JP4808944B2 - Gas oil desulfurization method and desulfurization equipment - Google Patents

Description

The present invention relates to a gas oil desulfurization method and a desulfurization apparatus for removing sulfur contained in gas oil .

As a method for desulfurizing petroleum, a hydrodesulfurization method has been developed (see Patent Document 1). The desulfurization method described in this publication includes an atmospheric distillation step of crude oil and a distillate composed of light oil and a lower boiling fraction than light oil in a reactor at 310 to 370 ° C. in the presence of a hydrogenation catalyst. , 30 to 70 kg / cm ² G, a first hydrotreating step for hydrodesulfurization, and then a second hydrotreating step for hydrodesulfurization at a lower temperature than the above.
Japanese Patent Laid-Open No. 11-80754

As described in this publication, the hydrodesulfurization method is a method of removing sulfur using hydrogen, and this method is performed in the presence of a hydrogenation catalyst such as a Co-Mo catalyst catalyst. Since sulfur is removed by hydrogenation at 370 ° C. and 30 to 70 kg / cm ² G at high temperature and high pressure, there is a drawback that it cannot be desulfurized easily and at low cost.

  The present invention was developed for the purpose of solving the drawbacks of the conventional desulfurization method. An important object of the present invention is to provide a gas oil desulfurization method and a desulfurization apparatus that can efficiently desulfurize petroleum without increasing the temperature and pressure.

The gas oil desulfurization method of the present invention separates petroleum containing less sulfur from petroleum containing sulfur. The gas oil desulfurization method is a method in which petroleum containing sulfur is ultrasonically vibrated and released in the form of atomized fine particles suspended in a carrier gas, atomized, and a mixed fluid of atomized atomized fine particles and carrier gas , An atomization process for separating the residual oil that is not atomized, and a recovery process for separating and recovering the oil from the mixed fluid obtained in the atomization process. In this desulfurization method, petroleum is separated into residual oil and a mixed fluid in an atomization process, and the petroleum is recovered from the mixed fluid in a recovery process to produce desulfurized petroleum.

In the gas oil desulfurization method of the present invention, sulfur is removed from the gas oil by using the gas oil as refined petroleum . Furthermore, in the method for desulfurizing light oil of the present invention, petroleum is heated and atomized in an atomization step. Furthermore, in the method for desulfurizing light oil of the present invention, the carrier gas can be air.

The gas oil desulfurization apparatus of the present invention separates petroleum containing less sulfur from petroleum containing sulfur. The gas oil desulfurization device is a fuel that contains ultrasonically vibrated sulfur and releases it in the form of atomized fine particles floating in the carrier gas, atomizing it, and a mixed fluid of the atomized atomized fine particles and the carrier gas. The oil is separated and recovered from the mixed fluid obtained by the atomization device 100, the atomizer 100 that separates the residual oil that is not atomized, the heater 76 that heats the oil in the atomization chamber 4, and the atomization device 100. And a recovery device 200. The oil to be desulfurized is light oil, and light oil with less sulfur is separated from light oil. In this desulfurization apparatus, petroleum that is light oil is separated into residual oil and mixed fluid by the atomization apparatus 100, and the mixed fluid is recovered by the recovery apparatus 200 to produce desulfurized light oil .

The desulfurization apparatus for light oil of the present invention includes an atomization chamber 4 in which an atomizer 100 supplies petroleum, and an atomizer 1 that atomizes the oil in the atomization chamber 4 into atomized fine particles by ultrasonic vibration. Can be provided. In the gas oil desulfurization apparatus of the present invention, the atomization apparatus 100 includes the ultrasonic vibrator 2, and the ultrasonic vibrator 2 ultrasonically vibrates the oil into atomized fine particles. Furthermore, in the light oil desulfurization apparatus of the present invention, the recovery apparatus 200 can recover the petroleum by cooling the fluid mixture of the atomized fine particles and the carrier gas.

The present invention ultrasonically vibrates petroleum, which is light oil, atomized with ultrasonic vibration energy and released as atomized fine particles floating in a carrier gas, a mixed fluid of atomized fine particles and air, and a residual that is not atomized Separated into oil. Oil is separated from the mixed fluid and recovered. That is, the present invention uses untreated petroleum that is not treated as a mixed fluid as atomized fine particles floating in a carrier gas, and separated oil separated from the mixed fluid and residual oil that remains without becoming atomized fine particles. To separate. Comparing the separated oil with the remaining oil, the separated oil has a lower sulfur content than the remaining oil and is desulfurized.

The present invention, as described above, atomizes petroleum oil, which is light oil, as atomized fine particles in a carrier gas by ultrasonic vibration, and recovers and desulfurizes it. Thus, as in the conventional hydrodesulfurization method, high temperature and high pressure There is a feature that light oil can be efficiently desulfurized with simple equipment.

  Embodiments of the present invention will be described below with reference to the drawings. However, the examples shown below illustrate a gas oil desulfurization method and a desulfurization apparatus for embodying the technical idea of the present invention, and the present invention does not specify the desulfurization method and the desulfurization apparatus below.

