CN1074454C - Process and apparatus for treatment of waste oils - Google Patents
Process and apparatus for treatment of waste oilsInfo
- Publication number
- CN1074454C CN1074454C CN97193273A CN97193273A CN1074454C CN 1074454 C CN1074454 C CN 1074454C CN 97193273 A CN97193273 A CN 97193273A CN 97193273 A CN97193273 A CN 97193273A CN 1074454 C CN1074454 C CN 1074454C
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- waste oil
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
- C10M175/0025—Working-up used lubricants to recover useful products ; Cleaning by thermal processes
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- 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
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- 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)
- Combustion & Propulsion (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Lubricants (AREA)
- Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
- Processing Of Solid Wastes (AREA)
- Coke Industry (AREA)
Abstract
The present invention is directed to a process and apparatus for the reclaiming and re-refining of waste oils. The process comprises raising a temperature of a feed mixture of fresh waste oil and a recycled non-volatile residue to a range of 400 DEG C to 490 DEG C for a time sufficient to cause pyrolysis of said heavy hydrocarbons contained in the feed mixture, but insufficient to permit substantial undesired polymerization, oxidation and dehydrogenation reactions to take place in said feed mixture; cooling the resulting pyrolized waste oil mixture to a temperature in the range of 300 DEG C to 425 DEG C, and maintaining said temperature while allowing volatile components in the pyrolyzed waste oil mixture to evaporate, leaving a non-volatile residue containing said contaminants; condensing the evaporated volatile components to form a reclaimed oil product; and mixing the non-volatile residue with fresh waste oil to form more of said feed mixture and repeating said temperature raising, cooling, evaporation and mixing steps on a continuous basis, while continuing to condense volatile components evaporated from said pyrolyzed waste oil mixture. The apparatus comprises a heating unit, a container, a condenser and pumping equipment and piping. The process and apparatus of the present invention generate #2 diesel fuel, gasoline and coke from waste oil.
Description
Technical field
The present invention relates to a kind of method and apparatus that reclaims various sources waste oil.
Background technology
Waste oil has an important environmental problem.For example, USEPA in 1992 estimates that the annual waste oil that produces of the U.S. is 4.9 * 10
6m
3(1.3 * 10
12Gallon), only about 2% is recovered, although existing existing a large amount of physics and chemical processes for reclaiming and re-refining industry and motor oil.Remaining waste oil supposition is stacked or is abandoned with various approach to enter environment.
A kind of important process method early comprises with sulfuric acid and the carclazyte waste oil of re-refining.Sulfuric acid is used for removing unsaturates, dirt, additive and band color substance as spe medium from waste oil.Carclazyte is used as sorbent material to remove impurity.This method has disadvantageously produced a large amount of acid sludges and carclazyte and must handle as a kind of technology waste.
For overcoming the offal treatment problem of acid-carclazyte method, developed dissimilar distillating methods, as at United States Patent (USP) 3,625, disclosed in 881 and 4,071,438.It is that primary product and a kind of carbon black are the technology waste that these methods are produced a kind of round-robin lubricating oil.
Recently, the development of reclaiming the usable fuel method has caused producing diesel oil from waste oil, and is for example at United States Patent (USP) 5,271, disclosed in 808 and 5,286,349.United States Patent (USP) 5,271,808 disclose a kind of method that reclaims waste oil, wherein use the container type well heater.In this method, because a large amount of chargings is held one than long residence time in the pyritous heating container, therefore produced undesirable polyreaction, oxidizing reaction and dehydrogenation reaction, cause the generation of unstable diesel oil and a large amount of ash cake slags.In addition, this method is very short working time.
DE-A-3,224,144 disclose a kind of method and apparatus with the useless motor vehicle engine oil of microwave heating cracking.This waste oil is removed volatile products being heated to cracking on the distillation point in condenser.
JP-56 082886 discloses a kind of method and has formed non-homogeneous slurry to eliminate the output of local coking and improvement light oil by catalyzer is mixed with mink cell focus.The catalytic cracking in liquid phase of this slurry.
EP-308669 discloses the processing material that is used in the halogen-containing hydrocarbon of thermo-cracking in the alkaline matter fluidized-bed.
US-5,143,597 disclose a kind of recovery method of waste lubricating oil, waste lubricating oil are injected the downstream of coking furnace delayed coking unit in method.Therefore waste oil is thermally cracked into the hydrocarbon fuel oil product.
Summary of the invention
An object of the present invention is by provide a kind of reclaim waste oil effectively and cost effective method and equipment to overcome the part or all of shortcoming of waste oil recovery technology in the past.
Another object of the present invention is to provide a kind of method that reclaims waste oil with its preferred styles at least, and it causes producing satisfied stability and valuable 2
#Diesel oil or gasoline.
The present invention has a purpose to provide a kind of method that reclaims waste oil in addition, and it causes forming than any method in the past still less residue, and can make simultaneously has the more long running time between the shut-down.
Further object of the present invention provides cracking apparatus and the cylindrical reactor that a cover is used for the inventive method.
