WO2007022636A1 - Method and apparatus for cracking hydrocarbons - Google Patents

Method and apparatus for cracking hydrocarbons Download PDF

Info

Publication number
WO2007022636A1
WO2007022636A1 PCT/CA2006/001396 CA2006001396W WO2007022636A1 WO 2007022636 A1 WO2007022636 A1 WO 2007022636A1 CA 2006001396 W CA2006001396 W CA 2006001396W WO 2007022636 A1 WO2007022636 A1 WO 2007022636A1
Authority
WO
WIPO (PCT)
Prior art keywords
coke
drum assembly
oil
vessel
drum
Prior art date
Application number
PCT/CA2006/001396
Other languages
French (fr)
Inventor
Karol Pawel Gawad
Original Assignee
Altene (Canada) Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Altene (Canada) Inc. filed Critical Altene (Canada) Inc.
Priority to EP06790576A priority Critical patent/EP1922388A4/en
Publication of WO2007022636A1 publication Critical patent/WO2007022636A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/02Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in retorts
    • C10G9/04Retorts

Definitions

  • the invention relates to both a method and apparatus for thermal cracking of hydrocarbons.
  • the apparatus includes a rotating conical drum assembly within a vessel containing a hydrocarbon feedstock.
  • the conical drum assembly is internally heated to cause cracking of hydrocarbons adjacent the conical drum surface and the formation of coke on its external surface as the conical drum rotates. Coke is removed from the drum surface by a coke removal system and cracked hydrocarbon product is collected as a vapour.
  • hydrocracking is a process by which large/heavy hydrocarbons are broken down into smaller and more useful hydrocarbons including paraffins and olefins.
  • thermal cracking in which the heavy hydrocarbons are subjected to high temperatures
  • catalytic cracking in which a catalyst is introduced into a reaction mixture to enable cracking to occur at lower temperatures.
  • Patent 5,356,530 describes a method for upgrading petroleum residuum and heavy crude oil
  • US Patent 1 ,677,758 describes the treatment of carbonaceous and other materials
  • US Patent 1 ,622,573 describes a coking still
  • US Patent 1 ,541 ,140 describes a process and apparatus for distilling and cracking hydrocarbon oils
  • US Patent 1 ,183,457 describes an oil distillation process
  • Patent 1 ,231 ,695 describes an apparatus for refining petroleum
  • US Patent 1 ,418,414 describes a process of making unsaturated hydrocarbon material
  • US Patent 148,806 describes oil-stills
  • PCT/EP 01/11016 describes a process and apparatus for the fractional distillation of crude oil
  • EP 1 067 171 describes a process for removing contaminants from oil
  • EP 0 667 799 describes a method for selective and/or unselective vapourization and/or decomposition of, particularly, hydrocarbon compounds and an apparatus for carrying out such a method
  • PCT/RU 00/00097 describes a method and device for resonance excitation of fluids and method and device for fractionating hydrocarbon liquids
  • DE 41 07 294 describes a cracking system.
  • a system for cracking hydrocarbons comprising: a vessel for operatively receiving and containing a volume of liquid hydrocarbon feedstock; a rotary drum assembly operably and rotatably contained with the vessel and in heating contact with the hydrocarbon feedstock, the rotary drum assembly including a heating system for heating the internal surfaces of the drum assembly during rotation of the drum assembly within the hydrocarbon feedstock wherein simultaneous rotation and heating of the drum assembly causes cracking of hydrocarbons; a vapour product collection system operatively connected to the vessel for receiving cracked hydrocarbon vapours; and a coke removal system operatively contained within the drum for removing coke from the drum assembly and vessel.
  • the drum assembly includes two frustoconical end sections and a central cylindrical section operatively mounted between front and back pipe sections.
  • the drum assembly and vessel includes a bearing system and the bearing system includes a cooling system for cooling the bearings during operation.
  • the bearing cooling system includes a spiral oil path within each of the front and back pipe sections and the bearing system.
  • the burner includes a secondary air injection system for injecting secondary air into an inside position of a conical flame.
  • the vapour product collection system includes a quenching system for quenching vapour product to prevent coking within the vapour product collection system.
  • the coke removal system includes a plurality of scrapers in operative contact with the exterior surface of the drum assembly, the coke removal system including at least one coke pit for allowing coke to be removed from the drum.
  • a process for cracking hydrocarbons comprising the steps of: heating a rotating surface to a given temperature; exposing the rotating surface to a volume of oil to be cracked thereby causing the volatization of light hydrocarbons and the formation of a thixotrophic suspension of cracked heavy oil and coke on the rotating surface; collecting evaporated cracked heavy oil; and scraping and removing coke from the rotating surface.
  • the rotation speed and rotating surface temperature are balanced to produce dry coke before coke is scraped from the rotating surface.
  • the rotating surface is operatively contained within a vessel and the volume of oil to be cracked is maintained at a fixed height relative to the rotating surface and the rotation speed of the rotating surface is controlled to produce a thin-film thixotropic mixture of olefins and paraffins on the rotating surface for a given temperature.
  • FIG. 1 is a cross sectional view of a rotary disc thermal cracker (RDTC) in accordance with one embodiment of the invention
  • Figure 2A is a perspective view of the rotating drum assembly in accordance with one embodiment of the invention.
  • Figure 2B is a cross-sectional perspective view of the rotating drum assembly in accordance with one embodiment of the invention.
  • Figure 3A is a perspective view of the external vessel assembly in accordance with one embodiment of the invention
  • Figure 3B is a cross-sectional perspective view of the external vessel and rotating drum assembly in accordance with one embodiment of the invention
  • Figure 4 is a perspective view of the scraper assembly in accordance with one embodiment of the invention
  • Figure 5A is a perspective view of the external vessel, rotating drum assembly and scraper assemblies in accordance with one embodiment of the invention
  • Figure 5B is a cross-sectional perspective view of the external vessel, rotating drum assembly and scraper assemblies in accordance with one embodiment of the invention
  • Figure 6A is a cross-sectional perspective view of the bearing assembly on the burner side of the RDTC in accordance with one embodiment of the invention
  • Figure 6B is a cross-sectional view of the bearing assembly on the exhaust side of the RDTC in accordance with one embodiment of the invention
  • Figure 7 is a cross-sectional perspective view of a quenching system in accordance with one embodiment of the invention.
  • Figure 8 are various cross-sectional views of a burner in accordance with one embodiment of the invention.
  • Figure 9 is a schematic cross sectional view of a burner and rotating drum assembly and external vessel assembly in accordance with one embodiment of the invention.
  • Figure 10 is a schematic diagram of the cracking process as a function of drum temperature and distance from the drum wall.
  • FIG 11 is a schematic diagram of a plant incorporating the RDTC in accordance with one embodiment of the invention.
  • the process includes, as described in relation to one rotation cycle, the steps of heating a rotating surface to a given temperature; exposing the rotating surface to a volume of oil to be cracked thereby causing the volatization of light hydrocarbons and the formation of a thixotrophic suspension of cracked heavy oil and solid coke on the rotating surface; collecting evaporated cracked product; continuing to heat the suspension until coking occurs; and, scraping and collecting coke from the rotating surface.
  • the preferred apparatus to carry out the process is a rotary disc thermal cracker (RDTC) 10 as shown in Figures 1-
  • the RDTC includes a drum assembly 12 preferably comprised of two conical surfaces 12a, 12b and a central cylindrical surface 12c.
  • the drum assembly 12 is hollow thus defining a fire chamber 12d allowing heated air and flame from a burner to heat the inner surface of the drum assembly.
  • the drum assembly 12 is rotatably mounted within an external cylindrical vessel 14 thereby defining an external liquid space 16 for containing a volume of feedstock heavy oil having a liquid level 18 within the external vessel casing 14.
  • Scrapers 30a ( Figures 4, 5A, 5B) mounted within the vessel 14 scrape the baked coke from the surfaces of the cylinder assembly into coke pits 32. The surface of the drum assembly is thereby cleaned prior to it being re-submerged within the feedstock oil of the drum.