  Further, in this specification, in order to facilitate understanding of the scope of claims, numbers corresponding to the members shown in the examples are indicated in the “claims” and “means for solving problems” sections. It is added to the members. However, the members shown in the claims are not limited to the members in the embodiments.

In the desulfurization method of the present invention, petroleum, which is light oil , is atomized into atomized fine particles, and then the atomized fine particles are recovered and desulfurized.

  When petroleum is atomized to form atomized fine particles, the sulfur content contained in the atomized fine particles and the residual oil is different. This is because the sulfur component contained in petroleum becomes atomized fine particles and is not easily transferred to the recovery device as a mixed fluid, and tends to remain in the residual oil. Therefore, when the atomized atomized fine particles are collected, the oil has a low sulfur content, and the petroleum can be desulfurized. Petroleum obtained by recovering from the mixed fluid has a low sulfur content. In addition, the petroleum recovered from the mixed fluid has a large amount of petroleum having a small carbon number (n), and the residual oil has a large amount of petroleum having a large carbon number (n).

  When the crude oil is separated into petroleum having different components, it can be separated into petroleum having a different carbon number (n) in the step of agglomerating and collecting the atomized atomized fine particles. This is because the degree of aggregation and liquefaction varies depending on the number of carbons (n) of petroleum. Petroleum having a large carbon number (n) is easily collected because it is easily liquefied, and oil having a small carbon number (n) is collected later because it is difficult to be liquefied. In the case of desulfurizing petroleum separated into light oil, kerosene, gasoline, heavy oil, etc., the petroleum is separated into residual oil and atomized fine particles, and the atomized fine particles are recovered to obtain desulfurized oil. When the crude oil is separated into residual oil, light oil, kerosene, naphtha, LP gas, light gas, and the like, it is separated into petroleum having a different carbon number (n) in the recovery step.

  The present invention does not extract only sulfur components from petroleum and desulfurize them. The petroleum as a raw material is desulfurized by separating it into separated petroleum with a low sulfur content and residual petroleum with a high sulfur content. Therefore, one separated oil has a low sulfur content and is desulfurized, but the residual oil has a high sulfur content. Petroleum with increased sulfur content can be desulfurized by desulfurization methods that are currently being developed or will be developed. In this case, since the oil having a low sulfur content is separated from the original oil and the amount of residual oil is reduced, the cost of desulfurization from the residual oil can be reduced. In applications where petroleum having a high sulfur content can be used, petroleum having a high sulfur content can be used without desulfurization.

  The present invention separates desulfurized petroleum by atomizing petroleum into atomized fine particles by ultrasonic vibration. The following shows that petroleum can be atomized into atomized fine particles by ultrasonic vibration to produce desulfurized petroleum with a low sulfur content.

Tables 1 to 3 show the components before and after purification of gasoline refined by the desulfurization method of the present invention. However, in this test, commercially available gasoline is put in a container, ultrasonic waves of 2.4 MHz and 16 W are irradiated from below the liquid level, the oil temperature is started from 28 ° C. and atomized into atomized fine particles, and ultrasonic fog This is a measurement of petroleum components before and after conversion. Although the present invention uses light oil as the petroleum to be desulfurized, the method and apparatus capable of desulfurizing from gasoline can also desulfurize gas oil, so the desulfurization of gasoline will be described in detail below.

  In the desulfurization method, air is introduced at 20 liters / minute as a carrier gas into the atomization surface of the atomization chamber, and the temperature of the introduced air is set to 23 ° C. Atomization time is 15 minutes. For the sulfur content, a trace current titration method defined in JIS K2541-2 is used. For PONA and hydrocarbon components in gasoline, all components are tested by the gas chromatography method specified in JIS K 2536-2, and are integrated and shown for each carbon chain length.

  In Tables 1 to 3, “data before the atomization process” and “data after the atomization process” indicate the measurement results of gasoline before and after the ultrasonic atomization process. The “data in the atomization zone gas phase concentration” is calculated based on the mass balance from the gasoline weight before and after the ultrasonic atomization and its composition. At this time, it seems that cracking due to cavitation hardly occurs in view of the generation conditions of the ultrasonic wave, so that the molecular weight of the petroleum component has not been reduced.

  As can be seen from these tables, when comparing the sulfur concentration of “before atomization treatment” and “concentration in atomized gas phase”, the sulfur content of “before atomization treatment” is 73.0 ppm. It can be seen that the sulfur content of the “atomized gas phase concentration” is 19.7 ppm, which is reduced to 1/3 or less. This indicates that the sulfur concentration in gasoline can be reduced to 10 ppm or less by two-stage atomization treatment.