Provide the method that a kind of processing contains the waste oil of heavy hydrocarbon and pollutent according to one aspect of the present invention.This method comprises fresh waste oil and the charging of the non-volatile Residual oil mixture of round-robin is warmed up to 400 ℃ to 490 ℃ (measuring in the heating installation outlet) certain hours, this time is enough to make the heavy hydrocarbon that is contained in the mixture charging to produce thermo-cracking, but also deficiency so that substantial undesirable polyreaction, oxidizing reaction and dehydrogenation reaction take place in the mixture charging.Then, waste oil mixture after the thermo-cracking that obtains is cooled to 300 ℃ to 455 ℃ temperature ranges.Preferably 300 ℃ to 425 ℃ and most preferred be 300 ℃ to 375 ℃ temperature ranges, and remain on this temperature and allow the evaporation of the volatile constituent in the waste oil mixture after the cracking simultaneously, and stay the non-volatile Residual oil that contains pollutent.The volatile constituent of evaporation forms the refiltered oil product through condensation, and non-volatile Residual oil is mixed the formation incoming mixture with fresh waste oil.Repeat intensification, cooling, evaporation and mixing step by successive processes then, and the volatile constituent that will evaporate the waste oil mixture continues condensation after cracking.
Waste oil is heated to the temperature that produces thermo-cracking and depends on predetermined transformation efficiency, that is to say, the gasoline output of higher percent must be with higher temperature, and the higher percent production of diesel oil will be used lesser temps.
In a preferred form of present method, when the output of refiltered oil product drops under the predetermined level, with the incoming mixture temperature be elevated to 400 ℃ to more than 490 ℃ to promote heavy hydrocarbon " drastic cracking ", then waste oil mixture after the resulting thermo-cracking is cooled off again, evaporation and mixing step.
In another preferred form of present method, when pollutent in the waste oil mixture after the thermo-cracking increases to predetermined level, the non-volatile Residual oil that will contain pollutent is heated to one period short period of time of 470 ℃ to 590 ℃ temperature ranges, allow temperature drop to 440 ℃ to 570 ℃ temperature ranges and remain in this temperature under 172kPa (3 to the 25psig) pressure then and stand further thermo-cracking and pyrogenic reaction to cause Residual oil at 21kPa, produce volatile constituent and solid coke again, subsequently should further volatile constituent remove and condensation and solid coke collected and abandon.
In another preferred form of present method, before heating up, charging earlier it is mixed with vapor phase.
Provide a cover according to another aspect of the present invention and handle the equipment that contains heavy hydrocarbon and pollutent waste oil.This equipment comprises the heating unit that is used for fresh waste oil and the non-volatile Residual oil mixture of round-robin charging intensification, the transformation efficiency predetermined according to cylindrical reactor is warmed up to 400 ℃ to 490 ℃ temperature range certain hours, this time is enough to make heavy hydrocarbon contained in incoming mixture to produce thermo-cracking, but deficiency is so that substantial undesirable polyreaction, oxidizing reaction and dehydrogenation reaction take place in the incoming mixture; Be used to receive the container of waste oil mixture after the thermo-cracking of gained, and after keeping thermo-cracking with this container the waste oil mixture in 300 ℃ to 455 ℃ temperature ranges.Be preferably 300 ℃ to 425 ℃, most preferably be 300 ℃ to 375 ℃ and allow volatile constituent evaporation in the waste oil mixture after the thermo-cracking, stay the non-volatile Residual oil that contains pollutent.The volatile constituent that is used for condensation evaporation forms the condenser of refiltered oil product; Be used for to mix with fresh waste oil with the non-volatile Residual oil of said vesse and form the said mixture charging, be used for continuously the said mixture feed cycle by above-mentioned heating installation to said vesse, and be used for above-mentioned volatile constituent is transported to pumping unit and pipeline the condenser from said vesse.
The heating of charging preferably at an energy with about 0.6m/s to 4.5m/s (2ft/s is to 15ft/s), be more preferably 1.2m/s and in the tubular type heating installation of the high flow rate of liquid of 3.0m/s (4ft/s is to 10ft/s) operation, carry out.Preferably with mixture cooling after the thermo-cracking and one as above-mentioned as the preferred cylindrical reactor of container in the evaporating volatile component.Control the temperature of cylindrical reactor by regulating the feed volume that feeds preheating in the cylindrical reactor.Since in the tubular type heating installation residence time short (promptly 1 second to 30 seconds, preferably 1 second to 15 seconds, most preferred was 3 seconds to 10 seconds) and in cylindrical reactor temperature relatively low, so reduced undesirable side reaction.
Be under the high-temperature condition at the tubular type heating unit, the whole metal ingredients in the waste oil and other pollutent all will resolve into metal, hydrocarbon and heavy still bottoms.With light Fuel steam with follow preferably to introduce and be used for the fresh waste oil charging of preheating (for example being preheating to 110 ℃ to 150 ℃ temperature ranges) in the heat exchanger by the steam of discharging in the cylindrical reactor.With in the cylindrical reactor all the other than heavy oil and fresh waste oil charging with heating with heat scission reaction once more in the pump input tubular type heating installation and repeating this process continuously.When high boiling point oil in cylindrical reactor stores up a kind of like this degree when descending with the product that causes present method, the temperature with tubular heater improves to carry out drastic cracking again.Temperature returned and drop to standard state thereafter.