  • the RDTC also includes two vapour quenchers 40, 42 ( Figure 7) designed to collect vaporized hydrocarbons and to cool the heavier fractions to below their cracking point temperature wherein the heavier hydrocarbons condense and fall back into the external vessel 14 of the RDTC for re-cracking.
  • the rotating drum assembly 12 and fire chamber 12d is preferably assembled from two frustoconical sections welded to opposite ends of a short central cylindrical section and two pipe shafts (front shaft 12e and back shaft 12f) welded to the narrow ends of the frustoconical sections.
  • Bearings 20 mounted to the pipe shafts support the drum assembly within a bearing support and cooling system 22 that enables the drum assembly 14 to rotate around its horizontal axis and maintain the bearing temperature within design limits.
  • the rotating drum assembly is designed to contain the heat of a burner operably connected to the input end H of the drum assembly 12.
  • the burner flame produces a flame temperature in the range of 3000 0 F within the drum assembly and fills the internal volume 12d of the assembly thereby providing an exterior surface temperature of the rotating drum in the range of 1200 0 F.
  • the resulting flue gas will have a temperature in the range of 1500 0 F that leaves the fired chamber through back shaft 12f at the exhaust end E.
  • the exhaust end E is preferably connected to a heat recovery furnace ( Figure 11) located downstream.
  • the design temperature of the exterior of the drum assembly is in the range of 1300 0 F.
  • materials such as 18Cr-8Ni-Ti type steels (ASTM A312 TP-321H) having creep limit of 4.5 kG/mm 2 @ 1292 0 F are preferably utilized in the construction of the drum assembly 12.
  • the external surfaces and bearing systems of the front and back shafts 12e, 12f are preferably cooled by a bearings cooling system 22 including vacuum oil in a spiral labyrinth system.
  • the front shaft 12e and back shaft 12f are protected against cooling oil leakage by spring rings 12g at the vessel side and packing gland 12h at the burner or exhaust side, respectively.
  • Figure 2A shows a perspective view of the drum assembly and Figure 2B shows a perspective view of the drum assembly in cross section.
  • Figure 2B also shows a preferred embodiment in which the burner ( Figures 8 and 9) enables secondary air flow distribution within the drum assembly.
  • Secondary air flow distribution generally operates oppositely to typical burner performance, where secondary air surrounds the flame core and allows control of the shape of the flame. Control of the shape of the flame enables the flame to effectively contact and heat the inner surface of the drum assembly.
  • the shape of the drum assembly requires a cigar-shaped flame where secondary air fills the fire core thereby providing effective contact of the flame with the drum assembly inner surface and that provides an equalization of the radial temperature profile across the length of the drum assembly.
  • Figure 8 shows details of the burner tip construction.
  • the external vessel 14 of the RDTC is a horizontal vessel as shown in Figures 1, 3A, 3B and 5A.
  • the vessel 14 is comprised of curved steel casing sections 14a, 14b with stiffening ribs 14c and plate ends 14d with radial stiffening ribs 14e.
  • Bearing supports and bearings are operably connected to the vessel casing through external base pipes 22a and 22b of bearing system
  • the vessel 14 is preferably assembled in two sections (bottom section shown in Figure 5A) to enable both initial assembly and disassembly of the vessel for inspection and maintenance of the internal components.
  • the vessel includes a feedstock inlet nozzle 15a located on the underside of the vessel to introduce feedstock into the system and appropriate outlets 15b, 15c for vapour products and the vapour quenching system 40, 42.
  • the vapour product nozzles 15b, 15c are preferably located on the opposite side of the casing to the scraping system (described below) to avoid contact between baked coke and quencher return oil.
  • the operating temperature of the feedstock within the drum is approximately 700 0 F with vapour temperatures in the range of 750 0 F.
  • the drum casing is manufactured from type SS 304 steel, ASTM A240 TP304 or equivalent.
  • the vessel casing 14 also operatively retains a scraping system 30 ( Figures 4, 5A, 5B) to remove coke adhered to the drum surface and remove scraped coke from the vessel.
  • the scraping system is maintained in contact with the rotating drum so as to cleanly remove adhered coke and channel the coke towards coke pits 32 where the coke falls by gravity from the vessel 14.
  • the scrapers are preferably adjustable in their linear position to maintain an appropriate contact position with the rotating drum within a clearance of c.a. 1/64"during the coke removal process.
  • the scrapers may be angled (and be adjustable by an adjustment system 34) both to ensure that coke is channelled to the coke pits 32 and to enable adjustment for any linear temperature gradient along the horizontal axis of the cylinder assembly.
  • Each of the surfaces of the drum assembly have a separate scraper and coke collection system such that coke can be removed along the full length of the rotating drum assembly.
  • the adjustment system 34 includes a scraper strap 34a fastened on a scraper base 34d. Whilst Figure 4 shows the scraping system on the left side of the RDTC only, separate scraping systems exist for each of the central and right hand side sections of the rotating drum. Each base is supported on a slide pair 34g, 34h.
  • each scraper can be adjusted by screw adjusters 34k passing through a gland assembly 34n on the exterior of the vessel 14 to enable adjustment of the scraper 34a from the exterior of the vessel.
  • the vessel may also include appropriate openings 30c, 3Od, 3Oe to enable an operator to visually inspect the position of each scraper.
  • the vessel casing will preferably also include appropriate internal baffles (shown as 30a) to ensure that coke falls towards the coke pits.
  • the system also includes a bearing cooling system 22 ( Figures 1 , 6A, 6B) to ensure that the bearings 20 and 21 are maintained with normal design temperatures during operation.
  • the rotating drum 12 is supported by shafts 12e, 12f on external bearings base 22h and internal bearings case 22i at the ends of each shaft.
  • the bearings are preferably located at the ends of the shafts to minimize the risk of the bearings jamming in the event that the bearing cooling system malfunctions. That is, by locating the bearings at the ends or towards the ends of the shafts, the bearings will be subjected to lower temperatures.
  • the typical design temperature of the rotating drum connections between the frustoconical surfaces and the shafts 12e, 12f is approximately 1300 0 F.
  • the design temperature of the vessel casing 14 at the connection to the external base pipes 22a and 22b is 840 0 F.
  • the typical design temperature of the bearings is less than 300 0 F.
  • the bearing cooling system includes a series of spiral channels 22c/d and 22e/g surrounding the shafts that enable the flow of cooling oil around the front and back shafts.
  • the spiral channel is preferably a trapezoidal thread fixed on the internal surface of the supporting pipes 22a, 22b. The distance between the crest of each thread to the shaft 22e, 22f is minimized to scrape any coke forming on hot shaft surfaces caused by the partial thermal cracking of the cooling oil during operation.
  • cooling oil entering the spiral channels on the burner side is split into two streams as shown in Figure 6A. Cooling oil enters an inlet chamber 23 located the midpoint of external supporting pipe 22a and is directed to both sides of the inlet into spiral channels 22c, 22d.
  • the cooling oil may be heated to temperatures in the range of 390 0 F thereby cooling both the base pipe 22a and shaft 12e.
  • the cooling oil exits the spiral channels through nozzles 23a, 23b adjacent the spring rings 12g and the bearings base 22h, respectively.
  • Heated cooling oil is collected within an external heat radiator system ( Figure 11).
  • the length of the spiral channels and nozzle diameters 23a, 23b are selected to control the pressure of the two cooling oil streams.
  • the back pressure of cooling oil through channel 22d is set to the cracker operation pressure, whereas the back pressure through channel 22c is set at atmospheric pressure.
  • the cooling system 22b on the exhaust side is comprised of three sections.
  • Cooling oil enters an inlet chamber located at the midpoint of external pipe 22b. As with the burner side, cooling oil is directed through a first spiral channel 22e adjacent the vessel 14 where it will be heated to approximately 390 0 F thereby cooling both base pipe 22b and shaft 12f. The cooling oil exits the spiral channel through an outlet nozzle 22q adjacent the spring ring 12g.
  • a second stream of cooling oil is directed through spiral channel 22f into an intermediate chamber 22m closed from the exhaust side bearing race by packing glands 12h.
  • the intermediate chamber 22m is connected to a system of cooling channels 22n within the bearing support adjacent a third series of spiral grooves
