Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING 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
  • C10G7/00—Distillation of hydrocarbon oils
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING 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
  • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
  • C10G31/06—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by heating, cooling, or pressure treatment
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING 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
  • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
  • C10G9/28—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid material

Definitions

• the invention relates to a process for the high-temperature, short-term distillation of a liquid residual oil from the processing of petroleum, natural bitumen or oil sand, wherein the residue sol is mixed with granular, hot coke as heat transfer medium (heat transfer medium coke) in a mixing unit, 60 to 90 %
• heat transfer medium coke heat transfer medium
• By weight of the residual oil is evaporated by converting the non-evaporated portion of the residue sol, which contains the metal-containing asphaltenes, in a mixture with the heat transfer medium in the mixer to old steam, gas and coke and to separate gases and vapors from the mixer from the granular coke Cools, gases and vapors and produces a product oil as condensate and gas, and wherein coke withdrawn from the mixer is heated again and returned to the mixer as a heat transfer medium.
• the invention has for its object to further develop the known method and to improve the conditions of continuous operation.
• the aim is to maximize the yield of the product oil and to minimize its content of heavy metals (nickel, vanadium), Konradson carbon (CCR) and heteroatoms (S, N).
• the object is achieved in that the liquid residue is mixed with heat-transfer coke at 500 to 700 ° C. in a weight ratio of 1: 3 to 1:30 in the mixer, in that at least 80% by weight of the heat transfer medium -Kokses grain sizes in the range of 0.1 to 4 mm, that through the mixing process on the grains of the heat transfer coke, a liquid residue film is first formed, which is preferably in the mixer at an operating temperature as low as possible in the range of 450 to 600 ° C. 500 to 560 ° C predominantly evaporated (z. B.
• Pollutants (heavy metals, heteroatoms, CCR) asphaltenes converted to oil, gas and coke. In this case, these pollutants preferably remain in the coke.
• the mixers in question for the process are e.g. B. screw mixer, rotary tube mixer, paddle mixer, ploughshare mixer or vibration mixer.
• Mixing units with intermeshing, co-rotating screws which are known per se and are described in German patent 12 52 623 and in the corresponding US patent 3 308 219 and also in German patent 22 13 861, can also be used. Due to the interaction of the screws, deposits can only form to a limited extent on their surfaces and in the mixer housing.
• a further embodiment of this method consists in passing the liquid residue sol during mixing with the hot heat transfer coke through a first mixing section and then through at least a second mixing section, the heat transfer coke and residue sol being fed to the mixer at the beginning of the first section feeds and in the first Section gases and vapors is released at temperatures in the range from 450 to 600 ° C., that hot heat transfer coke is again added to the mixture containing heat transfer coke and residual residue sol from the first section at the beginning of the second section and from the mixer in the first and / or second section of gases and vapors.
• Different temperatures in the range from 450 to 600 ° C can be set in the different mixture sections.
• the second mixing section begins where fresh heat transfer coke is again added from the outside into the coke mixture coming from the first section.
• the addition of coke increases the temperature in the second section, which also increases the temperature of the gases and vapors.
• An increase in the temperature of 5 to 50 ° C. is usually aimed for by adding heat transfer coke. This avoids the temperature falling below the dew point in the lines between the mixer and the condensation device.
• the coking of the remaining non-volatile liquid residue components on the coke is accelerated at a higher temperature, whereby the Coke dries faster in the mixer and thereby loses its stickiness. This is a prerequisite for the flowability of the coke in the heat transfer circuit system. It is also possible to provide more than two mixture sections and to supply hot coke from the outside at the beginning of each section.
• the hot heat transfer coke is usually fed to the first and second sections in a weight ratio of 20: 1 to 1: 1.
• a liquid residue sol which differs from the residue sol of the first section may be supplied to the second or a subsequent mixing section.
• the residue sol supplied to the second section may e.g. B. treated at a higher temperature than the first residue sol.
• Such a second residue sol can also be thermally treated in a second, partly parallel mixer, which, for. B. works at a higher temperature.
• liquid residue sol preheated to temperatures in the range from 100 to 450 ° C.
• Preheating reduces the viscosity of the residual oil and the heat required for evaporation, which means that the non-evaporable part of the residual oil reaches the desired conversion temperature more quickly.
• the inventive method achieves that about 80 to 95% of the heavy metals (Ni and V), about 50 to 70% of Konradson's carbon (CCR) and 30 to 70% of the heteroatoms (S and N) from the used Residue sol is removed with the coke produced and a C 5+ product oil is produced from the residue sol with a yield of 70 to 85% by weight. After separating the gasoline and possibly the kerosene and diesel fractions, this product oil is suitable for further catalytic processing.
• Fig. 2 a flow chart of the method with two
• FIG. 3 a flow diagram of the process with two