What can be used as option is that steam cracking can be injected tubular heater with water vapour.It has improved oily stability and the generation of having lowered coke, and water vapour can be produced by the tubular type heating unit.
Common charging with preheating is added to the top of cylindrical reactor and down sprays at the center.The heating of coming out from tubular type heating installation heating tube near the mixture adding cylindrical reactor bottom after the thermo-cracking.The feeding line that is used for heating tube is introduced from the cylindrical reactor bottom, enter tubular heater through pump then, the charging that comes from cylindrical reactor can be from the top or the bottom enter tubular heater, if requirement is arranged, the charging of preheating directly can be pumped into tubular heater, according to the temperature of cylindrical reactor inner fluid not by or part pass through cylindrical reactor.
Adopt method and apparatus of the present invention to comprise 2 from the product that recovery waste oil obtains
#Diesel oil, gasoline and coke.Utilization present method and equipment can not produce significant waste disposal problem.
The charging of present method can be the waste oil of any kind, for example the waste crude oil of automotive engine oil, industrial lubricant, vegetables oil, fish oil, industrial greasy filth and leakage.
The accompanying drawing summary
Fig. 1 is the synoptic diagram that a cover can be used to operate the device instance of the inventive method.
Fig. 2 is the synoptic diagram of a kind of preferred tubular heater of using in Fig. 1 equipment.
Fig. 3 is the synoptic diagram of a pref. cylindrical reactor using in Fig. 1 equipment.
Fig. 4 is the synoptic diagram that the device instance of 2 cylindrical reactors is arranged.
Fig. 5 is the synoptic diagram of the another kind of profile instance of present device.
Fig. 6 is the synoptic diagram of another kind of cylindrical reactor.
Implement best mode of the present invention
Referring to Fig. 1 entire method of the present invention and its used exemplary apparatus are described.In illustrated method, the fresh waste oil of the charging of present method is added to the top of heat exchange posts 14 (if any requiring from feed chute 10 usefulness pump (not shown)s through managing 12, can equip several this exchange columns), in post charging toward current downflow and with product vapor (back obtains the method for narrating) through heat exchange with its preheating (being preheating to 110 ℃ of temperature usually) to 150 ℃ of scopes.Then, charging after the preheating is passed to the cylindrical reactor 18 through pipeline 16 with pump from the bottom of heat exchange posts 14, this reactor constitutes and is used for receiving and preserve from tubular type heating installation 20 and the container of waste oil mixture after the thermo-cracking of coming, within 300 ℃ to 455 ℃ predetermined temperature ranges, preferably 300 ℃ to 425 ℃, most preferred is the mixture of preserving in reactor 18 within 300 ℃ to 375 ℃ after the preheating, and as the back with described in more detail being evaporated in this volatile constituent.After the waste oil of the preheating of pipeline 16 input down sprays the thermo-cracking that is stored in cylindrical reactor 18 bottoms the waste oil mixture, to produce after a kind of fresh waste oil that is used for the preheating further handled and the thermo-cracking waste oil mixture blended mixture mutually.The waste oil mixture was to desired 300 ℃ of effects to 455 ℃ of temperature ranges after the spray of fresh waste oil also had the cooling heat cracking.Lightweight oil and water from waste oil mixture after the fresh waste oil of preheating and the thermo-cracking are evaporated and distill, and stay non-volatile Residual oil, and resulting steam is removed from cylindrical vessel 18 through managing 22 and delivered in the heat exchange posts 14 simultaneously.
The mixture of the non-volatile Residual oil after fresh waste oil that forms with described method in cylindrical reactor 18 and the thermo-cracking in the waste oil mixture (is seen Fig. 2 with pump 24 as incoming mixture in pipeline 25 is transported to a series of heating tubes 26 of 20 li of tubular type heating units, 1 heating tube only draws among Fig. 1), device 20 as one incoming mixture is rapidly heated reach desired 400 ℃ to 490 ℃ scopes one period short period of time (be generally 1 second to 30 seconds, preferably 1 second to 15 seconds and most preferred be 3 seconds to 10 seconds) device.Heat is produced by the burner in the device 20 28, will install inside and become fiery chamber.Burner can burn with conventional fuel or by fuel or gas that recovery method itself obtains.
So promptly heated by managing 26 incoming mixture less relatively with incoming mixture volume in the pipe because the exhibiting high surface of pipe is long-pending, pipe 26 is straight tube preferably, and 1.8m is preferably arranged to 60m long (6ft grows to 20ft), although the number of heating tube and length depend on the feed volume added every day and ideal is that 1.2m/s is to 3.0m/s (4ft/s is to 10ft/s) by the incoming mixture speed (preferably 0.6m/s is to 4.5m/s (2ft/s is to 15ft/s)) of pipe.Heating tube 26 can be used serpentine tube, because only about 100 ℃ of the temperature difference between the inclusion of the inclusion of tubular type heating unit 20 and cylindrical reactor 18, so thermal losses is very low usually in the tubular type heating unit.Therefore, reduced the size of tubular type heating unit 20.The diameter of heating tube 26 most preferred for 1.25cm to 12.5cm (0.5in is to 5in) the scope interior incoming mixture of heating tube effectively.