  • Cooling oil passes through and exits spiral grooves 22g through outlet channel 22o.
  • the length of the spiral channels and outlet nozzle diameters are selected to control the pressure of the two cooling oil streams.
  • the back pressure of cooling oil through channel 22e and nozzle 22q is set to the cracker operation pressure, whereas the back pressure through channels 22f, 22g and nozzle 22o is set at atmospheric pressure.
  • the bearing system on the exhaust side is positioned at a greater radial distance than the bearing system on the burner side due to the higher temperatures on the exhaust side.
  • the exhaust side also preferably includes a refractory liner 12m on the inside of tube 12f.
  • Hot hydrocarbon vapours leaving the cracker will typically have temperatures higher than the cracking temperature of particular hydrocarbons.
  • the vapours are quenched by oily water injection into the quenching system 40.
  • the quenching system includes a quenching drum 40a, a product vapour tangential outlet 40b, a hot vapour inlet 40c, an eccentric circular weir 40d, an oil/water spray nozzle 40e and cleaning device access 40f.
  • vapour outlet nozzles 40b are tangential, thereby promoting a vortex flow of vapours through the quencher which promotes mixing of quenching liquids with the HC vapours.
  • the quenching system will also preferably include cleaning nozzles located in a diametrically opposite position to the outlet nozzle enabling the cleaning of the oil/water spray nozzles during normal cracker operation.
  • the decrease in vapour temperature also causes the condensation of small quantity of HC liquid that is collected on the lower surfaces of the quencher and that will spill back to the drum 14 over weir 4Od.
  • the internal surface of the hot vapour inlet nozzle 40c is wet by HC condensates at temperatures higher the cracking temperature of the HC condensates and, as a result, can be plugged by a coke layer.
  • the internal surface is preferably protected against coking by a silicate coating that is periodically washed by a small quantity of cooling oil.
  • the burner assembly is described.
  • the burner is mounted to the inside of shaft 12e.
  • the burner assembly 50 is fixed relative to the rotating front shaft 12e and includes a shaft contacting system 50k that isolates the burner within the shaft from the atmosphere at the inlet side of the shaft 12e and the vessel casing side.
  • the burner assembly includes a fixing burner pipe 50a, adjustable burner base 50b; fixed flame distribution tip 50c and adjustable air distribution tip 5Od.
  • Combustion air is supplied from a burner fan ( Figure 9) to burner base 50b and internal chamber C1 where the combustion air is split into primary and secondary air.
  • Primary air flows through four swirlers 5Oe to vortex chamber C2, where the air is heated by contact with shaft 12e.
  • Vortex space C2 is defined by contacting system 5Ok 1 such that heated air enters chamber C3 through four swirling nozzles 5Of.
  • heated primary air is cross-contacted with fuel oil spray streams and the resulting mixture is jetted into the drum assembly 12 through angled nozzles 5Og.
  • Pumped fuel oil also flows through four channels into four dispersing chambers C4 via central axial inlet nozzles 5Oh. Inside of chamber C4, the oil liquid is dispersed into droplets by contact with dispersing fuel gas or a steam vortex created by tangential nozzles 5Oi. The vortex of chamber C4 is accelerated by central axial outlet nozzles 5Oh and injected into mixing chamber C2.
  • the jets from nozzles 5Og have a lower cone angle than the drum cones 12b and are ignited by a small pilot flame created by an ignition and flame watch system.
  • a small turn of the burner base 50b around fixing pipe 50a restricts swirlers 5Oe and thus changes the ratio of primary to secondary airs. Tightening the distribution tip 5Od throttles the circular nozzle of secondary air and decreases its flow and impact. As a result of the secondary air conical shape, the flame angle can be controlled from a long cylindrical shape to full contact of fire to with the internal surface of rotating drum 12. As a result, control of the net heat power can be controlled in the range of 25% to 100%.
  • the thermal cracking process is simplified to the following steps; Heating to boiling point of lighter volatile compounds Vaporization of lighter volatile compounds Heating to crack point temperature and evaporation of cracked volatile products Heating up to carbonization temperature
  • the typical crack point temperature of heavy crude oil compound is usually 600 ⁇ 715 0 F, the carbonization temperature of 95 Wt% carbon products is c.a. 1000 0 F.
  • the cracking process can be simplified to a two-step reaction:
  • n As crude oil is a complex and indefinite mixture, the value of "n" will vary from 6 up to a few hundred. As an example,
  • FIG 10 illustrates boundary layer effects of drum temperature, drum velocity and distance to the drum in the coke and cracking reactions.
  • the temperature decreases and, as the velocity of the drum increases, the time for reaction decreases.
  • the temperature of the drum surface will also affect the coke forming reactions where coke formation is increased with increasing surface temperatures.
  • a thin film boundary layer comprising olefins and paraffins will exist that separates the heated surface from forming coke.
  • the boundary layer will be thinner due to shear forces and the coke layer becomes thicker.
  • the thickness of the boundary layer is controlled to ensure that the boundary layer is sufficiently thin in order to ensure an optimum dry coke layer and to prevent contact of a thick boundary layer (comprising a thixotropic mixture of olefins and paraffins) with the scrapers.
  • various operational parameters of the system may be controlled to ensure desired product formation based on feedstock composition and desired products.
  • Flame temperature and rotational speed of the rotary drum are the primary parameters adjustable to optimize the operation of the system.
  • the liquid feedstock level within the drum is preferably controlled to maintain a consistent time relationship between wetting time and coking time at about 1 :2. That is, the liquid level within the drum casing is maintained such that approximately one third of the outer circumference of the drum is wetted at any given time.
  • the speed of rotation of the drum assembly provides a coking time in the range of 3-8 seconds for a given flame temperature.
  • Feedstock is unloaded into 3-day tank 20-T-01 equipped with a steam coil, where it is heated to 140 0 F and subsequently pumped through pump 20-P-01 into heat recovery furnace 10-F-01 , where it is further heated to 608 0 F.
  • the resulting two- phase stream enters the 8-th tray of oil fractionation column 11-C-01.
  • the liquid phase flows down column 11-C-01 over trays 9-12, where a light fraction is liberated. Tar bottoms flow by gravity from column 11-C-01 into a mixer 10-M-01 at a temperature of 644 0 F, where hydrated lime powder is added.
  • the resulting suspension is pumped by centrifugal pump 10-P-01 to the RDTC 10-R-01 through vapour trap 10-V-02.
  • the liquid level in 10-V-02 and, as a consequence, in 10-R- 01 is controlled by pump 10-P-01.
  • the RDTC cracker 10-R-01 is operated within a temperature range of 779 0 F (evaporation) and 1238 0 F (end of coking).
  • the HC vapours produced in the thermal cracking reaction flow to two parallel quenchers 10-V-01 A/B where they are cooled to 680 0 F by oily water injection.
  • Product vapours feed the bottom of oil wash columns 11-C-01, where they are contacted with fresh feedstock at trays 9- 12 and with product oil at trays 1-8. A small withdraw of oil is taken from tray 7 to cover losses of the cooling oil circuit within the RDTC.
  • the water phase flows by gravity to the oily water drum 11-B-02, also serving as a sump pump for the oily water header connected to quenchers 10-V-01 A/B and coke pit 10-S-01.
  • the cracked oil phase returns back to column 11-C-01 top as the reflux through pump 11-P-01 with net production being sent to an export facility.
  • Excess carbon and calcium sulphide resulting from the thermal cracking reaction is rejected from cracker 10-R-01 into the coke receiver 10-S-01 , where it is cooled down to 212 0 F in contact with oily water. Following cooling, it is removed by a bottom grate conveyor and transported in handle bins into a stacking yard, where contact with air causes intrinsic oxidation of calcium sulphide into water insoluble gypsum.
  • the RDTC cracker utilizes a cooling oil circuit, to keep bearing temperatures lower than 300 0 F.
  • the return oil typically temperature of 266 0 F
  • the return oil flows by gravity into cooling oil bin 10-B-02 after which it is pumped by 10-P-02 back to the cracker through the cooling oil cooler 10-A-01 , where it is cooled down up to 140 0 F. If the product viscosity is out of range (for example due to an insufficient reflux), a portion of the cooling oil can be transferred to export facility using the pump 10-P-02.
  • Viscosity ® 212 0 F 9.9 cSt Gasoline fraction NBP 160-355 0 F 4.9 Wt%