• FIG. 5 a horizontal section through a mixer with conically enlarged screws in a representation analogous to FIG. 4
• FIG. 6 a vertical section through a mixer with screws working in opposite directions in a representation analogous to FIG. 1.
• the mixer (1) through the line (3) 500 to 700 ° C hot heat transfer coke from the collection bunker (2) is supplied.
• a residue sol is injected through line (4) at a temperature of preferably 100 to 450 ° C.
• the weight ratio of coke: residue sol is in the range from 3: 1 to 30: 1, a temperature of the mixture (conversion temperature) in the range from 450 to 600 ° C. being established in the mixing unit.
• At least 80% by weight of the heat transfer coke has grain sizes in the range from 0.1 to 4 mm, and the grain size d 50 is in the range from 0.2 to 2 mm, as a result of which the coke is largely separated from the gases formed in the mixer and oil vapors at the mixer outlet.
• the mixer (1) has two intermeshing screws (8) and (9) which rotate in the same direction and which are shown schematically in FIG. 4.
• the mixing mechanism can also have three or more intermeshing, co-rotating screws, which can also be flared, see Fig. 5.
• Each screw is designed in the manner of a screw conveyor and provided with conveying surfaces (8a) and (9a) (Figs. 4 and 5).
• the coiled conveying surfaces (8a) and (9a) have different slopes at different points, as is shown in simplified form in FIGS. 4, 5 and 6.
• the gradient of the conveying surfaces before the residual oil is fed into the mixing unit is lower than in the reaction zone of the mixing unit, in order first to convey the coke axially into the reaction zone and then to increase it at a larger rate Mix the gradient of the conveying surfaces in the reaction zone intensively with the residue sol.
• the hot, oil-free, granular coke leaves the mixer (1) at the end of the mixer at a temperature of 450 to 600 ° C and falls through a channel (10) in a post-degassing bunker (11), the A strip gas (33) can be supplied in the lower part. Residual gases and vapors can be drawn out of the bunker (11) through the channel (10). Coke is withdrawn from the bunker (11) through line (12), and part of the coke is removed from the system through line (12a) or also through line (2a). The remaining coke passes through line (12) to the bottom of a pneumatic conveyor line (15), to which combustion air is fed through line (16) and, if necessary, fuel is supplied through line (17).
• Combustion gases convey the coke upwards in the conveyor section (15), with part of the coke and / or the supplied fuel being burned off at the same time.
• the coke heated in the conveyor section (15) reaches the collecting bunker (2), from which exhaust gas is removed through the line (18).
• the coke in the bunker (2) has temperatures in the range from 500 to 700 ° C and usually 550 to 650 ° C.
• Gases and vapors leave the mixer (1) through the channel (22) and enter the condensation (23), in which the gases and vapors are rapidly cooled.
• Product oil and gas are drawn off separately through lines (35) and (34).
• the mixer (1) has two mixing sections (la) and (lb). At the beginning of the first section (la), the mixer is led through the line (3) of hot coke from the collection bunker (2) too. At the same time, the first section (la) is fed through the line (4) residue sol. At the beginning of the second mixing section (lb) further hot coke is added through line (3a) and, if desired, a second residue sol through line (4a). The gases and vapors formed in the mixing sections (la) and (lb) are withdrawn together through the line (22) or (22a) from the mixing unit and fed to the condensation device (23).
• Fig. 3 two different residual oils are fed through lines (4) and (4a) into two different mixers (1) and (5) and converted there at different temperatures that are optimal for the respective residue.
• the mixer (1) of Fig. 6 is equipped with pairs of screws (25) and (26) which work in opposite directions, so that there are opposite transport directions (27) and (28).
• Heat transfer coke is added through lines (3) and (3a), and residual sol is supplied through lines (4) and (4a). The coke is drawn off centrally through the channel (10), and gases and vapors are drawn off through the line (22). Otherwise, as already explained together with FIG. 1, the method can be carried out.
• 10 t per hour of a vacuum residue formed during the distillation of crude oil are injected into the mixer (1) at 250 ° C. and mixed with 100 t / h of heat transfer coke at 600 ° C.
• the vacuum residue contains 20% by weight of CCR, 740 mg / kg vanadium and 120 mg / kg nickel.
• a temperature of 540 ° C is set in the mixer, at which 8.2 t / h oil vapors and gas and 1.8 t / h fresher Coke are formed.
• the mixer has two intermeshing screws rotating in the same direction. The mixture of old steam and gas is withdrawn from the mixer and subjected to condensation.

Landscapes

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

Applications Claiming Priority (3)

Publications (2)

Family

ID=7831796

Family Applications (1)

Country Status (9)

Families Citing this family (30)

Family Cites Families (3)

• 1997
  • 1997-06-07 DE DE19724074A patent/DE19724074C2/de not_active Expired - Lifetime
• 1998
  • 1998-06-03 JP JP50150599A patent/JP4111550B2/ja not_active Expired - Fee Related
  • 1998-06-03 CA CA002293392A patent/CA2293392C/fr not_active Expired - Fee Related
  • 1998-06-03 US US09/445,163 patent/US6413415B1/en not_active Expired - Fee Related
  • 1998-06-03 DE DE59802658T patent/DE59802658D1/de not_active Expired - Lifetime
  • 1998-06-03 AT AT98932111T patent/ATE212048T1/de active
  • 1998-06-03 AU AU82125/98A patent/AU8212598A/en not_active Abandoned
  • 1998-06-03 WO PCT/EP1998/003319 patent/WO1998055564A1/fr not_active Ceased
  • 1998-06-03 EP EP98932111A patent/EP1009785B1/fr not_active Expired - Lifetime
  • 1998-06-03 ES ES98932111T patent/ES2172160T3/es not_active Expired - Lifetime

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events