As above pointed out, incoming mixture is heated to desired 400 ℃ of temperature certain hours to 490 ℃ of scopes in pipe 26, this time is enough to make the heavy hydrocarbon in the incoming mixture to produce thermo-cracking, but not enough so that substantial undesirable polyreaction, oxidizing reaction and dehydrogenation reaction generation.Time length depends on the type of incoming mixture to a certain extent, but usually 1 second to 30 seconds scope, preferably 1 second to 15 seconds and most preferred be 3 seconds to 10 seconds.
The bottom of cylindrical reactor 18 is led in the hot logistics of waste oil mixture through pipeline 30 after manage 26 thermo-crackings that obtain.Owing to the heat absorption heat scission reaction that recurs in reactor 18 with owing to the fresh waste oil charging spray by pipeline 16 causes cooling, the fluid temperature (F.T.) in the place cylindrical reactor 18 descends from bottom to top.Ethereal oil in the reactor 18 and water component are removed from reactor by pipeline 22, earlier up by heat exchange posts 14, as described come the fresh waste oil charging of preheating with it, be transported in the distillation column 32 to form desired product refiltered oil cut by pipeline 34 then, will narrate as the back simultaneously, water can recycle.
In equipment shown in Figure 1, obtain three kinds of cuts and be sent to groove 36,38 and 40 from distillation column 32.Give off remaining gas and lightweight oil and condensation in liquid collection trough 44 by pipeline 42.The product of wanting most 2
#Diesel oil (usually 110 ℃ of-360 ℃ of condensations) is generally collected in groove 38, and light Fuel (usually 75 ℃ of-150 ℃ of condensations) and water are collected in the groove 40, and heating fuel (in temperature condensation more than 360 ℃) is collected in the groove 36.
Press another scheme of said process, can be when the waste oil mixture does not need further to cool off after warmly separating in cylindrical reactor 18, fresh waste oil charging after heat exchange posts 14 effusive preheatings can be changed the inlet of delivering to tubular type heating installation 20 by cylindrical reactor 18 whole or in part through pipeline 46.Then, before the incoming mixture that obtains is delivered into pipe 26 fresh waste oil charging directly in pump 24 with the thermo-cracking of coming autoreactor 18 after the non-volatile Residual oil of waste oil mixture mix mutually.
By another scheme, before incoming mixture is delivered into heating tube 26, the incoming mixture that to will deliver to heating installation 20 from cylindrical reactor 18 with from the steam of steam heater 48 with 3mol% to 50mol%, preferably 10mol% carries out blending to the 50mol% quantity of steam.Steam heater 48 is coil pipe type or steam boiler, and they can be placed on the top position of tubular type heating installation 20.As preceding, mixed logistics heats in heating tube 26 and enters cylindrical reactor 18.The steam that is added together with light Fuel steam through pipeline 22 by after the heat exchanger 14, through distillation column 32 separated and collected in storage tank 40.But the hot water pump in the groove 40 is passed to steam heater 48 and reuses.
The inventive method run duration is supplied with 276kPa usually to 1034kPa (40psig is to 150psig) pressure in heating tube 26.Control this pressure by the valve (not shown) on the suitable adjusting tubular type heater outlet pipeline 30.
The fresh waste oil quantity that is added from groove 10 should with the product quantity balance that produces by system so that present method can be operated chronically by successive processes.Yet, behind the operation some cycles, can find that generally desired refiltered oil product output can descend with mixture internal contamination thing content increase after the round-robin thermo-cracking.For example output can drop to 75% of the output that requires.When this situation occurring, found and the fluid temperature (F.T.) in the tubular type heating installation 20 can be elevated to 460 ℃ to 520 ℃ scopes, to allow the intravital heavy hydrocarbon of stream produce " degree of depth thermo-cracking ", be that hydrocarbon produces than cracking greatly usually, also have although it is so to emit and produce undesirable polyreaction or the like danger, but it has increased the distillatory volatile constituent amount from reactor 18 that makes significantly, has therefore improved output.In this step, generally keep equally, thereby under above-mentioned high temperature, be about 1 second to 15 seconds at intraductal retention time with ordinary method operating period by managing 26 fluid flow rate.Degree of depth thermo-cracking step required time and thereby the output that obtains improve the character that depends on charging to a great extent, the content of sludge and other pollutent for example.
According to a key character of the present invention, present method is moved behind the certain hour (promptly 1 to 6 months continuously, the character that depends on waste oil), when in cylindrical reactor, containing the heavy still bottoms of the metal of waste oil additive and dirt and sludge and being accumulated to unacceptable degree, must carry out coking and handle.Handle for implementing coking, with Residual oil in pipe 26 or in one group of independent coking pipe (not shown), be heated to the pipe temperature out and reach 470 ℃ to 590 ℃ scopes, logistics after the heating is transmitted back to cylindrical reactor, and the heat that logistics is carried by it under 172kPa (3psig is to 25psig) pressure and 440 ℃ to the 570 ℃ temperature at 21kPa in reactor helps to produce its pressure of heat scission reaction and controlled by control valve 50.Consequent oil vapour steams with usual method and forms desired product, and the sedimentation of coke of containing metal etc. is in cylindrical reactor.After having formed coke, stop work and carry out coke cleaning.Therefore the final resistates of the inventive method is the few relatively coke of quantity, can handle to overcome environmental pollution with common measure and maybe can do industrial fuel use.