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention relates to both a method and apparatus for thermal cracking of hydrocarbons. The apparatus includes a rotating conical drum assembly within a vessel containing a hydrocarbon feedstock. The conical drum assembly is internally heated to cause cracking of hydrocarbons adjacent the conical drum surface and the formation of coke on its external surface as the conical drum rotates. Coke is removed from the drum surface by a coke removal system and cracked hydrocarbon product is collected as a vapour.

Description

METHOD AND APPARATUS FOR CRACKING HYDROCARBONS
FIELD OF THE INVENTION
The invention relates to both a method and apparatus for thermal cracking of hydrocarbons. The apparatus includes a rotating conical drum assembly within a vessel containing a hydrocarbon feedstock. The conical drum assembly is internally heated to cause cracking of hydrocarbons adjacent the conical drum surface and the formation of coke on its external surface as the conical drum rotates. Coke is removed from the drum surface by a coke removal system and cracked hydrocarbon product is collected as a vapour.
BACKGROUND OF THE INVENTION
As is known hydrocracking is a process by which large/heavy hydrocarbons are broken down into smaller and more useful hydrocarbons including paraffins and olefins. There are generally two methods of cracking namely thermal cracking, in which the heavy hydrocarbons are subjected to high temperatures; and catalytic cracking, in which a catalyst is introduced into a reaction mixture to enable cracking to occur at lower temperatures.
While the cracking of hydrocarbons is known, it is desirable to provide improved thermal cracking processes in which the formation of lighter olefins and paraffins can be effectively controlled in an efficient and continuous process. More specifically, it is desirable to provide a process in which the smaller hydrocarbons are efficiently produced at reaction temperatures between the cracking temperature and the carbonization temperature of a heavy hydrocarbon mixture while also continuously removing coke and sulphur from the reaction mixture.
A review of the prior art reveals that such a system has not been previously described. For example, US Patent 6,005,149 describes a method and apparatus for processing organic materials to produce chemical gases and carbon char; US
Patent 5,356,530 describes a method for upgrading petroleum residuum and heavy crude oil; US Patent 1 ,677,758 describes the treatment of carbonaceous and other materials; US Patent 1 ,622,573 describes a coking still; US Patent 1 ,541 ,140 describes a process and apparatus for distilling and cracking hydrocarbon oils; US Patent 1 ,183,457 describes an oil distillation process; US
Patent 1 ,231 ,695 describes an apparatus for refining petroleum; US Patent 1 ,418,414 describes a process of making unsaturated hydrocarbon material; US Patent 148,806 describes oil-stills; PCT/EP 01/11016 describes a process and apparatus for the fractional distillation of crude oil; EP 1 067 171 describes a process for removing contaminants from oil; EP 0 667 799 describes a method for selective and/or unselective vapourization and/or decomposition of, particularly, hydrocarbon compounds and an apparatus for carrying out such a method; PCT/RU 00/00097 describes a method and device for resonance excitation of fluids and method and device for fractionating hydrocarbon liquids; and DE 41 07 294 describes a cracking system.
SUMMARY OF THE INVENTION
In accordance with the invention, there is provided a system for cracking hydrocarbons comprising: a vessel for operatively receiving and containing a volume of liquid hydrocarbon feedstock; a rotary drum assembly operably and rotatably contained with the vessel and in heating contact with the hydrocarbon feedstock, the rotary drum assembly including a heating system for heating the internal surfaces of the drum assembly during rotation of the drum assembly within the hydrocarbon feedstock wherein simultaneous rotation and heating of the drum assembly causes cracking of hydrocarbons; a vapour product collection system operatively connected to the vessel for receiving cracked hydrocarbon vapours; and a coke removal system operatively contained within the drum for removing coke from the drum assembly and vessel.
In one embodiment, the drum assembly includes two frustoconical end sections and a central cylindrical section operatively mounted between front and back pipe sections.
In another embodiment, the drum assembly and vessel includes a bearing system and the bearing system includes a cooling system for cooling the bearings during operation. In a preferred embodiment, the bearing cooling system includes a spiral oil path within each of the front and back pipe sections and the bearing system.
In one embodiment, the burner includes a secondary air injection system for injecting secondary air into an inside position of a conical flame.
In yet another embodiment, the vapour product collection system includes a quenching system for quenching vapour product to prevent coking within the vapour product collection system.
In yet still another embodiment, the coke removal system includes a plurality of scrapers in operative contact with the exterior surface of the drum assembly, the coke removal system including at least one coke pit for allowing coke to be removed from the drum.
In another aspect of the invention, a process for cracking hydrocarbons is provided, comprising the steps of: heating a rotating surface to a given temperature; exposing the rotating surface to a volume of oil to be cracked thereby causing the volatization of light hydrocarbons and the formation of a thixotrophic suspension of cracked heavy oil and coke on the rotating surface; collecting evaporated cracked heavy oil; and scraping and removing coke from the rotating surface. Preferably, the rotation speed and rotating surface temperature are balanced to produce dry coke before coke is scraped from the rotating surface.
In further embodiments, the rotating surface is operatively contained within a vessel and the volume of oil to be cracked is maintained at a fixed height relative to the rotating surface and the rotation speed of the rotating surface is controlled to produce a thin-film thixotropic mixture of olefins and paraffins on the rotating surface for a given temperature.
BRIEF DESCRIPTON OF THE DRAWINGS
The invention is described with reference to the drawings in which:
Figure 1 is a cross sectional view of a rotary disc thermal cracker (RDTC) in accordance with one embodiment of the invention;
Figure 2A is a perspective view of the rotating drum assembly in accordance with one embodiment of the invention;
Figure 2B is a cross-sectional perspective view of the rotating drum assembly in accordance with one embodiment of the invention;
Figure 3A is a perspective view of the external vessel assembly in accordance with one embodiment of the invention; Figure 3B is a cross-sectional perspective view of the external vessel and rotating drum assembly in accordance with one embodiment of the invention; Figure 4 is a perspective view of the scraper assembly in accordance with one embodiment of the invention;
Figure 5A is a perspective view of the external vessel, rotating drum assembly and scraper assemblies in accordance with one embodiment of the invention; Figure 5B is a cross-sectional perspective view of the external vessel, rotating drum assembly and scraper assemblies in accordance with one embodiment of the invention;
Figure 6A is a cross-sectional perspective view of the bearing assembly on the burner side of the RDTC in accordance with one embodiment of the invention; Figure 6B is a cross-sectional view of the bearing assembly on the exhaust side of the RDTC in accordance with one embodiment of the invention;
Figure 7 is a cross-sectional perspective view of a quenching system in accordance with one embodiment of the invention;
Figure 8 are various cross-sectional views of a burner in accordance with one embodiment of the invention;
Figure 9 is a schematic cross sectional view of a burner and rotating drum assembly and external vessel assembly in accordance with one embodiment of the invention;
Figure 10 is a schematic diagram of the cracking process as a function of drum temperature and distance from the drum wall; and,
Figure 11 is a schematic diagram of a plant incorporating the RDTC in accordance with one embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
In accordance with the invention and with reference to the figures, a process and apparatus for cracking hydrocarbons using a rotating heated surface is described.
Overview of Apparatus and Process
More specifically, the process includes, as described in relation to one rotation cycle, the steps of heating a rotating surface to a given temperature; exposing the rotating surface to a volume of oil to be cracked thereby causing the volatization of light hydrocarbons and the formation of a thixotrophic suspension of cracked heavy oil and solid coke on the rotating surface; collecting evaporated cracked product; continuing to heat the suspension until coking occurs; and, scraping and collecting coke from the rotating surface.
Furthermore, in accordance with the invention, the preferred apparatus to carry out the process is a rotary disc thermal cracker (RDTC) 10 as shown in Figures 1-
9. The RDTC includes a drum assembly 12 preferably comprised of two conical surfaces 12a, 12b and a central cylindrical surface 12c. The drum assembly 12 is hollow thus defining a fire chamber 12d allowing heated air and flame from a burner to heat the inner surface of the drum assembly. The drum assembly 12 is rotatably mounted within an external cylindrical vessel 14 thereby defining an external liquid space 16 for containing a volume of feedstock heavy oil having a liquid level 18 within the external vessel casing 14.
More specifically, in operation, as the drum assembly 12 rotates within the external vessel 14, a portion of the outer surface of the drum assembly 12 is always partly submerged within the feedstock oil. As the outer surface of the drum assembly 12 rotates in the feedstock oil, the hot surface will rapidly heat the oil, resulting in flash evaporation of light hydrocarbons and cracking of the heavy hydrocarbons as the drum assembly rotates. A high temperature gradient is created within the oil in proximity to the drum assembly, which causes the formation of a thixotropic suspension of solid coke and cracked products that adhere to the outside of the cylinder and cone surfaces.
As the coated surface of the drum assembly 12 rotates out of the oil, adhered hydrocarbons continue to be heated, evaporating the cracked products and forming dry coke against the heated surface. Scrapers 30a (Figures 4, 5A, 5B) mounted within the vessel 14 scrape the baked coke from the surfaces of the cylinder assembly into coke pits 32. The surface of the drum assembly is thereby cleaned prior to it being re-submerged within the feedstock oil of the drum.
The RDTC also includes two vapour quenchers 40, 42 (Figure 7) designed to collect vaporized hydrocarbons and to cool the heavier fractions to below their cracking point temperature wherein the heavier hydrocarbons condense and fall back into the external vessel 14 of the RDTC for re-cracking.
Rotating Drum Assembly 12
With reference to Figures 1 , 2A, 2B, 3B and 5A, the rotating drum assembly 12 and fire chamber 12d is preferably assembled from two frustoconical sections welded to opposite ends of a short central cylindrical section and two pipe shafts (front shaft 12e and back shaft 12f) welded to the narrow ends of the frustoconical sections. Bearings 20 mounted to the pipe shafts support the drum assembly within a bearing support and cooling system 22 that enables the drum assembly 14 to rotate around its horizontal axis and maintain the bearing temperature within design limits.