  Furthermore, FIG. 23 looked at a change ratio of each component concentration of each carbon chain length of “atomization portion gas phase concentration” with respect to each component concentration of each carbon chain length “before atomization treatment”, that is, a separation ratio. Is. Separation degree 1 is equal to the ratio of the original petroleum component remaining in the solution and the distribution ratio in the gas phase, and when the separation degree exceeds 1, the component is easily transferred to the mixed fluid as atomized fine particles and is 1 or less. It is easy to stay on the remaining oil side. As is clear from this figure, the shorter the carbon chain length with a smaller number of carbons (n), the easier it is to transfer to the mixed fluid as atomized fine particles.

  In addition, comparing the composition of the components in the gas phase of the atomization part and before the atomization process, the ratio of paraffins and olefins in the gas phase increased, and naphthenes and aromas in the residual oil. The concentration of is increasing. As described above, the desulfurization method of the present invention can greatly change the petroleum composition. Further, when the energy consumption was measured, in the case of the gasoline separation test, the total value of the ultrasonic vibration energy (16 J / s) and the gas phase enthalpy reduction (3.4 J / s) was the gasoline vaporization energy (52 J / s). ), It is possible to ultrasonically atomize and separate gasoline by energy saving.

Hereinafter, the light oil desulfurization apparatus of the present invention will be described in detail.
The desulfurization apparatus shown in FIGS. 1 to 4 includes an atomization apparatus 100 and a recovery apparatus 200. The atomization apparatus 100 includes an atomization chamber 4 having a closed structure to which oil is supplied, and an atomizer 1 that atomizes the oil in the atomization chamber 4 into atomized fine particles. The recovery device 200 separates air from the mixed fluid of atomized fine particles atomized in the atomization chamber 1 and air, and the mixed fluid from which a part of the air is separated by the air separator 50. A recovery chamber 5 for separating and recovering oil and a forced transfer machine 35 for transferring the mixed fluid are provided.

  Oil is supplied to the atomization chamber 4 by a pump 10. The atomization chamber 4 does not atomize all supplied petroleum as atomized fine particles. This is because when all the oil is atomized and collected in the collection chamber 5, the oil supplied to the atomization chamber 4 and the oil-containing components collected in the collection chamber 5 become the same. However, in the process of atomizing petroleum into a mixed fluid, and separating the oil from this mixed fluid, the method and equipment for desulfurizing while separating into petroleum with different components, atomizes all the petroleum into atomized fine particles. Separation into petroleum containing different components. In this case, since the sulfur is difficult to be contained in the mixed fluid as atomized fine particles by ultrasonic vibration, the petroleum separated as petroleum having a large carbon number (n) has a large sulfur content and a small carbon number (n). Oil separated as petroleum has a low sulfur content.

  Part of the oil supplied to the atomization chamber 4 is atomized into atomized fine particles. Therefore, the amount is reduced. Decreased oil has a lower oil content that tends to atomize. For this reason, when oil is continuously atomized into atomized fine particles without supplying oil to the atomization chamber 4, the concentration of petroleum that is easily atomized decreases in the atomized fine particles. This is because the oil that is easily atomized is first removed in the form of atomized fine particles, so that the concentration of the oil that is easily atomized decreases in the residual oil. Replacing the oil in the atomization chamber 4 with a new one can prevent a decrease in the concentration of the easily atomized oil contained in the residual oil.

  The atomizing chamber 4 is a method of replacing the oil with a new one after a certain period of time, that is, exchanging the oil in a batch manner. However, the stock solution tank 11 storing the oil can be connected to the atomization chamber 4 via the pump 10, and the oil can be continuously supplied from the stock solution tank 11. This apparatus can supply the oil from the raw liquid tank 11 while discharging the residual oil in the atomization chamber 4, and can prevent the concentration of the oil that is easily atomized contained in the oil in the atomization chamber 4 from decreasing. Moreover, as shown by the arrow B in FIG. 4, the residual oil in the atomization chamber 4 is discharged to the outside without being circulated to the stock solution tank 11, and the concentration of the oil that is easily atomized contained in the stock solution tank 11 decreases. Can also be prevented.

  The oil in the atomization chamber 4 is atomized into atomized fine particles by the atomizer 1. The atomized fine particles have a lower sulfur content than the residual oil. Therefore, the atomized machine 1 can atomize petroleum into atomized fine particles, collect the atomized fine particles, and produce desulfurized petroleum.

  The atomizer 1 includes a plurality of ultrasonic transducers 2 and an ultrasonic power source 3 that supplies high-frequency power to the ultrasonic transducers 2. The atomizer 1 is preferably ultrasonically vibrated at a frequency of 1 MHz or more to atomize petroleum. When this atomizer 1 is used, petroleum can be atomized into very fine atomized fine particles. The present invention does not specify the frequency of ultrasonic vibration. The vibration frequency of the ultrasonic vibration can be made lower than 1 MHz.