Referring to Fig. 2, its more detailed tubular type heating unit 20 of having represented a kind of preferred form.As can be seen, heating tube is straight and do not have coiled pipe.When using steam, for the residence time that increases heavier charging can be equipped serpentine tube in addition.These pipes can vertically, obliquely or flatly be provided with.The charging and the steam (when using steam) of heat enter heating tube 26 by valve 52, leave through valve 54 then and deliver in the cylindrical reactor 18.Plug on every reaction tubes lower end is decoking and uses when cleaning.
Mixture temperature usable temp metrical instrument 57 is measured after leaving the thermo-cracking of tubular type heating installation 20, for example uses the thermopair of remote monitor.
Can isolate every reaction tubes with indicator valve, so the fault of certain root pipe can't influence the total system operation and can continue in service retubing in system.As mentioned above, if requirement is arranged,, various coking pipe group (not shown)s can be installed carry out pyrogenic reaction for avoiding over-drastic deposition in heating tube 26.These pipes should be very similar with pipe 26, but the diameter of 5cm to 12.5cm (2in is to 5in) scope should be arranged, and should and manage 26 parallel arrangements in heating unit 20 simultaneously, only sends into fluid by operating suitable valve (not shown) toward these pipes when needing coking.Yet as has been noted, available reaction tubes 26 itself carries out pyrogenic reaction, thereby owing to adopt high flow rate of liquid [for example, from 0.6m/s to 4.5m/s (2ft/s is to 15ft/s)], straight heating tube and optional injecting steam, sedimentation of coke drops to seldom.
The more detailed preferred embodiment of representing a cylindrical reactor 18 of Fig. 3.Fig. 6 has represented another cylindrical reactor.Managing 16 introducing being fed to cylindrical reactor of preheating in these reactors and managing 25 is to carry the pipeline of mixture to tubular type heating unit 20.In fact, pipeline 25 can be the pipe of different heights in a series of insertion cylindrical reactors.Hot-fluid from heating tube 26 is recycled in the cylindrical reactor 18 through pipeline 30, and pipeline 30 can be with 1 pipe perhaps many pipes, and this depends on the size of tubular type heating installation 20.Oil and steam are sent to heat exchange posts 14 by the pipeline 22 that is arranged in cylindrical reactor 18 tops, and plug 58 is installed for coke cleaning, and pipeline 60 is in order to take a sample.Because economical and better keep common reaction pressure, reactor is made columniform, but as need also can be made into other shape.On request, the top of cylindrical reactor and bottom can be flat or tapers.
Usually between the usage period, owing to enter the high turbulent flow of cause at the reactor inner fluid because of and steam oily from the high speed of tubular type heating unit 20, and cylindrical reactor is lower than 455 ℃ temperature of reaction, thus in cylindrical reactor 18 coke to form be limited.Therefore, present method can reach long-term operation.Carried out needing decoking usually after the coking processing, this used vapour decoking, the water decoking, mechanical decoking or other method realize.
For operate continuously does not make system's shut-down decoking, can install another cylindrical reactor continue the reaction and first reactor carries out decoking and cleaning.These two cylindrical reactors should have same spline structure basically.Fig. 4 has represented that in more detail one is with the preferred embodiment of the equipment of two cylindrical reactor 18a and 18b.When a cylindrical reactor 18a carries out decoking when handling, can by valve 62 and 64 in the future automatic heat-exchanger 14 charging and switch among another cylindrical reactor 18b from the hot effluent of tubular type heating unit 20.The other parts of Fig. 4 equipment are identical with Fig. 1's.
By another kind of scheme, when having used cylindrical reactor 18a one time with method of the present invention, the heavy still bottoms among the cylindrical reactor 18a and sludge be passed to tubular type heating installation 20 with pump and be heated to make the heater outlet temperature reach 470 ℃ to 590 ℃.To switch to from the hot-fluid fluid of tubular type heating installation 20 among another cylindrical reactor 18b and under 172kPa (3psig is to 25psig) pressure and 440 ℃ to 570 ℃ temperature, carry out pyrogenic reaction at 21kPa.When the heavy still bottoms among the cylindrical reactor 18a and sludge are passed to tubular type heating unit 20 with pump, with fresh waste oil with carrying out steps such as common cooling, evaporation, mixing and intensification among the pump input cylindrical reactor 18a.Cylindrical reactor 18b carries out the decoking processing then.After decoking is finished dealing with, will switch among the cylindrical reactor 18b from the hot-fluid fluid of tubular type heating installation 20 and stop to cylindrical reactor 18a for fresh feed.Cylindrical reactor 18b carries out conventional cooling, evaporation, mixing and warming temperature step, and cylindrical reactor 18a prepares to carry out coking next time and decoking is handled.
By another other scheme, can more efficient use equipment and circulation and utilize in the preheating neutralization method each step institute heat content to finish present method.For example, another program operation as in Fig. 5, representing.
