Patent Application
20240294835
The present invention relates to a preheating process module for preheating the hydrocarbon feedstock and routing the same into hydrocarbon cracking furnace for cracking to obtain cracked gases, wherein the preheating process module is integrated with coke handling system for supply of petcoke from coke storage yard required for combustion in the preheating module. Further, the module is configured such that the hydrocarbon feedstock is preheated using energy sourced from combustion of petcoke indirectly through a circulating stream of heat carrier particles instead of hot flue gases from convection section thereby saving the convection section energy of the conventional steam cracker furnace and utilizing it for generating very high-pressure steam as a source of utility and also addressing the issues of CO2 emissions which are attributed to steam cracker unit and Delayed coking unit along with petcoke disposal issue.
Steam cracking, also referred to as pyrolysis, is a petrochemical process in which saturated hydrocarbons are broken down into smaller, often unsaturated, hydrocarbons. It is the principal industrial method for producing lighter alkenes (olefins), including ethene (or ethylene) and propene (or propylene). Conventional steam cracking utilizes a steam cracking furnace which has two main sections: a convection section and a radiant section. The hydrocarbon feedstock typically enters the convection section of the furnace as a liquid (except for light feedstocks which enter as a vapor) wherein it is typically heated and vaporized by indirect contact with hot flue gas from the radiant section and by direct contact with dilution steam. The vaporized feedstock and dilution steam mixture is then introduced into the radiant section where the cracking takes place. The resulting products, including olefins, leave the steam cracking furnace are subjected to sudden quenching to stop the cracking reaction and the quenched products is then routed for further downstream processing.
WO 2019/116122 A1 describes a method for converting naphtha to olefins that includes pre-heating the naphtha in stages in a plurality of heating units such as first heating unit (economizer), second heating unit (firebox) & third heating unit (superheater) where third heating unit is a part of reactor in which catalytic cracking of naphtha occurs.
US 2019/0284485 A1 discloses the invention to perform steam cracking of hydrocarbon feedstock while conserving steam cracking furnace convection section energy consumption for evaporating the hydrocarbon feedstock. Naphtha coming from crude distillation is preheated in three stages using LP, MP, and low quantity HP steam. 16% VHP steam energy is saved however feed is preheated up to 210° C. then again it is preheated in convection zone using flue gas and superheaters.
U.S. Pat. No. 5,538,625 A relates to a method for contacting the light-hydrocarbon feedstock like light paraffins, ethane, propane, butane, gasolines, naphtha and gas oils with heat-transfer particles in a continuous flow reactor wherein the thermal cracking reactions occur in the said reactor itself. Further discloses that at least 90 percent of the particles are regenerated before recycling. The process also provides for the separation of the effluent hydrocarbons using a ballistic separator.
US 2020/0172814 A1 relates to a method and system for preheating hydrocarbon feedstock in a cracking furnace system, by hot flue gasses. The process is environmentally friendly and suitable for carbon capturing.
Accordingly, the main object of the present invention is to provide a preheating process module for preheating the hydrocarbon feedstock and routing the same into hydrocarbon cracking furnace for cracking, wherein the preheating process module is integrated with coke handling system for supply of petcoke from coke storage yard required for combustion in the preheating module.
Another object of the invention is to provide a preheating module wherein the hydrocarbon feedstock is preheated using energy sourced from combustion of petcoke indirectly through a circulating stream of heat carrier particles while capturing the generated CO2 and thereby producing CO2 rich flue gas which can be further sent for purification, capture or utilization. This enables capture of CO2 emitted during petcoke burning, which otherwise would not have been feasible if burned as petcoke in multiple locations of the customers purchasing the petcoke, produced in the Delayed Coking unit, thereby reducing the overall SCOPE-III CO2 emissions.
Another object of the invention is to provide an improved preheating section/convection section for Steam cracker unit wherein the rate of feed preheat, temperature of preheated feed can be controlled without affecting the heat flux/fuel flow rate etc. of radiation section.