  The atomizer 1 that ultrasonically vibrates petroleum scatters oil from the oil surface W as atomized fine particles having a sulfur content lower than the residual oil remaining in the atomization chamber 4, that is, desulfurized oil. When petroleum is ultrasonically vibrated, a liquid column P is formed on the oil surface W, and mist-like fine particles are generated from the surface of the liquid column P. In the atomizer 1 shown in FIG. 5, the ultrasonic vibrator 2 of the atomizer 1 is disposed upward at the bottom of the atomization chamber 4 filled with petroleum. The ultrasonic vibrator 2 emits ultrasonic waves upward from the bottom toward the oil surface W, and the oil surface W is ultrasonically vibrated to generate the liquid column P. The ultrasonic transducer 2 emits ultrasonic waves in the vertical direction.

  The atomizer 1 shown in the figure includes a plurality of ultrasonic transducers 2 and an ultrasonic power source 3 that ultrasonically vibrates these ultrasonic transducers 2. The ultrasonic transducer 2 is fixed to the bottom of the atomization chamber 4 in a watertight structure. The apparatus in which the plurality of ultrasonic vibrators 2 vibrate oil ultrasonically atomizes the oil into atomized particles more efficiently.

  As shown in FIGS. 6 and 7, the plurality of ultrasonic transducers 2 are fixed to the attachment / detachment plate 12 with a waterproof structure. As shown in FIGS. 8 and 9, the detachment plate 12 fixing the plurality of ultrasonic transducers 2 is attached to the casing 13 of the atomization chamber 4 so as to be detachable with a waterproof structure. The desorption plate 12 is attached to the casing 13 of the atomization chamber 4, and each ultrasonic vibrator 2 ultrasonically vibrates the oil in the atomization chamber 4.

  6 and FIG. 7 includes a front plate 12A and a back plate 12B, and the ultrasonic wave vibrator is disposed between the front plate 12A and the back plate 12B by laminating the front plate 12A and the back plate 12B. 2 is sandwiched with a waterproof structure. The surface plate 12A has a through hole 12a. The vibration surface 2A is positioned in the through hole 12a, and the ultrasonic vibrator 2 is sandwiched and fixed between the surface plate 12A and the back plate 12B. The back plate 12B is provided with a concave portion 12b into which the ultrasonic transducer 2 is fitted, and the ultrasonic transducer 2 is fitted into the concave portion 12b. 6 is provided with a recess 12b in the back plate 12B, it is also possible to provide a recess in the front plate and insert an ultrasonic transducer into the recess.

  In order to provide a waterproof structure between the ultrasonic transducer 2 and the surface plate 12A, a packing 16 is sandwiched between the surface plate 12A and the ultrasonic transducer 2. The atomizer 1 shown in FIG. 6 has a waterproof structure in which a packing 16 is sandwiched between the ultrasonic transducer 2 and the back plate 12B. However, the atomizer need not necessarily have a waterproof structure between the ultrasonic transducer and the back plate. This is because a desorption plate having a waterproof structure between the ultrasonic transducer and the surface plate can be fixed to the lower surface of the casing of the atomization chamber to prevent oil in the atomization chamber from leaking. The packing 16 is a rubber-like elastic O-ring. The O-ring packing 16 is disposed on a surface facing the outer peripheral edge of the vibration surface 2A of the ultrasonic transducer 2 and the surface plate 12A, and between the vibration surface 2A of the ultrasonic transducer 2 and the surface plate 12A. As a waterproof structure, it prevents water from leaking through this space. Furthermore, the outer periphery of the ultrasonic transducer 2 and the back plate 12B are connected with a waterproof structure.

  The packing 16 is a rubber-like elastic body such as Teflon (registered trademark), silicon, natural or synthetic rubber. The packing 16 is sandwiched between the ultrasonic transducer 2 and the front plate 12A, and between the ultrasonic transducer 2 and the back plate 12B in a state of being elastically deformed and crushed. And the surface plate 12A and the back plate 12B are in close contact with the surface of the back plate 12B without a gap, and the connecting portion is made waterproof. However, the packing 16 can also be a metal packing obtained by processing a metal such as copper, shinchu, aluminum, and stainless steel into a ring shape.

  6 and 7 has a hinge 17 connecting one side edges of the front plate 12A and the back plate 12B. The desorption plate 12 can easily desorb the ultrasonic transducer 2 by opening the back plate 12B and the front plate 12A. When the ultrasonic vibrator 2 is replaced, the back plate 12B and the front plate 12A are opened. In this state, the old ultrasonic transducer is taken out and the new ultrasonic transducer 2 and the packing 16 are put in a predetermined position. Thereafter, the back plate 12B and the front plate 12A are closed, and the ultrasonic transducer 2 is replaced. The closed back plate 12B and the front plate 12A are connected to the opposite side of the hinge 17 with a set screw (not shown) or fixed to the casing 13 of the atomizing chamber 4.

  The atomizer 1 described above has a waterproof structure using the packing 16, but can also have a waterproof structure by filling the position of the packing with a caulking material. Further, in the atomizer 1 shown in FIG. 6, the desorption plate 12 is constituted by two metal plates composed of a front plate 12A and a back plate 12B, or a non-metallic hard plate. Or it can also be set as one plate as shown in FIG. The detaching plate 12 is a metal plate or a non-metal hard plate, and is provided with a concave portion 12b in which the ultrasonic vibrator 2 is disposed upward or through a through hole 12a.