Be transported in the heat exchanger 14 with steam feeding preheating to about 115 ℃ of temperature through pump 65 from the waste oil charging of groove 10.Charging after the preheating feeds flash tank 67 through pipeline 66, evaporates water outlet and feed heat exchangers 69 through pipeline 68 to cool off in flash tank from charging.The water of moving evaporation.Be transported to the hot steam logistics that in distillation column 32 be used for from cylindrical reactor 18a and 18b with pump 70 through pipeline 71 from the hot feed of flash tank 67 and carry out preheating once more.Be passed in the tubular heater 20 through pipeline 73 with pump 72 after the vapor mixing from the heavy oil fraction of distillation column 32 bottoms and 3% to 10%, the temperature of tubular heater 20 is raised to 450 ℃ to 530 ℃, and the bottom that feeds one of cylindrical reactor 18a or 18b from the hot-fluid fluid of tubular heater 20 through pipeline 74 is with 375 ℃ to 455 ℃ further reactions.Lead to the bottom of distillation column 32 through pipeline 75 with the charging of preheating from the gas phase fuel of cylindrical reactor 18a or 18b from flash tank 70.Gas phase fuel in the distillation column 32 up moves through post and is separated into 2
#Fuel, it feeds in the heat exchanger 77 behind stripper 76; Light Fuel feeds heat exchanger 79 through pipeline 78 and is used for cooling and recovery, and some are 4 years old
#Fuel feeds heat exchanger 81 through pipeline 80 and is used for cooling and recovery.
The mixture that can be after pipeline 82 down sprays the thermo-cracking of the bottom of cylindrical reactor 18a or 18b containing be used for waste oil after the waste oil of the fresh preheating further handled and the thermo-cracking from a part of charging of flash tank 70 in the waste oil mixture with generation.Waste oil reaches desired 375 ℃ to 455 ℃ effect after from the spray of the waste oil charging of flash tank 70 the cooling heat cracking being arranged.Residual oil in cylindrical reactor 18a or the 18b bottom through circulation line 83 with send into tubular heater 20 after charging in distillation column 32 bottoms mixes.When one of cylindrical reactor 18a or 18b are full of by coke, will switch to another reactor from the hot-fluid fluid of tubular heater 20 to carry out thermo-cracking and pyrogenic reaction.First reactor carries out the decoking processing then.
Decoking can adopt as steam decoking, and methods such as water decoking and mechanical decoking are finished.
Although the present invention has done being described in detail as above, obviously under the spirit and scope of the present invention, can carry out various improvement and conversion.
Claims (15)
1. a processing contains the method for the waste oil of heavy hydrocarbon and pollutent, and it comprises:
The mixture of fresh waste oil and non-the waving property Residual oil of round-robin is warmed up to 1 second to the 15 second time of 400 ℃ to 490 ℃ scopes under about 40 to 150psig pressure, this time is enough to make heavy hydrocarbon contained in the incoming mixture to produce thermo-cracking, but deficiency is so that substantial undesirable polyreaction, oxidizing reaction and dehydrogenation reaction take place in the said mixture;
Waste oil mixture to 300 is ℃ to 455 ℃ of range temperature after the thermo-cracking that obtains of cooling, and keeps this temperature allow volatile constituent evaporation in the waste oil mixture after the thermo-cracking, stays the non-volatile Residual oil that contains described pollutent;
The volatile constituent of condensation evaporation becomes the refiltered oil product;
Non-volatile Residual oil and fresh waste oil mixed forming described incoming mixture, and repeat above-mentioned intensification, cooling, evaporation and mixing step, simultaneously the condensation volatile constituent of after above-mentioned thermo-cracking, evaporating the waste oil mixture continuously by successive processes.
2. according to the method for claim 1, wherein, when the output of above-mentioned refiltered oil product drops under the predetermined level, the said temperature of above-mentioned incoming mixture is raise to impel above-mentioned heavy hydrocarbon drastic cracking, then waste oil mixture after the thermo-cracking that obtains is cooled off, evaporation, mixing and heating step again.
3. according to the method for claim 1, wherein, when pollutent is increased to predeterminated level in the waste oil mixture after above-mentioned thermo-cracking, the non-volatile Residual oil that will contain above-mentioned pollutent is heated to 470 ℃ to 590 ℃ temperature range, drop to 440 ℃ to 570 ℃ temperature ranges then, and under 21kPa to 172kPa pressure, keep said temperature and make above-mentioned Residual oil carry out thermo-cracking and pyrogenic reaction further generates volatile constituent and solid-state coke.Wherein above-mentioned volatile constituent is removed and condensation, and above-mentioned solid-state coke is abandoned after collecting.
4. steam is introduced in the above-mentioned incoming mixture before above-mentioned heating step by the process of claim 1 wherein, and wherein water is separated from above-mentioned volatile constituent.
5. by the process of claim 1 wherein that above-mentioned incoming mixture bears the pressure of 276kPa to 1034kPa scope when in above-mentioned intensification.
6. according to the process of claim 1 wherein that incoming mixture maintains 400 ℃ to 490 ℃ temperature ranges and reaches 1 second to 15 second time.
7. according to the method for claim 6, wherein the time is 3 seconds to 10 seconds.
8. according to the process of claim 1 wherein that waste oil mixture after the thermo-cracking that will obtain is cooled to 300 ℃ to 425 ℃ temperature range.
9. according to the process of claim 1 wherein that waste oil mixture after the thermo-cracking that will obtain is cooled to 300 ℃ to 375 ℃ temperature range.