Another object of the invention is to provide an improved thermal cracking pattern for the hydrocarbon feedstock by being able to control the residence time distribution among the convection and radiation sections of the Steam cracker as and when required.
Another object of the present invention is to enable reduction of SCOPE-II emission of CO2 from the Steam cracker unit wherein the CO2 emissions that could have occurred elsewhere, while generation of additional utility steam & process steam that are generated through modified convection section design of the present invention.
Another object of the present invention is to generate additional power by use of steam generated additionally from the convection section of the process of present invention.
Another object of the invention is to utilize the coke sourced from either delayed coker unit or fluid coking unit or waste material (biomass, plastic, municipal solid waste etc.) pyrolysis unit or coal plant. Further, heating rate of heat carrier particles can be controlled as the quantity of coke used for combustion is in user control.
Still another object of the invention is to use cyclone separator to remove any contaminants back to the heat sink thus preventing hydrocarbon vapor contamination & deposition.
The present invention has the following advantages over the prior art:
Increasing control on the pre-heating rate and temperature of hydrocarbon feed as compared to conventional convection section of steam cracker furnace by controlling the rate of coke input, heat carrier particle flow rate and other combustion parameters
It is seen that different process routes have been described in the prior art for preheating the hydrocarbon feedstock for conversion to light olefins and aromatics. It is worthwhile to note that in the prior art where the hydrocarbon feedstock is pre-heated in stages in a plurality of heating units; steam cracking of light-hydrocarbon feedstock using heat-transfer particles in a continuous flow reactor wherein the thermal cracking reactions occur in the said reactor itself; and preheating hydrocarbon feedstock in a convection section of cracking furnace system by hot flue gases. However, these prior arts have not disclosed any preheating setup which is integrated with coke handling system for supply of petcoke from coke storage yard for combustion in order to preheat the hydrocarbon feedstock using energy sourced from combustion of petcoke indirectly through a circulating stream of heat carrier particles instead of hot flue gases from convection section thereby saving the convection section energy of the conventional steam cracker furnace and utilizing it for generating very high-pressure steam as a source of utility. From this it is seen that there is a requirement for a preheating process module which not only preheat the hydrocarbon feedstock for cracking into cracked gases but also addressing the issues of CO2 emissions which are attributed to steam cracker unit and Delayed coking unit along with petcoke disposal issue.
The current invention overcomes the following limitation which exists in the prior arts:
In some embodiments, the present disclosure provides a cracking furnace system for converting a hydrocarbon feedstock into cracked gas comprising a convection section used for generation of very high-pressure steam, a radiant section for hydrocarbon feedstock cracking, while the hydrocarbon feedstock is preheated by a preheating process module integrated with coke handling system.
In some embodiments, the present disclosure provides an improved preheating section/convection section for Steam cracker unit wherein the rate of feed preheat, temperature of preheated feed can be controlled without affecting the heat flux/fuel flow rate etc. of radiation section. This is not generally feasible in conventional Steam cracker units wherein, to change the feed preheat temperature of the feedstock at the outlet of convection section, it is required to increase/decrease the fuel flow rate to the burners, which could also impact the heat flux and heat transfer of the radiation section. This also might induce additional coke formation in the radiation section in case the temperature overshoots etc. occur in the radiation section while trying to modify the convection section operating parameters. This also might affect the overall product yields from the Steam cracker unit.
In one embodiment, the present disclosure also provides a preheating process module integrated with coke handling system for preheating the hydrocarbon feedstock and routing the same into the hydrocarbon cracking furnace for conversion into cracked gases, comprising steps of:
In preferred embodiment, the hydrocarbon feedstock is selected from Ethane, Propane, C4 hydrocarbons, straight run naphtha, kerosene from atmospheric distillation unit, other paraffinic/olefinic naphtha, kerosene from secondary processing units of refinery such as Fluid Catalytic cracking, Hydrocracking, light oils produced from waste oils such as waste plastic pyrolysis oil, used lubricating oil, bio-oil and other waste oils and combination(s) thereof and requires preheating temperature up to 550-650° C., preferably from 590 to 625° C.