The rotating drum assembly is designed to contain the heat of a burner operably connected to the input end H of the drum assembly 12. Preferably, the burner flame produces a flame temperature in the range of 3000 0F within the drum assembly and fills the internal volume 12d of the assembly thereby providing an exterior surface temperature of the rotating drum in the range of 1200 0F. The resulting flue gas will have a temperature in the range of 1500 0F that leaves the fired chamber through back shaft 12f at the exhaust end E. The exhaust end E is preferably connected to a heat recovery furnace (Figure 11) located downstream.
As noted above, the design temperature of the exterior of the drum assembly is in the range of 1300 0F. As the torque forces and material stresses are highest in the area of pipe section welding to the cone, materials such as 18Cr-8Ni-Ti type steels (ASTM A312 TP-321H) having creep limit of 4.5 kG/mm2 @ 1292 0F are preferably utilized in the construction of the drum assembly 12.
As described in greater detail below, the external surfaces and bearing systems of the front and back shafts 12e, 12f are preferably cooled by a bearings cooling system 22 including vacuum oil in a spiral labyrinth system. The front shaft 12e and back shaft 12f are protected against cooling oil leakage by spring rings 12g at the vessel side and packing gland 12h at the burner or exhaust side, respectively.
Figure 2A shows a perspective view of the drum assembly and Figure 2B shows a perspective view of the drum assembly in cross section.
Figure 2B also shows a preferred embodiment in which the burner (Figures 8 and 9) enables secondary air flow distribution within the drum assembly. Secondary air flow distribution generally operates oppositely to typical burner performance, where secondary air surrounds the flame core and allows control of the shape of the flame. Control of the shape of the flame enables the flame to effectively contact and heat the inner surface of the drum assembly. In the specific design described herein, the shape of the drum assembly requires a cigar-shaped flame where secondary air fills the fire core thereby providing effective contact of the flame with the drum assembly inner surface and that provides an equalization of the radial temperature profile across the length of the drum assembly. Figure 8 shows details of the burner tip construction.
External Vessel 14
The external vessel 14 of the RDTC is a horizontal vessel as shown in Figures 1, 3A, 3B and 5A. In a preferred embodiment the vessel 14 is comprised of curved steel casing sections 14a, 14b with stiffening ribs 14c and plate ends 14d with radial stiffening ribs 14e. Bearing supports and bearings are operably connected to the vessel casing through external base pipes 22a and 22b of bearing system
22. The vessel 14 is preferably assembled in two sections (bottom section shown in Figure 5A) to enable both initial assembly and disassembly of the vessel for inspection and maintenance of the internal components.
The vessel includes a feedstock inlet nozzle 15a located on the underside of the vessel to introduce feedstock into the system and appropriate outlets 15b, 15c for vapour products and the vapour quenching system 40, 42. The vapour product nozzles 15b, 15c are preferably located on the opposite side of the casing to the scraping system (described below) to avoid contact between baked coke and quencher return oil. The operating temperature of the feedstock within the drum is approximately 700 0F with vapour temperatures in the range of 750 0F. As the system is normally operated with high sulphur concentrations within the typical feedstock, it is preferred that the drum casing is manufactured from type SS 304 steel, ASTM A240 TP304 or equivalent.
Scraping System 30
The vessel casing 14 also operatively retains a scraping system 30 (Figures 4, 5A, 5B) to remove coke adhered to the drum surface and remove scraped coke from the vessel. The scraping system is maintained in contact with the rotating drum so as to cleanly remove adhered coke and channel the coke towards coke pits 32 where the coke falls by gravity from the vessel 14. The scrapers are preferably adjustable in their linear position to maintain an appropriate contact position with the rotating drum within a clearance of c.a. 1/64"during the coke removal process. The scrapers may be angled (and be adjustable by an adjustment system 34) both to ensure that coke is channelled to the coke pits 32 and to enable adjustment for any linear temperature gradient along the horizontal axis of the cylinder assembly. Each of the surfaces of the drum assembly have a separate scraper and coke collection system such that coke can be removed along the full length of the rotating drum assembly.
The adjustment system 34 includes a scraper strap 34a fastened on a scraper base 34d. Whilst Figure 4 shows the scraping system on the left side of the RDTC only, separate scraping systems exist for each of the central and right hand side sections of the rotating drum. Each base is supported on a slide pair 34g, 34h.
The position of each scraper can be adjusted by screw adjusters 34k passing through a gland assembly 34n on the exterior of the vessel 14 to enable adjustment of the scraper 34a from the exterior of the vessel. The vessel may also include appropriate openings 30c, 3Od, 3Oe to enable an operator to visually inspect the position of each scraper. The vessel casing will preferably also include appropriate internal baffles (shown as 30a) to ensure that coke falls towards the coke pits.
Coke leaving the drum through chutes 3Of and 3Og is quenched with stagnant water as will be described below. Bearings cooling system 22
In a preferred embodiment, the system also includes a bearing cooling system 22 (Figures 1 , 6A, 6B) to ensure that the bearings 20 and 21 are maintained with normal design temperatures during operation. The rotating drum 12 is supported by shafts 12e, 12f on external bearings base 22h and internal bearings case 22i at the ends of each shaft. The bearings are preferably located at the ends of the shafts to minimize the risk of the bearings jamming in the event that the bearing cooling system malfunctions. That is, by locating the bearings at the ends or towards the ends of the shafts, the bearings will be subjected to lower temperatures.
As noted above, the typical design temperature of the rotating drum connections between the frustoconical surfaces and the shafts 12e, 12f is approximately 1300 0F. In addition, the design temperature of the vessel casing 14 at the connection to the external base pipes 22a and 22b is 840 0F. The typical design temperature of the bearings is less than 300 0F. As a result, it is necessary that both the shafts 12e and 12f and base pipes 22a and 22b be cooled down against the heat flux by metal conduction and heat radiation from the rotating drum 12 to the bearing races through the shafts.
In a preferred embodiment, the bearing cooling system includes a series of spiral channels 22c/d and 22e/g surrounding the shafts that enable the flow of cooling oil around the front and back shafts. The spiral channel is preferably a trapezoidal thread fixed on the internal surface of the supporting pipes 22a, 22b. The distance between the crest of each thread to the shaft 22e, 22f is minimized to scrape any coke forming on hot shaft surfaces caused by the partial thermal cracking of the cooling oil during operation.
In operation, cooling oil entering the spiral channels on the burner side is split into two streams as shown in Figure 6A. Cooling oil enters an inlet chamber 23 located the midpoint of external supporting pipe 22a and is directed to both sides of the inlet into spiral channels 22c, 22d.
During passage through the spiral channels, the cooling oil may be heated to temperatures in the range of 390 0F thereby cooling both the base pipe 22a and shaft 12e. The cooling oil exits the spiral channels through nozzles 23a, 23b adjacent the spring rings 12g and the bearings base 22h, respectively.
Heated cooling oil is collected within an external heat radiator system (Figure 11).
The length of the spiral channels and nozzle diameters 23a, 23b are selected to control the pressure of the two cooling oil streams. Preferably, the back pressure of cooling oil through channel 22d is set to the cracker operation pressure, whereas the back pressure through channel 22c is set at atmospheric pressure.
The cooling system 22b on the exhaust side is comprised of three sections.
Cooling oil enters an inlet chamber located at the midpoint of external pipe 22b. As with the burner side, cooling oil is directed through a first spiral channel 22e adjacent the vessel 14 where it will be heated to approximately 390 0F thereby cooling both base pipe 22b and shaft 12f. The cooling oil exits the spiral channel through an outlet nozzle 22q adjacent the spring ring 12g.
A second stream of cooling oil is directed through spiral channel 22f into an intermediate chamber 22m closed from the exhaust side bearing race by packing glands 12h. The intermediate chamber 22m is connected to a system of cooling channels 22n within the bearing support adjacent a third series of spiral grooves
22g. Cooling oil passes through and exits spiral grooves 22g through outlet channel 22o.
As with the burner side, the length of the spiral channels and outlet nozzle diameters are selected to control the pressure of the two cooling oil streams.
Preferably, the back pressure of cooling oil through channel 22e and nozzle 22q is set to the cracker operation pressure, whereas the back pressure through channels 22f, 22g and nozzle 22o is set at atmospheric pressure.
In a preferred embodiment, the bearing system on the exhaust side is positioned at a greater radial distance than the bearing system on the burner side due to the higher temperatures on the exhaust side. The exhaust side also preferably includes a refractory liner 12m on the inside of tube 12f.
Quenching System 40
Hot hydrocarbon vapours leaving the cracker will typically have temperatures higher than the cracking temperature of particular hydrocarbons. As a result, and in order to avoid coke accumulation within the vapour line, the vapours are quenched by oily water injection into the quenching system 40. The quenching system includes a quenching drum 40a, a product vapour tangential outlet 40b, a hot vapour inlet 40c, an eccentric circular weir 40d, an oil/water spray nozzle 40e and cleaning device access 40f.
The injection of oily water with the resulting water evaporation is applied to decrease the temperature of HC vapour down to 600~680 0F which is a safer temperature for its further handling and to prevent coke formation. Preferably, the vapour outlet nozzles 40b are tangential, thereby promoting a vortex flow of vapours through the quencher which promotes mixing of quenching liquids with the HC vapours. The quenching system will also preferably include cleaning nozzles located in a diametrically opposite position to the outlet nozzle enabling the cleaning of the oil/water spray nozzles during normal cracker operation.
The decrease in vapour temperature also causes the condensation of small quantity of HC liquid that is collected on the lower surfaces of the quencher and that will spill back to the drum 14 over weir 4Od.