10. the processing that is used for claim 1 method contains the equipment of heavy hydrocarbon and pollutent waste oil, and it comprises:
Heating unit, be used for fresh waste oil and non-the waving property resid feed of round-robin mixture are warmed up to 400 ℃ to 490 ℃ temperature range certain hours, this time is enough to make contained heavy hydrocarbon generation thermo-cracking in the incoming mixture, but not enough so that produce substantial undesirable polyreaction, oxidizing reaction and dehydrogenation reaction in the above-mentioned incoming mixture;
Container is used to receive waste oil mixture after the hot tearing that obtains, and be used for keeping and keep hot tearing after the waste oil mixture in 300 ℃ to 455 ℃ temperature ranges, allow volatile constituent evaporation in the waste oil mixture after the thermo-cracking, stay the non-volatile Residual oil that contains pollutent;
Condenser, the volatile constituent that is used for condensation evaporation forms the refiltered oil product;
Pumping unit and pipeline, be used for to mix with fresh waste oil from the non-volatile Residual oil of said vesse and form above-mentioned incoming mixture and the above-mentioned incoming mixture that is used for circulating continuously is used for above-mentioned volatile constituent is transported to above-mentioned condenser from said vesse to above-mentioned container neutralization by above-mentioned heating unit.
11. press the equipment of the processing waste oil of claim 10, wherein above-mentioned heating unit contains a kind of heating tube at least.
12. according to the equipment of the processing waste oil of claim 11, wherein above-mentioned at least one heating tube is straight tube.
13. according to the equipment of the processing waste oil of claim 11, wherein above-mentioned at least a heating tube is vertical to be selected from, inclination and horizontal direction are installed on the above-mentioned heating unit.
14. according to the equipment of the processing waste oil of claim 10, two kinds of above-mentioned containers are arranged and comprise pipe and valve, allow said vesse to be used alternatingly.
15. according to the equipment of the processing waste oil of claim 14, two kinds of wherein above-mentioned containers are identical basically.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US59247896A | 1996-01-26 | 1996-01-26 | |
| US08/592,478 | 1996-01-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1214720A CN1214720A (en) | 1999-04-21 |
| CN1074454C true CN1074454C (en) | 2001-11-07 |
Family
ID=24370811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97193273A Expired - Lifetime CN1074454C (en) | 1996-01-26 | 1997-01-24 | Process and apparatus for treatment of waste oils |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0879273B1 (en) |
| JP (1) | JP2000503336A (en) |
| KR (1) | KR19990082068A (en) |
| CN (1) | CN1074454C (en) |
| AT (1) | ATE236239T1 (en) |
| AU (1) | AU719165B2 (en) |
| BR (1) | BR9707470A (en) |
| CA (1) | CA2242742C (en) |
| DE (1) | DE69720427D1 (en) |
| EA (1) | EA000667B1 (en) |
| HK (1) | HK1019616A1 (en) |
| IL (1) | IL125496A (en) |
| NO (1) | NO983434L (en) |
| WO (1) | WO1997027273A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102517066A (en) * | 2011-12-10 | 2012-06-27 | 吴国存 | Unbalanced oily waste material high-temperature buffer pyrolysis distillation unit and technology |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5885444A (en) * | 1992-11-17 | 1999-03-23 | Green Oasis Environmental, Inc. | Process for converting waste motor oil to diesel fuel |
| ES2131022B1 (en) * | 1997-10-21 | 2000-03-01 | Landa Axpe Francisco J | PROCEDURE FOR THE CONTINUOUS PRODUCTION OF THE CRAKE OF USED LUBRICATING OIL. |
| US7976699B2 (en) | 2006-06-16 | 2011-07-12 | Kesler Michael L | Distillation apparatus and method of use |
| JP2008169343A (en) * | 2007-01-15 | 2008-07-24 | Orient Sokki Computer Kk | Oil regeneration method, oil regeneration apparatus, desulfurization method, and desulfurization apparatus |
| CN101974363B (en) * | 2010-09-29 | 2013-04-03 | 潘校良 | Method for recovering and treating waste industrial oil and equipment for implementing method |
| RU2448145C1 (en) * | 2010-12-02 | 2012-04-20 | Общество С Ограниченной Ответственностью "Проминтех" | Method for slow coking |
| CN102140359A (en) * | 2011-02-22 | 2011-08-03 | 唐山南光实业有限公司 | Cracking evaporation type oil sand and oil sludge treatment device |
| CN102140360A (en) * | 2011-02-22 | 2011-08-03 | 唐山南光实业有限公司 | High-temperature steam jetting type oil sand and oil sludge treatment device |
| CN102140358A (en) * | 2011-02-22 | 2011-08-03 | 唐山南光实业有限公司 | Progressive cracking evaporative type oil sand and oil sludge treatment device |