In another preferred embodiment, the location of injection of the mixed feedstock (35) in the hydrocarbon cracking furnace is made at a location in convection section or radiation section inlet which shall be selected based on the temperature of the mixed feedstock.
In another preferred embodiment, fraction of dilution steam (17) is injected in the heat sink vessel (20) and remaining fraction injection in hydrocarbon cracking furnace is made at a location in convection section or radiation section inlet which shall be selected based on the temperature of the mixed feedstock.
In another preferred embodiment, the coke used for combustion is not produced on heat carrier particles internally instead taken either from Delayed Coker Unit or fluid coking unit or waste material (biomass, plastic, municipal solid waste etc.) pyrolysis unit or coal plant.
In yet another preferred embodiment, coke used in the process can be fuel grade coke, fluid coke, anode grade coke, bio char, coal or combination(s) thereof.
In yet another preferred embodiment, the combustion of coke for heat generation along with fluidization of heat carrier particles in heat source vessel can be done either through pure oxygen or air or a combination thereof. Further, excess oxygen is supplied in comparison to stoichiometric oxygen requirement, in the range of 1 to 40 mol %
In yet another preferred embodiment, top section of heat source vessel comprises shell and tube heat exchanger which superheats the steam to generate dilution steam which is then mixed with vaporized hydrocarbon feedstock for reducing the residence time in heat sink vessel before routing to radiation section.
In yet another preferred embodiment, the steam used for generation of dilution steam can be Low Pressure (LP) or Medium Pressure (MP) steam.
While the invention is susceptible to various modifications and alternative forms, specific embodiment thereof will be described in detail below. It should be understood, however that it is not intended to limit the invention to the particular forms disclosed, but on the contrary, the invention is to cover all modifications, equivalents, and alternative falling within the scope of the invention as defined by the appended claims.
The following description is of exemplary embodiments only and is not intended to limit the scope, applicability, or configuration of the invention in any way. Rather, the following description provides a convenient illustration for implementing exemplary embodiments of the invention. Various changes to the described embodiments may be made in the function and arrangement of the elements described without departing from the scope of the invention.
The hydrocarbon feedstock used in the process is selected from Ethane, Propane, C4 hydrocarbons, straight run naphtha from atmospheric distillation unit, other paraffinic/olefinic naphtha from secondary processing units of refinery such as Fluid Catalytic cracking, Hydrocracking, light oils produced from waste oils such as waste plastic pyrolysis oil, used lubricating oil, bio-oil and other waste oils and combination(s) thereof.
The present invention utilizes low value coke for combustion in heat source vessel of preheating module. This low value coke is transported to the heat source vessel via coke handling system which comprises of first coke screener to screen the coke lumps from coke yard, hopper for holding the screened coke, conveyer belt for carrying the screen coke to roller crusher, roller crusher for coke crushing, second coke screener for screening/particle size separation of crushed coke to obtain desired particle size coke particles of size in the range of 40 microns to 10 mm, hopper for storing the crushed and screened coke, conveyer belt for carrying the coke from hopper to coke storage vessel, which is finally injected to heat source vessel by means of conveyer belt or pneumatic conveying system.
The present invention focused on utilizing the low value coke for generating the energy required for heating the heat carrier particles which in turn heat the hydrocarbon feedstock. Coke handling system is integrated with preheating module for supply of desired particle size coke in the range of 40 microns to 10 mm for combustion. This coke/coke powder is not produced internally within the system instead is taken from external source which can be either from delayed coker unit, or fluid coking unit or waste material (biomass, plastic, municipal solid waste etc.) pyrolysis plants, coal plant. The coke used for combustion in the process can be fuel grade coke, fluid coke, anode grade coke, bio char, coal or combination(s) thereof.