  In the atomizer 1 of FIG. 10, the ultrasonic vibrator 2 is placed in the concave portion 12 b of the desorption plate 12, and the packings 16 are arranged above and below the outer peripheral portion of the ultrasonic vibrator 2. Further, the ring plate 18 is fixed to the opening of the detachable plate 12. The ring plate 18 presses the packing 16 disposed on the upper surface of the ultrasonic transducer 2, and fixes the ultrasonic transducer 2 to the recess 12b with a waterproof structure. The recess 12b is provided with a through hole 12c at the bottom, and the lead wire 19 is drawn out to the outside.

  In the atomizer 1 of FIG. 11, the ultrasonic vibrator 2 placed in the recess 12b of the detachment plate 12 is bonded with a caulking material 20 and fixed with a waterproof structure without using a packing and a ring plate. The ultrasonic transducer 2 also draws the lead wire 19 to the outside from the through hole 12c opened at the bottom of the recess 12b. The caulking material 20 is also filled between the through hole 12c and the lead wire 19 to provide a waterproof structure that does not leak water.

  The atomizer 1 in FIG. 12 has a through-hole 12 a opened in the desorption plate 12, the vibration surface 2 A is positioned in the through-hole 12 a, and the ultrasonic vibrator 2 is fixed to the lower surface of the desorption plate 12. Yes. In order to fix the ultrasonic transducer 2 to the detachable plate 12, a fixture 21 is fixed to the bottom surface of the detachable plate 12. The ultrasonic transducer 2 is fixed to the attachment / detachment plate 12 with a waterproof structure via packings 16 disposed above and below the outer peripheral portion. The fixing tool 21 has a ring shape having a stepped recess, and a fixing screw 22 penetrating the outer peripheral edge is screwed into the detaching plate 12 and fixed to the detaching plate 12. The fixing tool 21 presses the packing 16 disposed on the lower surface of the ultrasonic transducer 2 at the bottom surface of the stepped concave portion, and fixes the ultrasonic transducer 2 to the attachment / detachment plate 12 with a waterproof structure. The fixture 21 is provided with a through hole 21A on the bottom surface of the stepped recess, and the lead wire 19 is drawn out from the through hole 21A.

  8 and 9 show an atomization chamber 4 in which the atomizer 1 is fixed. In the atomization chamber 4 shown in these drawings, an opening 13A is provided on the bottom surface of the casing 13, and the attachment / detachment plate 12 is fixed so as to close the opening 13A with a waterproof structure. The detaching plate 12 is fixed to the casing 13 with a waterproof structure via a packing 23. In order to fix the detachable plate 12, a fixing bracket 24 is fixed to the bottom surface of the casing 13. The fixing bracket 24 is L-shaped, and is fixed to the casing 13 of the atomization chamber 4 by pressing the detaching plate 12 with a set screw 25 penetrating the fixing bracket 24. The plurality of ultrasonic vibrators 2 fixed to the atomization chamber 4 with this structure ultrasonically vibrates petroleum from the bottom surface of the casing 13 toward the top surface. The desorption plate 12 is mounted on the bottom surface of the casing 13 of the atomization chamber 4 so as to close the opening 13A and be removable.

  As shown in FIG. 13, the desorption plate 12 can be immersed in the petroleum in the atomizing chamber 4 to ultrasonically vibrate the petroleum. This structure can be arranged so that the desorption plate 12 can be easily desorbed from the atomizing chamber 4. The atomizer 1 immersed in oil has a structure shown in FIG. 11, for example, and a portion excluding the vibration surface 2 </ b> A of the ultrasonic vibrator 2 is fixed to the attachment / detachment plate 12 as a waterproof structure.

  When the oil in the atomizing chamber 4 is heated to a high temperature by the ultrasonic vibrator 2 or the ultrasonic power source 3, the quality may be deteriorated. This problem can be solved by forcibly cooling the ultrasonic transducer 2. Furthermore, the ultrasonic power source 3 is preferably cooled. The ultrasonic power source 3 does not directly heat petroleum, but heats the surroundings to indirectly heat petroleum. The ultrasonic vibrator 2 and the ultrasonic power source 3 can be arranged and cooled in a state in which the cooling pipe is thermally coupled thereto, that is, in a state in which the cooling pipe is brought into contact therewith. The cooling pipe cools the ultrasonic vibrator and the ultrasonic power source by flowing liquid or refrigerant cooled by a cooler, or cooling water such as ground water or tap water.

  Furthermore, the desulfurization apparatus shown in FIG. 4 includes a temperature control mechanism 75 that controls the petroleum temperature of the atomization chamber 4. The temperature control mechanism 75 heats the petroleum so that the temperature becomes a predetermined temperature. The temperature control mechanism 75 detects the temperature of the petroleum stored in the atomization chamber 4 with the temperature sensor 77 and controls the warmer 76 to keep the temperature of the petroleum at a set temperature of 40 ° C. As described above, the desulfurization apparatus that controls the temperature of petroleum by the temperature control mechanism 75 can efficiently atomize petroleum into atomized fine particles.