| CN103013554B (en) * | 2012-12-18 | 2015-05-13 | 青岛福瑞斯生物能源科技开发有限公司 | Device and method for producing biodiesel with illegal cooking oil and waste engine oil |
| WO2014135966A1 (en) * | 2013-03-07 | 2014-09-12 | Verolube, Inc. | Method and apparatus for recovering synthetic oils from composite oil streams |
| CN104629796A (en) * | 2013-11-14 | 2015-05-20 | 东营争峰新能源技术有限公司 | Device for producing diesel oil by using waste diesel oil |
| RU2562999C1 (en) * | 2014-06-25 | 2015-09-10 | Общество с ограниченной ответственностью "Информ-технология" (ООО "Информ-технология") | Method of decelerated coking of oil residues |
| KR101783764B1 (en) | 2015-09-23 | 2017-11-06 | 충북대학교 산학협력단 | Waste oil recycling system comprising oil vapor treatment equipment |
| CN106984439B (en) * | 2017-04-18 | 2019-04-05 | 长春工程学院 | A kind of drain oil recovery equipment |
| CN113801681A (en) * | 2021-10-14 | 2021-12-17 | 广州新奥达云科技有限公司 | Waste engine oil pyrolysis device under low temperature state |
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| JPS5682886A (en) * | 1979-12-12 | 1981-07-06 | Mitsubishi Heavy Ind Ltd | Method for converting heavy oil into light oil |
| DE3224114A1 (en) * | 1982-06-29 | 1983-12-29 | Rivi Establishment, 9490 Vaduz | Process for heating liquids having constituents with a tendency to form deposits |
| EP0308669A1 (en) * | 1987-08-29 | 1989-03-29 | Asea Brown Boveri Aktiengesellschaft | Process for utilising a halogenated hydrocarbon-containing starting material |
| US5143597A (en) * | 1991-01-10 | 1992-09-01 | Mobil Oil Corporation | Process of used lubricant oil recycling |
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| DE3839799A1 (en) * | 1988-11-25 | 1990-07-05 | Rwe Entsorgung Ag | METHOD FOR PROCESSING CONTAMINATED OILS |
| US5362381A (en) * | 1993-03-25 | 1994-11-08 | Stanton D. Brown | Method and apparatus for conversion of waste oils |
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1997
- 1997-01-24 KR KR1019980705790A patent/KR19990082068A/en not_active Application Discontinuation
- 1997-01-24 BR BR9707470-5A patent/BR9707470A/en not_active Application Discontinuation
- 1997-01-24 WO PCT/CA1997/000053 patent/WO1997027273A1/en not_active Application Discontinuation
- 1997-01-24 AU AU14337/97A patent/AU719165B2/en not_active Ceased
- 1997-01-24 EA EA199800657A patent/EA000667B1/en not_active IP Right Cessation
- 1997-01-24 CA CA002242742A patent/CA2242742C/en not_active Expired - Lifetime
- 1997-01-24 DE DE69720427T patent/DE69720427D1/en not_active Expired - Lifetime
- 1997-01-24 AT AT97900905T patent/ATE236239T1/en not_active IP Right Cessation
- 1997-01-24 IL IL12549697A patent/IL125496A/en active IP Right Grant
- 1997-01-24 CN CN97193273A patent/CN1074454C/en not_active Expired - Lifetime
- 1997-01-24 EP EP97900905A patent/EP0879273B1/en not_active Expired - Lifetime
- 1997-01-24 JP JP9526380A patent/JP2000503336A/en active Pending
-
1998
- 1998-07-24 NO NO983434A patent/NO983434L/en not_active Application Discontinuation
-
1999
- 1999-10-20 HK HK99104654A patent/HK1019616A1/en not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5682886A (en) * | 1979-12-12 | 1981-07-06 | Mitsubishi Heavy Ind Ltd | Method for converting heavy oil into light oil |
| DE3224114A1 (en) * | 1982-06-29 | 1983-12-29 | Rivi Establishment, 9490 Vaduz | Process for heating liquids having constituents with a tendency to form deposits |
| EP0308669A1 (en) * | 1987-08-29 | 1989-03-29 | Asea Brown Boveri Aktiengesellschaft | Process for utilising a halogenated hydrocarbon-containing starting material |
| US5143597A (en) * | 1991-01-10 | 1992-09-01 | Mobil Oil Corporation | Process of used lubricant oil recycling |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102517066A (en) * | 2011-12-10 | 2012-06-27 | 吴国存 | Unbalanced oily waste material high-temperature buffer pyrolysis distillation unit and technology |
Also Published As
| Publication number | Publication date |
|---|---|
| NO983434D0 (en) | 1998-07-24 |
| IL125496A (en) | 2001-05-20 |
| CN1214720A (en) | 1999-04-21 |
| ATE236239T1 (en) | 2003-04-15 |
| CA2242742C (en) | 2005-06-14 |
| HK1019616A1 (en) | 2000-02-18 |
| EP0879273B1 (en) | 2003-04-02 |
| NO983434L (en) | 1998-09-21 |
| KR19990082068A (en) | 1999-11-15 |
| WO1997027273A1 (en) | 1997-07-31 |
| IL125496A0 (en) | 1999-03-12 |
| EA000667B1 (en) | 2000-02-28 |
| AU1433797A (en) | 1997-08-20 |
| DE69720427D1 (en) | 2003-05-08 |
| EP0879273A1 (en) | 1998-11-25 |
| JP2000503336A (en) | 2000-03-21 |
| CA2242742A1 (en) | 1997-07-31 |
| AU719165B2 (en) | 2000-05-04 |
| EA199800657A1 (en) | 1999-02-25 |
| BR9707470A (en) | 2000-01-04 |
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