Heat source vessel is used for heating the heat carrier particles which in turn heats up the hydrocarbon feedstock. The vessel comprises of coke inlet from side wall and recycle heat carrier particles enters just above the coke inlet while oxygen containing gas enters from bottom of the vessel. Combustion reaction takes place between coke particles and oxygen containing gas, with excess oxygen is supplied in comparison to stoichiometric oxygen requirement, in the range of 1 to 40 mol %, which generates CO2 rich hot flue gases. The top section of vessel comprises of shell and tube heat exchanger orientated in a way to allow counter current flow steam for heat exchanging with flue gases generated due to combustion of coke. The operating temperatures of heat source vessel is in the range of 600-800° C., operating pressure is in the range of 0.5-3 bar, coke to feed ratio is the range of 0.02-1 (wt/wt). The temperature of dilution steam is the range of 400-650° C. and pressure in the range of 0.5-3 bar. The dilution steam coming out of heat source vessel is mixed with hydrocarbon feedstock in heat sink vessel such that dilution steam to hydrocarbon feedstock ratio is in the range of 0.1-1.5 and residence time of mixture in the heat sink vessel is in the range of 0.1-5 sec. The temperature of steam used for generation of dilution steam is in the range of 110-300° C., pressure in the range of 3-20 Kg/cm2. The steam used for generation of dilution steam can be LP or MP steam. Further, the additional steam generated in convection section can be utilized for power generation using turbines thereby obtaining low pressure & medium pressure steam which can be utilized back in this process itself. The exhaust mixture (28) containing CO2 rich gas and steam leave the top section of heat source vessel and is fed to separator where CO2 rich gas is obtained from top having CO2 in the range of 80-99% is obtained which can be further purified and utilized for carbon capture & utilization.
Heat carrier particles is utilized for preheating the hydrocarbon feedstock wherein the same present in the heat source vessel is transported to heat sink vessel by fluidization using oxygen containing gas via stripper in between to ensure no oxygen reaches to heat sink vessel. The heat carrier particles comprise spent FCC catalyst, spent reformer catalyst, inert aluminosilicate particles, alumina balls, silicon carbide, fly ash, metallic oxides and combination(s) thereof with minimum fluidization velocity in the range of 0.01-0.8 m/s, heat capacity is in the range of 300-1000 J/Kg-K and particle size distribution in the range of 40 microns to 3 mm.
The hydrocarbon feedstock stream supplied to the heat sink vessel is directly contacted with the heat carrier particles in the heat sink vessel, having contact time ranging from 0.5-30 sec and heat carrier particles to hydrocarbon feedstock ratio is the range of 1-10 (wt/wt), which in turn preheats the hydrocarbon feedstock upto desired temperatures. After contacting, heat carrier particles are recycled back to heat source section using pneumatic conveying through steam for reheating. The operating temperatures of heat sink vessel is in the range of 400-700° C., operating pressure is in the range of 0.1-3 bar.
The operating temperature of the radiation/cracking section is in the range of 750-950° C., pressure drop is in the range of 0.5-2 bar, residence time in the range of 0.1-1 sec, steam to feed ratio in the range of 0.3 to 1.
In the process and system of present invention as depicted in
In preferred embodiment, the hydrocarbon feedstock is selected from Ethane, Propane, C4 hydrocarbons, straight run naphtha, kerosene from atmospheric distillation unit, other paraffinic/olefinic naphtha, kerosene from secondary processing units of refinery such as Fluid Catalytic cracking, Hydrocracking, light oils produced from waste oils such as waste plastic pyrolysis oil, used lubricating oil, bio-oil and other waste oils and combination(s) thereof and requires preheating temperature up to 550-650° C., preferably from 590 to 625° C.