  The temperature of the oil affects the efficiency of atomizing the oil into atomized fine particles by ultrasonic vibration. When the temperature of petroleum becomes low, the efficiency of atomizing into atomized fine particles decreases. When the oil temperature is low, the efficiency of atomizing into atomized fine particles decreases. Therefore, the temperature of the oil is set to a temperature at which atomization into atomized fine particles can be efficiently performed in consideration of separation efficiency. High viscosity petroleum such as crude oil can be efficiently atomized into atomized fine particles by increasing the temperature and decreasing the viscosity.

  Furthermore, in the desulfurization apparatus shown in FIG. 4, in the atomization chamber 4, air is blown from the blower mechanism 27 to the liquid column P that is ultrasonically vibrated to form the oil surface W. The illustrated blower mechanism 27 includes a fan 29 that blows air to the liquid column P. As described above, the desulfurization device that blows air to the liquid column P by the blower mechanism 27 has an advantage that it can be efficiently atomized from the surface of the liquid column P into atomized fine particles. However, as shown in FIGS. 1 to 3, the desulfurization apparatus of the present invention does not necessarily need to be provided with a blower mechanism to blow wind onto the liquid column.

  The air separator 50 separates air from the mixed fluid supplied from the atomization chamber 4. The air separator 50 is partitioned by an air permeable membrane 51 into a primary side passage 52 and a secondary side exhaust passage 53. The primary side passage 52 is connected to the atomizer 1 and allows the mixed fluid to pass therethrough. The secondary side exhaust passage 53 exhausts air separated from the mixed fluid through the air permeable membrane 51.

  The air permeable membrane 51 allows only air to pass and does not allow atomized oil to pass. Therefore, this air permeable membrane 51 uses a molecular sieve which is a pore-size membrane that does not allow petroleum to pass but allows air to pass. Air consists of about 80% nitrogen and 20% oxygen. Therefore, the air permeable membrane 51 is a pore-sized membrane that allows nitrogen and oxygen to pass through. The pore size of the air permeable membrane 51 is preferably 0.4 nm to 0.5 nm. The air permeable membrane 51 does not pass petroleum larger than the pore size, but allows air composed of nitrogen and oxygen smaller than the pore size to pass through. The pore-sized air-permeable membrane 51 is manufactured, for example, by coating a ceramic surface with zeolite.

  The air separator 50 connects the primary side passage 52 to the atomization chamber 4 and brings the mixed fluid into contact with the primary side surface of the air permeable membrane 51. 1, 3, and 4, the secondary exhaust passage 53 is connected to the forced exhaust device 54, and the device of FIG. 2 is connected to the primary passage 52 and a compressor 55 to connect the primary side The pressure of the surface is made higher than that of the secondary surface on the opposite side, and the air of the mixed fluid is permeated through the air permeable membrane 51 to separate part or all of the air of the mixed fluid.

  The forced exhauster 54 is a suction pump such as a vacuum pump that forcibly sucks and discharges air. The forced exhauster 54 connects the suction side to the secondary exhaust path 53 to forcibly exhaust the air in the secondary exhaust path 53. The secondary side exhaust passage 53 through which air is exhausted has a pressure lower than the atmospheric pressure and lower than the primary side passage 52. That is, the pressure in the primary side passage 52 is relatively higher than that in the secondary side exhaust passage 53. In this state, the air contained in the mixed fluid passes through the air permeable membrane 51, passes from the primary side passage 52 to the secondary side exhaust passage 53, and is separated from the mixed fluid.

  In the apparatus of FIG. 2, the mixed fluid is press-fitted into the primary passage 52 by the compressor 55. The compressor 55 is connected to the atomization chamber 4 on the suction side. The secondary side exhaust path 53 is open to the atmosphere. However, a forced exhaust machine can be connected to the secondary exhaust path to reduce the pressure in the secondary exhaust path to atmospheric pressure or lower. The compressor 55 pressurizes the mixed fluid to atmospheric pressure or higher and press-fits the mixed fluid into the primary side passage 52 to make the pressure of the primary side passage 52 higher than that of the secondary side exhaust passage 53. In this state, the air contained in the mixed fluid passes through the air permeable membrane 51 due to a pressure difference between the primary side surface and the secondary side surface. The air that permeates the air permeable membrane 51 is transferred from the primary side passage 52 to the secondary side exhaust passage 53 and separated from the mixed fluid. This structure can increase the pressure difference between the primary surface and the secondary surface of the air permeable membrane 51. For this reason, the air of the mixed fluid can be quickly separated. This is because the compressor 55 can press-fit the mixed fluid into the primary passage 52 at a high pressure.