The internal surface of the hot vapour inlet nozzle 40c is wet by HC condensates at temperatures higher the cracking temperature of the HC condensates and, as a result, can be plugged by a coke layer. To avoid coking, the internal surface is preferably protected against coking by a silicate coating that is periodically washed by a small quantity of cooling oil.
Burner Assembly 50
With reference to Figures 8 and 9, the burner assembly is described. The burner is mounted to the inside of shaft 12e. The burner assembly 50 is fixed relative to the rotating front shaft 12e and includes a shaft contacting system 50k that isolates the burner within the shaft from the atmosphere at the inlet side of the shaft 12e and the vessel casing side. The burner assembly includes a fixing burner pipe 50a, adjustable burner base 50b; fixed flame distribution tip 50c and adjustable air distribution tip 5Od.
Combustion air is supplied from a burner fan (Figure 9) to burner base 50b and internal chamber C1 where the combustion air is split into primary and secondary air. Primary air flows through four swirlers 5Oe to vortex chamber C2, where the air is heated by contact with shaft 12e. Vortex space C2 is defined by contacting system 5Ok1 such that heated air enters chamber C3 through four swirling nozzles 5Of. Inside chamber C3, heated primary air is cross-contacted with fuel oil spray streams and the resulting mixture is jetted into the drum assembly 12 through angled nozzles 5Og.
Pumped fuel oil also flows through four channels into four dispersing chambers C4 via central axial inlet nozzles 5Oh. Inside of chamber C4, the oil liquid is dispersed into droplets by contact with dispersing fuel gas or a steam vortex created by tangential nozzles 5Oi. The vortex of chamber C4 is accelerated by central axial outlet nozzles 5Oh and injected into mixing chamber C2.
The jets from nozzles 5Og, have a lower cone angle than the drum cones 12b and are ignited by a small pilot flame created by an ignition and flame watch system.
A small turn of the burner base 50b around fixing pipe 50a restricts swirlers 5Oe and thus changes the ratio of primary to secondary airs. Tightening the distribution tip 5Od throttles the circular nozzle of secondary air and decreases its flow and impact. As a result of the secondary air conical shape, the flame angle can be controlled from a long cylindrical shape to full contact of fire to with the internal surface of rotating drum 12. As a result, control of the net heat power can be controlled in the range of 25% to 100%.
Process Thermodynamics
The thermal cracking process is simplified to the following steps; Heating to boiling point of lighter volatile compounds Vaporization of lighter volatile compounds Heating to crack point temperature and evaporation of cracked volatile products Heating up to carbonization temperature
The typical crack point temperature of heavy crude oil compound is usually 600 ~ 715 0F, the carbonization temperature of 95 Wt% carbon products is c.a. 1000 0F. The cracking process can be simplified to a two-step reaction:
1 : Hydrocarbon chain breaks into olefin and short paraffin:
Cnri2n+2 — * CmH2m+ CpH2p+2 n=p+m 2: Olefin chain breaks into paraffin and carbon:
Figure imgf000014_0001
C
As crude oil is a complex and indefinite mixture, the value of "n" will vary from 6 up to a few hundred. As an example,
n-decane cracked at the end of its chain: C10H22 = Cents"*" C2H4 — Qb C2H4 = CH4+ C + Qc
Qb = 25.0 kJ/kmol @ 77 0F and 25.9 kJ/kmol @ 1031 0F Qc = 35.4 kJ/kmol @ 77 0F and 35.3 kJ/kmol @ 1031 0F
n-decane cracked at the midpoint of its chain:
Figure imgf000014_0002
— Qb
C3H6 = C2H6+ C + Qc Qb = 21.4 kJ/kmol @ 77 0F and 22.8 kJ/kmol @ 1031 0F
Qc = 29.0 kJ/kmol @ 77 0F and 28.8 kJ/kmol @ 1031 0F
Taking the Le-Chatelier rule into consideration, the expected thermodynamic effects of oil cracking are: • Olefin formation is an endothermic reaction, thus heating of the feedstock over its crack point temperature will cause formation of olefins
• Olefin chain breaking is an exothermic reaction, thus oil cooling at temperatures higher than crack point will cause the formation of carbon
• Over-force oil heating moves the C-C bond breaking towards the endpoint, such that any increase of heat flux increases light product yield
The total reaction heat of long paraffin breakage into a mixture of lighter paraffin and olefins and free carbon is exothermic. Thus, during the thermal cracking, olefin product losses by evaporation will be limited and the content of olefins in the reaction end-product will be reduced.
Operational Parameters Figure 10 illustrates boundary layer effects of drum temperature, drum velocity and distance to the drum in the coke and cracking reactions. Generally, as the distance from the heated surface increases, the temperature decreases and, as the velocity of the drum increases, the time for reaction decreases. The temperature of the drum surface will also affect the coke forming reactions where coke formation is increased with increasing surface temperatures. Within the liquid phase, a thin film boundary layer comprising olefins and paraffins will exist that separates the heated surface from forming coke. As the velocity of the rotating drum increases, the boundary layer will be thinner due to shear forces and the coke layer becomes thicker.
It is important that the thickness of the boundary layer is controlled to ensure that the boundary layer is sufficiently thin in order to ensure an optimum dry coke layer and to prevent contact of a thick boundary layer (comprising a thixotropic mixture of olefins and paraffins) with the scrapers.
Thus, various operational parameters of the system may be controlled to ensure desired product formation based on feedstock composition and desired products. Flame temperature and rotational speed of the rotary drum are the primary parameters adjustable to optimize the operation of the system. The liquid feedstock level within the drum is preferably controlled to maintain a consistent time relationship between wetting time and coking time at about 1 :2. That is, the liquid level within the drum casing is maintained such that approximately one third of the outer circumference of the drum is wetted at any given time. Preferably the speed of rotation of the drum assembly provides a coking time in the range of 3-8 seconds for a given flame temperature.
As indicated above, the process described above provides:
Oil heating by convection by the heated disc within the feedstock liquid Formation of a coke / liquid suspension adjacent the submerged disc
Flash evaporation of light contaminants adjacent the submerged disc Formation of an adhered oil layer on the emerging disc Evaporation of cracked product from the oil layer on the emerged disc Continued heating to carbonization temperatures on the emerged disc Coke removal before the disk is re-submerged Process Example
With reference to Figures 11 a process example for reducing the viscosity of a heavy oil feedstock is described.
Feedstock is unloaded into 3-day tank 20-T-01 equipped with a steam coil, where it is heated to 140 0F and subsequently pumped through pump 20-P-01 into heat recovery furnace 10-F-01 , where it is further heated to 608 0F. The resulting two- phase stream enters the 8-th tray of oil fractionation column 11-C-01. The liquid phase flows down column 11-C-01 over trays 9-12, where a light fraction is liberated. Tar bottoms flow by gravity from column 11-C-01 into a mixer 10-M-01 at a temperature of 644 0F, where hydrated lime powder is added. The resulting suspension is pumped by centrifugal pump 10-P-01 to the RDTC 10-R-01 through vapour trap 10-V-02. The liquid level in 10-V-02 and, as a consequence, in 10-R- 01 is controlled by pump 10-P-01.
The RDTC cracker 10-R-01 is operated within a temperature range of 779 0F (evaporation) and 1238 0F (end of coking). The HC vapours produced in the thermal cracking reaction flow to two parallel quenchers 10-V-01 A/B where they are cooled to 680 0F by oily water injection. Product vapours feed the bottom of oil wash columns 11-C-01, where they are contacted with fresh feedstock at trays 9- 12 and with product oil at trays 1-8. A small withdraw of oil is taken from tray 7 to cover losses of the cooling oil circuit within the RDTC.
HC vapours from 11-C-01 at a temperature of 549 0F flow to the main condenser
11-A-01, where the resulting water/cracked oil/fuel gas streams are separated in three-phase separator 11-B-01. The gas phase feeds the FG header and any excess is burnt in bottom flare 11-X-01 equipped with flame arrestor 11-X-02.
The water phase flows by gravity to the oily water drum 11-B-02, also serving as a sump pump for the oily water header connected to quenchers 10-V-01 A/B and coke pit 10-S-01.
The cracked oil phase returns back to column 11-C-01 top as the reflux through pump 11-P-01 with net production being sent to an export facility. Excess carbon and calcium sulphide resulting from the thermal cracking reaction is rejected from cracker 10-R-01 into the coke receiver 10-S-01 , where it is cooled down to 212 0F in contact with oily water. Following cooling, it is removed by a bottom grate conveyor and transported in handle bins into a stacking yard, where contact with air causes intrinsic oxidation of calcium sulphide into water insoluble gypsum.
The RDTC cracker utilizes a cooling oil circuit, to keep bearing temperatures lower than 300 0F. The return oil (typical temperature of 266 0F) from the bearing cooling systems flows by gravity into cooling oil bin 10-B-02 after which it is pumped by 10-P-02 back to the cracker through the cooling oil cooler 10-A-01 , where it is cooled down up to 140 0F. If the product viscosity is out of range (for example due to an insufficient reflux), a portion of the cooling oil can be transferred to export facility using the pump 10-P-02.
Representative Data for Feedstock and Heavy and Light Cracked
Products
Feedstock data:
At dry conditions: Specific gravity 0.95
API gravity 17.6
MWt 365.4 Ib/lb mole
Viscosity @ 122 0F 105.6 cSt
Viscosity ® 212 0F 9.9 cSt Gasoline fraction NBP 160-355 0F 4.9 Wt%
Diesel oil fraction NBP 355-680 0F 33.7 Wt%
Vacuum oils fraction NBP 680-1025 0F 25.7 Wt% Tars fraction NBP 1025-13000F 11.0 Wt%
Asphalts fraction NBP >1300 0F 24.7 Wt% Flash point 149 0F
Water content 0.005 Ib / Ib (dry)
ASTM D86 760 mmHg, by volume: 1% 294.3 0F
5% 375.1 0F 10% 604.0 0F
30% 661.3 0F 50% 764.40F
70% 1049.9 0F
90% 1470.9 0F
95% 1686.9 0F
97% 2084.50F
Cracked oil data:
At work conditions:
Specific gravity 0.87 API gravity 31.3
MWt 227.5 Ib/lb mole
Viscosity ® 113 0F 3.8 cSt
Viscosity @ 39 0F 15.8 cSt
C1 -C5 1.0 Wt% Gasoline fraction NBP 160-355 0F 9.3 Wt%
Diesel oil fraction NBP 355-680 0F 69.5 Wt% Vacuum oils fraction NBP 680-1025 0F 20.3 Wt%
Tars fraction NBP 1025-1300 0F <0.1 Wt%
Flash point 41 0F Water content < 500 Wt ppm
ASTM D86 760 mmHg, by volume:
1 % < 113 °F
5% 287.1 0F
10% 354.6 0F
30% 536.9 0F
50% 614.8 0F
70% 670.5 0F
90% 721.6 0F
95% 735.6 0F
97% 746.8 0F
Heavy crack oil data:
At work conditions:
Specific gravity 0.92
API gravity 22.4
MWt 341.3 Ib/lb mole Viscosity ® 113 0F 23.4 cSt
Viscosity @ 39 0F 320.3 cSt
C1 ~C5 < 50 Wt ppm
Gasoline fraction NBP 160-355 0F < 0.1 Wt% Diesel oil fraction NBP 355-6800F 20.2 Wt%
Vacuum oils fraction NBP 680-10250F 79.6 Wt%
Tars fraction NBP 1025-1300 0F < 0.1 Wt%
Flash point 293 0F
Water content < 500 Wt ppm ASTM D86 760 mmHg, by volume:
1% 554.0 0F
5% 632.1 0F
10% 663.6 0F
30% 715.6 0F
50% 752.5 0F
70% 777.9 0F
90% 823.6 0F
95% 830.8 0F
97% 867.9 0F
The above-described embodiments of the present invention are intended to be examples only. Alterations, modifications and variations may be effected to the particular embodiments by those of skill in the art without departing from the scope of the invention, which is defined solely by the claims appended hereto.

