gas current contains 2-10%, in moles, of hydrogen, and, in stage (d), the selective hydrogenation is essentially in ethylene with the hydrogen contained in the first head gas current of stage (c), and the temperature at the hydrogenation ranges from 0° C. and 160° C. 
     
     
       4. The process according to  claim 1 , including using only hydrogen dissolved in the evaporated fractions introduced into the part of the distillation column called the de-ethanizer for the hydrogenation in stage (d). 
     
     
       5. The process according to  claim 1 , including obtaining at least two condensates after successive passage of the gas resulting from pyrolysis, respectively, into at least two heat-exchange zones of stage (a) and sending into an upper part of the de-ethanizer of stage (c). 
     
     
       6. The process according to  claim 1 , including purifying the second head gas fraction exiting the de-methanizer by distillation to recover ethylene and ethane. 
     
     
       7. The process according to  claim 1 , wherein the gas resulting from pyrolysis is a gas from pyrolysis of one of ethane and an ethane/propane mixture, and including mixing the second head gas fraction exiting the de-methanizer with the gas resulting from pyrolysis without ethylene recovery, for treatment in mixture with the gas resulting from pyrolysis in stage (a). 
     
     
       8. The process according to  claim 1 , including increasing hydrogen content of the first head gas current exiting the de-ethanizer by addition of hydrogen from a separator, separating a partly condensed fluid produced by refrigeration, in a heat-exchange zone, of a residual gaseous fluid flowing from the successive heat-exchange zones. 
     
     
       9. The process according to  claim 1 , including recycling part of the second liquid bottom fraction from the de-methanizer into the de-ethanizer, to reduce acetylene concentration of the first head gas current from the de-ethanizer. 
     
     
       10. The process according to  claim 1 , including, in stage (d), extracting acetylene with a solvent. 
     
     
       11. The process according to  claim 1 , wherein the first head gas current includes carbon monoxide in a concentration moderating effect on reaction catalysis in the acetylene elimination zone. 
     
     
       12. An apparatus for fractionation of a gas resulting from pyrolysis of hydrocarbons containing hydrogen and hydrocarbons, including ethylene, propylene, and acetylene, in at least one of a hydrogen and a methane-rich current, at least one of an ethylene-rich and acetylene poor current, and at least one propylene-rich current, the apparatus including:
 a) means for progressively cooling and liquefying the gas from the pyrolysis of hydrocarbons, under pressure, by passage into a series of increasingly colder successive heat-exchange zones, means for separating from the pyrolysis gas at least one condensate after passage into each heat-exchange zone, a first of the condensates being propylene-enriched and a second of the condensate being ethylene- and ethane-enriched and containing, in solution, a smaller proportion of hydrogen, methane, and acetylene, and means for collecting a residual hydrogen-rich gas;  
 b) means for evaporating, at least in part, by a reduction of pressure, the second, ethylene- and ethane-enriched condensate and the first, propylene-enriched condensate and means for heating the condensates, independently, in at least one of the successive heat-exchange zones by thermal exchange with fluids to be cooled, to provide, respectively, a first fraction at least partly evaporated, resulting from the reduction of pressure, and means for heating the ethylene- and ethane-enriched condensate, and a second fraction at least partly evaporated, resulting from the reduction of pressure and the heating of the propylene-enriched condensate, to provide for progressive cooling and liquefaction of at least the gas from the-pyrolysis of hydrocarbons upon successive passage through the successive heat-exchange zones;  
 c) means for introducing the partially evaporated first and second fractions from (b) into a part of a distillation column called a de-ethanizer, the ethylene- and ethane-enriched partly evaporated first fraction being admitted at a point of the part of the distillation column higher than a point of introduction of the propylene-rich partly evaporated second fraction, the part of the distillation column operating under conditions of temperature and pressure for separating, in an upper part, a first ethylene- and ethane-rich head gas current containing, in a smaller proportion, acetylene, hydrogen, and methane, and, in a lower part, a propylene-rich first bottom liquid current, which is collected;  
 d) means for sending the first ethylene- and ethane-rich head gas current from (c) into an acetylene elimination zone for elimination of acetylene by one of extraction with a solvent and selective hydrogenation of acetylene with hydrogen contained in the first head gas current, to provide a current essentially free of acetylene, and  
 e) means for cooling and fractionating, in a part of a distillation column called a de-methanizer, the gas current essentially free of acetylene from (d), in a second hydrogen-and/or methane-enriched head gas fraction, which is collected, and a second bottom liquid fraction which is enriched with ethylene and ethane and is essentially free of acetylene, and which is also collected.