  Further, in the apparatus of FIG. 2, the suction side of the compressor 55 is connected to the atomization chamber 4 via the pre-stage recovery chamber 60. The desulfurization apparatus can collect the atomized fine particles by connecting any of a cyclone, a punching plate, a demister, a chevron, a scrubber, a spray tower, and an electrostatic recovery machine as the pre-stage recovery chamber 60. In the desulfurization apparatus of FIG. 2, these mechanisms are arranged between the air separator 50 and the atomization chamber 4 to form a pre-stage recovery chamber 60. This apparatus supplies the air separator 50 with the mixed fluid obtained by collecting some of the mist-like fine particles in the upstream collection chamber 60. However, although not shown, the desulfurization unit collects atomized particulates by connecting any of a cyclone, punching plate, demister, chevron, scrubber, spray tower, and electrostatic collector between the air separator and the recovery chamber. You can also

  The air separated by the air separator 50 is air that does not contain petroleum. The apparatus of FIG. 1 supplies the air separated by the air separator 50 to the atomization chamber 4. The apparatus that supplies the air separated by the air separator 50 to the atomization chamber 4 can efficiently atomize atomized fine particles in the atomization chamber 4. This is because the air separated from the mixed fluid by the air separator 50 does not contain petroleum. Further, since the air separated by the air separator 50 is air that is controlled in the atomization chamber 4 to an optimum temperature for generating the atomized fine particles, the air is supplied to the atomization chamber 4 and the atomized fine particles are supplied. It can be generated efficiently.

  The mixed fluid from which the air is separated by the air separator 50 has a small air content. In other words, the amount of atomized fine particles relative to the air increases, and the oil in the atomized fine particles becomes supersaturated. 5, the atomized fine particles can be efficiently recovered. Since the mixed fluid supplied to the recovery chamber 5 is separated from the air by the air separator 50, the amount of air is smaller than that of the mixed fluid discharged from the atomization chamber 4.

  The mixed fluid from which part of the air is separated by the air separator 50 is transferred to the recovery chamber 5. The mixed fluid is supplied to the collection chamber 5 by a forced transfer machine 35 including a blower or a compressor. The forced transfer device 35 is connected between the air separator 50 and the recovery chamber 5 in order to supply the mixed fluid from the air separator 50 to the recovery chamber 5. The forced transfer machine 35 absorbs the mixed fluid from which part of the air has been separated by the air separator 50 and supplies it to the recovery chamber 5.

  The apparatus shown in FIGS. 3 and 4 uses a compressor 35 </ b> A for the forced transfer machine 35. When the compressor 35 </ b> A is used for the forced conveyance device 35, the mixed fluid can be pressurized to atmospheric pressure or higher and supplied to the recovery chamber 5. In this desulfurization apparatus, in the recovery chamber 5, the saturated vapor partial pressure of petroleum in the gas phase is reduced below the saturated vapor partial pressure under atmospheric pressure, and the atomized fine particles can be more effectively aggregated and recovered.

  As the compressor 35A, a piston type compressor, a rotary type compressor, a diaphragm type compressor, a Rishorum type compressor or the like can be used. The compressor 35A is preferably of a type that can feed the mixed fluid to a pressure of 0.2 to 1 MPa.

  A device that uses the compressor 35 </ b> A for the forced transfer machine 35 to increase the pressure in the recovery chamber 5 connects a throttle valve 36 to the discharge side of the recovery chamber 5. However, when the flow rate of the mixed fluid supplied to the recovery chamber by the compressor is large, it is not always necessary to provide a throttle valve on the discharge side of the recovery chamber. This is because when the passage resistance on the discharge side of the recovery chamber is large, the compressor can supply a large amount of mixed fluid to the recovery chamber, and the pressure in the recovery chamber can be increased to atmospheric pressure or higher. However, it is possible to efficiently pressurize the recovery chamber above atmospheric pressure by connecting a throttle valve to the discharge side of the recovery chamber. The throttle valve 36 increases the passage resistance of the mixed fluid discharged from the recovery chamber 35 </ b> A and increases the pressure of the recovery chamber 5. The throttle valve 36 is a valve that can adjust the opening of the mixed fluid to adjust the passage resistance of the mixed fluid, a pipe that increases the passage resistance of the mixed fluid with a narrow tube such as a capillary tube, or the mixed fluid in the pipe. What filled the resistance material which enlarges passage resistance etc. can be used. As the throttle valve 36 increases the passage resistance, the pressure in the recovery chamber 5 increases.