Claims

WHAT IS CLAIMED IS:
I . A system for cracking hydrocarbons comprising: a vessel for operatively receiving and containing a volume of liquid hydrocarbon feedstock; a rotary drum assembly operably and rotatably contained with the vessel and in heating contact with the hydrocarbon feedstock, the rotary drum assembly including a heating system for heating the internal surfaces of the drum assembly during rotation of the drum assembly within the hydrocarbon feedstock wherein simultaneous rotation and heating of the drum assembly causes cracking of hydrocarbons; a vapour product collection system operatively connected to the vessel for receiving cracked hydrocarbon vapours; and, a coke removal system operatively contained within the drum for removing coke from the drum assembly and vessel.
2. A system as in claim 1 wherein the drum assembly includes two frustoconical end sections and a central cylindrical section operatively mounted between front and back pipe sections.
3. A system as in any one claims 1 or 2 wherein the heating system is operatively contained within the front pipe section.
4. A system as in any one claims 1 to 3 wherein the drum assembly and vessel includes a bearing system and the bearing system includes a cooling system for cooling the bearings during operation.
5. A system as in claim 4 wherein the bearing cooling system includes a spiral oil path within each of the front and back pipe sections and the bearing system.
6. A system as in claim 4 wherein the bearing system on the back pipe section is external to the back pipe.
7. A system as in claim 1 wherein the heating system is a flame burner statically mounted within the rotating front pipe section.
8. A system as in claim 6 wherein the burner includes a secondary air injection system for injecting secondary air into an inside position of a conical flame.
9. A system as in any one claims 1 to 8 wherein the vapour product collection system includes a quenching system for quenching vapour product to prevent coking within the vapour product collection system.
10. A system as in claim 9 wherein the quenching system includes an oil/water spray system for contacting vapour product exiting the drum.
11. A system as in any one of claims 1 to 10 wherein the coke removal system includes a plurality of scrapers in operative contact with the exterior surface of the drum assembly, the coke removal system including at least one coke pit for allowing coke to be removed from the drum.
12. A system as in claim 11 wherein the scrapers are adjustable with respect to the rotating drum assembly.
13. A process for cracking hydrocarbons comprising the steps of: a. heating a rotating surface to a given temperature; b. exposing the rotating surface to a volume of oil to be cracked thereby causing the volatization of light hydrocarbons and the formation of a thixotrophic suspension of cracked heavy oil and coke on the rotating surface; c. collecting evaporated cracked heavy oil; and, d. scraping and removing coke from the rotating surface.
14. A process as in claim 13 wherein the rotation speed and rotating surface temperature are balanced to produce dry coke before coke is scraped from the rotating surface.
15. A process as in claim 13 or claim 14 wherein the rotating surface is operatively contained within a vessel and the volume of oil to be cracked is maintained at a fixed height relative to the rotating surface.
16. A process as in any one of claims 13 to 15 wherein the rotation speed of the rotating surface is controlled to produce a thin-film thixotropic mixture of olefins and paraffins on the rotating surface for a given temperature.
17. A system for reducing hydrocarbon viscosity comprising: a system for cracking hydrocarbons as described in claim 1 operably connected to a product distillation and collection system and a feed delivery system, the product distillation and collection system including a distillation column and reflux and the feed delivery system including a heating system for preheating feed before delivery to the system for cracking hydrocarbons.
18. A system as in claim 17 wherein the feed delivery system is operably connected to the distillation column for preheating and providing preliminary separation of light and heavy fractions of the feed.
19. A system as in claim 18 wherein the feed delivery system is operably connected to the exhaust side of the system for cracking hydrocarbons for preheating the feed.
PCT/CA2006/001396 2005-08-26 2006-08-23 Method and apparatus for cracking hydrocarbons WO2007022636A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP06790576A EP1922388A4 (en) 2005-08-26 2006-08-23 Method and apparatus for cracking hydrocarbons

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US11/213,381 2005-08-26
US11/213,381 US7550063B2 (en) 2005-08-26 2005-08-26 Method and apparatus for cracking hydrocarbons

Publications (1)

Publication Number Publication Date
WO2007022636A1 true WO2007022636A1 (en) 2007-03-01

Family

ID=37114232

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CA2006/001396 WO2007022636A1 (en) 2005-08-26 2006-08-23 Method and apparatus for cracking hydrocarbons

Country Status (4)

Country Link
US (1) US7550063B2 (en)
EP (1) EP1922388A4 (en)
CA (1) CA2554715C (en)
WO (1) WO2007022636A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011143770A1 (en) * 2010-05-18 2011-11-24 Wheeler Lucie B Thermal processing reactor for mixtures, fabrication of the reactor, processes using the reactors and uses of the products obtained
US10173146B2 (en) 2014-04-11 2019-01-08 Thermtech Holdings As Method of treating a material

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0810299D0 (en) * 2008-06-06 2008-07-09 Rolls Royce Plc An apparatus and method for evaluating a hydrocarbon to determine the propensity for coke formation
WO2011038027A1 (en) * 2009-09-22 2011-03-31 Neo-Petro, Llc Hydrocarbon synthesizer
WO2012000115A1 (en) * 2010-06-30 2012-01-05 Jose Lourenco Method to upgrade heavy oil in a temperature gradient reactor (tgr)
WO2013049911A1 (en) 2011-10-04 2013-04-11 Mackenzie Millar Cascading processor
US9187699B2 (en) * 2011-11-08 2015-11-17 Exxonmobil Chemical Patents Inc. Hydrocarbon pyrolysis process
CA2783608A1 (en) 2012-07-23 2014-01-23 Lucie Wheeler Environmental process to transform contaminated or uncontaminated feed materials into useful products, uses of the process, products thereby obtained and uses thereof, manufacturing of the corresponding plant
CA2801035C (en) 2013-01-07 2019-11-26 Jose Lourenco Method and apparatus for upgrading heavy oil
WO2014121368A1 (en) 2013-02-06 2014-08-14 Envirollea Inc. Thermal process to transform contaminated or uncontaminated feed materials into useful oily products, uses of the process, products thereby obtained and uses thereof, manufacturing of the corresponding plant
WO2017059515A1 (en) 2015-10-08 2017-04-13 1304338 Alberta Ltd. Method of producing heavy oil using a fuel cell
CA2914070C (en) 2015-12-07 2023-08-01 1304338 Alberta Ltd. Upgrading oil using supercritical fluids
CA2920656C (en) 2016-02-11 2018-03-06 1304342 Alberta Ltd. Method of extracting coal bed methane using carbon dioxide
CA2973210A1 (en) 2017-07-13 2019-01-13 Louis Bertrand Process for producing liquid fuel from waste hydrocarbon and/or organic material, managing system thereof
CA2997634A1 (en) 2018-03-07 2019-09-07 1304342 Alberta Ltd. Production of petrochemical feedstocks and products using a fuel cell
US20200148956A1 (en) * 2018-11-09 2020-05-14 Exxonmobil Research And Engineering Company Delayed coker vapor line coke lancing
CA3032769C (en) 2019-02-04 2020-04-21 Envirollea Inc. Flotation oils, processes and uses thereof