In another preferred embodiment, the location of injection of the mixed feedstock (35) in the hydrocarbon cracking furnace is made at a location in convection section or radiation section inlet which shall be selected based on the temperature of the mixed feedstock.
In another preferred embodiment, fraction of dilution steam (17) is injected in the heat sink vessel (20) and remaining fraction injection in hydrocarbon cracking furnace is made at a location in convection section or radiation section inlet which shall be selected based on the temperature of the mixed feedstock.
In another preferred embodiment, the coke used for combustion is not produced on heat carrier particles internally instead taken either from Delayed Coker Unit or fluid coking unit- or waste material (biomass, plastic, municipal solid waste etc.) pyrolysis unit or coal plant.
In yet another preferred embodiment, coke used in the process can be fuel grade coke, fluid coke, anode grade coke, bio char, coal or combination(s) thereof.
In yet another preferred embodiment, the combustion of coke for heat generation along with fluidization of heat carrier particles in heat source vessel can be done either through pure oxygen or air or a combination thereof. Further, excess oxygen is supplied in comparison to stoichiometric oxygen requirement, in the range of 1 to 40 mol %.
In yet another preferred embodiment, top section of heat source vessel comprises shell and tube heat exchanger which superheats the steam to generate dilution steam which is then mixed with vaporized hydrocarbon feedstock for reducing the residence time in heat sink vessel before routing to radiation section.
In yet another preferred embodiment, the steam used for generation of dilution steam can be Low Pressure (LP) or Medium Pressure (MP) steam.
Comparison of the Convection Section of Present Invention with Conventional Furnace
In conventional furnace as depicted in
In the present invention as depicted in
It is to be note that the location of injection of the mixed feedstock (23) in the hydrocarbon cracking furnace is made at a location in convection section or radiation section inlet which shall be selected based on the temperature of the mixed feedstock. When we implement this system commercially, the additional very high-pressure steam can be generated from idle convection section or part of convection section using flue gases heat depending on the location of injection of the mixed feedstock in the hydrocarbon cracking furnace.
As the underlying chemical engineering principles of the process could be estimated by mathematical calculations known in the art of chemical engineering, the process data given in the same has been generated using said approach. A single heater of steam cracker furnace was considered wherein Straight Run Naphtha (SRN) is taken with inlet temperature 60° C. & heated & dilution steam was heated at 200° C. upto 590° C. using heater. Taking the capacity of typical naphtha cracker unit as 0.5 MMTPA, the amount of heat required is close to 32 MMKcal/hr. Also, the quantity of coke required to maintain the temperature of heat source vessel at 700° C. & preheat the said capacity feed is close to 33.5 kTA (considering heat of combustion of coke ˜32 KJ/gm coke). This way, we can say that by utilizing low value coke, we are saving almost 32 MMKcal/hr of energy required in the convection section which is further utilized in generating very high-pressure steam of 46 MT/hr which further can be utilized in generating electric power using steam turbines as shown in Table 1. The LP steam produced as result of that can be further utilized in plant operations and utility. The total amount of SCOPE-II CO2 which could have been produced due to generation of additional 46 MT/hr Very High-Pressure steam is close to 82 TMTPA per 0.5 MMTPA of hydrocarbon processed is getting reduced from the present process. The Coke utilized in generating the energy for preheating hydrocarbon feedstocks in turn results in reduction of equivalent SCOPE III CO2 of 107 TMTPA per 0.5 MMTPA of hydrocarbon processed, owing to carbon capture. Total CO2 emission reduction potential of present invention is close to 296 TMTPA CO2/0.5 MMTPA hydrocarbon processed compared to conventional steam cracker furnace as shown in Table 2.
Energy Balance of Convection Section of Furnace with/without Preheating of Naphtha Using Coke:
The calculations of heat requirements in convection section of conventional furnace and present invention are shown in Table 1 and CO2 emissions reduction is shown in Table 2 respectively.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202321014174 | Mar 2023 | IN | national |