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1231695A (en) * 1916-05-10 1917-07-03 Arthur F L Bell Apparatus for refining petroleum.
US1418414A (en) * 1916-10-09 1922-06-06 Seth B Hunt Process of making unsaturated hydrocarbon material
US1541140A (en) * 1922-08-21 1925-06-09 Alfonce H Heller Process of and apparatus for distilling and cracking hydrocarbon oils
GB244275A (en) * 1924-12-22 1925-12-17 American Shale Reduction Compa Process of and apparatus for distilling oil shale, bituminous coal and the like to obtain light hydrocarbons
US1677758A (en) * 1928-07-17 Treatment of carbonaceous and other materials
GB457960A (en) * 1935-03-19 1936-12-09 Edouard Georges Marie Romain L Continuous distillation retort
US4127473A (en) * 1975-10-20 1978-11-28 Kureha Kagaku Kogyo Kabushiki Kaisha Method for the thermal cracking of heavy oil
US4443328A (en) * 1982-06-01 1984-04-17 Toyo Engineering Corporation Method for continuous thermal cracking of heavy petroleum oil
US4512873A (en) * 1983-01-07 1985-04-23 Veba Oel Entwicklungs-Gesellschaft Mbh Process for low temperature carbonization of hydrogenation residues
CA1227970A (en) * 1983-07-28 1987-10-13 Walter C. Saeman Method and apparatus for combustion of diverse materials and heat utilization
US5356530A (en) * 1992-10-16 1994-10-18 Albert Calderon Method for upgrading petroleum residuum and heavy crude oil
US5821396A (en) * 1997-01-10 1998-10-13 Bouziane; Richard Batch process for recycling hydrocarbon containing used materials
US6005149A (en) * 1998-08-18 1999-12-21 Engineering, Separation & Recycling, Ltd. Co. Method and apparatus for processing organic materials to produce chemical gases and carbon char
EP1067171A2 (en) * 1996-09-27 2001-01-10 Alberta Oil Sands Technology, and Research Authority Process for removing contaminants from oil

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US148806A (en) 1874-03-24 Improvement in oil-stills
BE336479A (en) *
US1183457A (en) 1915-12-07 1916-05-16 Samuel M Herber Oil distillation.
US1622573A (en) 1924-04-12 1927-03-29 Gasoline Products Co Coking still
GB313159A (en) * 1928-06-08 1930-08-21 Trent Process Corp Improvement in process and apparatus for cracking liquid hydrocarbons
US1876789A (en) * 1929-03-06 1932-09-13 Taylor John Lewis Retort for mineral oils
GB2094336B (en) * 1981-02-26 1984-01-18 Spencer Peter Method and apparatus for the thermal cracking of heavy hydrocarbons
EP0050030B1 (en) * 1980-10-13 1985-01-09 Peter Spencer Reactor for the thermal cracking of heavy hydrocarbons and a process and apparatus for the distillation and thermal cracking of a crude oil feedstock using such a reactor
DE4107294A1 (en) 1991-03-07 1992-09-10 Spitzer Geb Kirchhof Ingrid Cracking plant - has hot body for fractional distn. of highly viscous waste oil
NO175847C (en) 1992-10-09 1994-12-21 Olav Ellingsen Process by selective and / or non-selective evaporation and / or decomposition of particular hydrocarbon compounds in liquid form and device for carrying out such process
US5885444A (en) * 1992-11-17 1999-03-23 Green Oasis Environmental, Inc. Process for converting waste motor oil to diesel fuel
CA2170908A1 (en) * 1993-09-03 1995-03-09 Herbert Tratz Rotatable heating chamber for solid material
NO312303B1 (en) * 1999-02-11 2002-04-22 Thermtech As Process for catalytic upgrading and hydrogenation of hydrocarbons
FR2797642B1 (en) * 1999-08-16 2003-04-11 Inst Francais Du Petrole METHOD AND INSTALLATION FOR PRODUCING A COMBUSTIBLE GAS FROM A FEED RICH IN ORGANIC MATTER
RU2178337C2 (en) 2000-02-14 2002-01-20 Селиванов Николай Иванович Method and device for resonance excitation of liquids and method and plant for fractioning of hydrocarbon liquids
IT1318933B1 (en) 2000-09-27 2003-09-19 Vomm Chemipharma Srl PROCESS AND EQUIPMENT FOR THE FRACTIONAL DISTILLATION OF CRUDE OIL.

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1677758A (en) * 1928-07-17 Treatment of carbonaceous and other materials
US1231695A (en) * 1916-05-10 1917-07-03 Arthur F L Bell Apparatus for refining petroleum.
US1418414A (en) * 1916-10-09 1922-06-06 Seth B Hunt Process of making unsaturated hydrocarbon material
US1541140A (en) * 1922-08-21 1925-06-09 Alfonce H Heller Process of and apparatus for distilling and cracking hydrocarbon oils
GB244275A (en) * 1924-12-22 1925-12-17 American Shale Reduction Compa Process of and apparatus for distilling oil shale, bituminous coal and the like to obtain light hydrocarbons
GB457960A (en) * 1935-03-19 1936-12-09 Edouard Georges Marie Romain L Continuous distillation retort
US4127473A (en) * 1975-10-20 1978-11-28 Kureha Kagaku Kogyo Kabushiki Kaisha Method for the thermal cracking of heavy oil
US4443328A (en) * 1982-06-01 1984-04-17 Toyo Engineering Corporation Method for continuous thermal cracking of heavy petroleum oil
US4512873A (en) * 1983-01-07 1985-04-23 Veba Oel Entwicklungs-Gesellschaft Mbh Process for low temperature carbonization of hydrogenation residues
CA1227970A (en) * 1983-07-28 1987-10-13 Walter C. Saeman Method and apparatus for combustion of diverse materials and heat utilization
US5356530A (en) * 1992-10-16 1994-10-18 Albert Calderon Method for upgrading petroleum residuum and heavy crude oil
EP1067171A2 (en) * 1996-09-27 2001-01-10 Alberta Oil Sands Technology, and Research Authority Process for removing contaminants from oil
US5821396A (en) * 1997-01-10 1998-10-13 Bouziane; Richard Batch process for recycling hydrocarbon containing used materials
US6005149A (en) * 1998-08-18 1999-12-21 Engineering, Separation & Recycling, Ltd. Co. Method and apparatus for processing organic materials to produce chemical gases and carbon char

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1922388A4 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011143770A1 (en) * 2010-05-18 2011-11-24 Wheeler Lucie B Thermal processing reactor for mixtures, fabrication of the reactor, processes using the reactors and uses of the products obtained
RU2572981C2 (en) * 2010-05-18 2016-01-20 Энвайролли Инк. Reactor for heat treatment of mixes, fabrication of reactor, its application and application of produced products
US10173146B2 (en) 2014-04-11 2019-01-08 Thermtech Holdings As Method of treating a material

Also Published As

Publication number Publication date
EP1922388A4 (en) 2011-10-19
CA2554715C (en) 2008-01-08
EP1922388A1 (en) 2008-05-21
US20070045098A1 (en) 2007-03-01
CA2554715A1 (en) 2006-10-17
US7550063B2 (en) 2009-06-23

Similar Documents

Publication Publication Date Title
CA2554715C (en) Method and apparatus for cracking hydrocarbons
JP5027660B2 (en) Vapor / liquid separator used for pyrolysis of hydrocarbon feedstock containing residual oil
RU2572981C2 (en) Reactor for heat treatment of mixes, fabrication of reactor, its application and application of produced products
CA2683943C (en) Hydrocarbon thermal cracking using atmospheric residuum
US7550642B2 (en) Olefin production utilizing whole crude oil/condensate feedstock with enhanced distillate production
CN1957069B (en) Vapor/liquid separation apparatus for use in cracking hydrocarbon feedstock containing residual oil
KR101512208B1 (en) Olefin production utilizing a feed containing condensate and crude oil
US9052109B1 (en) Pyrolytic gas processor and tire conversion system therefrom
CA2642797A1 (en) Olefin production utilizing condensate feedstock
CA2938502A1 (en) Mobile plant for thermally treating a contaminated or uncontaminated feed stream, processes thereof and uses of products thereof
MXPA04008942A (en) A compact rectifying unit for separation of mixed fluids and rectifying process for separation of such mixed fluids.
CA2750129A1 (en) Thermal process to transform contaminated or uncontaminated feed materials into useful products, uses of the process, products thereby obtained and uses thereof, manufacturing of the corresponding plant
EA011643B1 (en) Pyrolysis of residual hydrocarbons
CA2926434C (en) Rotating kiln and apparatus for thermal conversion of organic wastes, method for converting organic wastes into useful products, manufacturing of rotating kilns and apparatus and uses thereof
RU2701860C1 (en) Pyrolysis method of liquid and gaseous hydrocarbons and device for its implementation
CA2757061A1 (en) Mobile plant for thermally treating a contaminated or uncontaminated feed stream, processes thereof and uses of products thereof
CA1120418A (en) Process and apparatus for thermally processing heavy hydrocarbon-containing liquids
US11427771B2 (en) Process and apparats for recovering cracked hydrocarbons
RU2017789C1 (en) Method and aggregate for hydrocarbon raw materials steam-cracking

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2006790576

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 2006790576

Country of ref document: EP