  FIG. 14 shows a state where the amount of oil contained in the air that is the mixed fluid decreases as the recovery chamber 5 is pressurized to atmospheric pressure or higher. As can be seen from this graph, the amount of petroleum that can be contained in the gaseous state increases as the temperature of the mixed fluid air increases. However, as the pressure increases, the amount of oil that can be contained in the gaseous state decreases rapidly. For example, in the case of ethanol, the amount of ethanol that can be contained in dry air at 30 ° C. is remarkably reduced to about 1/5 when the pressure is increased from 0.1 MPa of atmospheric pressure to 0.5 MPa. When the maximum amount of ethanol that can be contained in the gaseous state is reduced, all of the ethanol larger than the maximum amount of ethanol becomes a supersaturated atomized fine particle and can be efficiently recovered. Ethanol contained in the gaseous state cannot be collected by aggregation unless it is made into atomized fine particles. Moreover, even if the ultrasonic vibration atomizes petroleum into a state of atomized fine particles, if it is vaporized into a gaseous state, the oil cannot be aggregated and recovered. Moreover, even if the atomized fine particles are vaporized, they can be liquefied and recovered again in a supersaturated state. Pressurize the mixed fluid containing atomized fine particles to atmospheric pressure or higher to lower the saturated vapor partial pressure of petroleum, thereby efficiently recovering the oil contained in the mixed fluid as atomized fine particles instead of gas it can. The figure shows the characteristics of ethanol, but light oil, gasoline, and kerosene show the same trend, although the values are different. The mixed fluid can be cooled to lower the saturated vapor partial pressure. However, the method of pressurizing is very simple with a compressor and has the feature that the saturated vapor partial pressure can be efficiently reduced with less energy. Furthermore, by pressurizing while cooling, it becomes possible to further reduce the saturated vapor partial pressure of the oil and recover the oil more efficiently.

  When the compressor 35A compresses the mixed fluid, the mixed fluid is adiabatically compressed and generates heat. Further, when the mixed fluid passes through the throttle valve 36, it is adiabatically expanded and cooled. The mixed fluid supplied from the compressor 35A to the recovery chamber 5 is preferably cooled in order to efficiently recover the atomized fine particles, and the recovery efficiency deteriorates when heat is generated. In order to reduce this harmful effect, the apparatus of FIG. 3 includes a heat exchanger 37 for exhaust heat that exchanges heat between the discharge side of the throttle valve 36 and the discharge side of the compressor 35A and the inflow side of the recovery chamber 5. Provided. The heat exchanger 37 for exhaust heat cools the mixed fluid heated by adiabatic compression by the compressor 35A with a mixed fluid that is adiabatically expanded and cooled on the discharge side of the throttle valve 36.

  The heat exchanger 37 for exhaust heat circulates a refrigerant inside the circulation pipe 38. One of the circulation pipes 38 is thermally coupled to the discharge side of the throttle valve 36, and the other is thermally coupled to the discharge side of the compressor 35A. The refrigerant circulating through the circulation pipe 38 is cooled on the discharge side of the throttle valve 36. The refrigerant cooled here cools the discharge side of the compressor 35A. Although not shown, the circulation pipe 38 has a double pipe structure as a portion to be thermally coupled, and the mixed fluid and the refrigerant are thermally coupled.

  Further, the apparatus shown in FIG. 3 includes a second exhaust heat exchanger 39 that connects the discharge side of the throttle valve 36 to a condenser 40 that cools the cooling heat exchanger 33. The second heat exhaust heat exchanger 39 has the same structure as the heat exhaust heat exchanger 37 described above, cools the refrigerant on the discharge side of the throttle valve 36, and cools the condenser 40 with the cooled refrigerant. Thus, the refrigerant circulating in the condenser 40 is liquefied.

  The apparatus shown in FIGS. 2 to 4 connects the atomizing chamber 4, the air separator 50, and the recovery chamber 5 with a circulation duct 30 to circulate the mixed fluid between the atomizing chamber 4 and the recovery chamber 5. Further, outside air is sucked by the suction fan 78 and supplied to the atomizing chamber 4. The device in which the suction fan 78 supplies the outside air to the atomization chamber 4 can efficiently atomize the oil in the atomization chamber 4 using the thermal energy of the outside air. The thermal energy of the outside air sucked by the suction fan 78 efficiently atomizes the oil in the atomizing chamber 4 into atomized fine particles, and further atomizes the atomized atomized fine particles efficiently. This is because the oil in the atomization chamber 4 can improve the atomization efficiency by increasing the temperature of the supplied air. The outside air sucked by the suction fan 78 itself has thermal energy. A device that vaporizes atomized fine particles by effectively using the thermal energy contained in the outside air efficiently atomizes oil into atomized fine particles by effectively using the heat energy of the outside air, and also efficiently vaporizes the atomized fine particles. To do. Therefore, this apparatus can efficiently atomize the oil in the atomizing chamber 4 into atomized fine particles and efficiently vaporize the atomized fine particles without heating the air supplied to the atomizing chamber 4 with a heater, a burner or the like. . The suction fan 78 supplies air corresponding to the amount of air exhausted by the air separator 50 to the atomization chamber 4. In other words, the amount of air sucked into the atomization chamber 4 from the suction fan 78 is separated from the mixed fluid by the air separator 50 and exhausted to the outside.

  The apparatus shown in FIG. 15 circulates the air in which petroleum contained in the mixed fluid is separated into the atomizing chamber 4 without providing an air separator. The air circulated through the atomizing chamber 4 is heated by the outside air heat exchanger 79. The outside air heat exchanger 79 heats the circulating air circulated to the atomization chamber 4 with the heat energy of outside air. The outside air heat exchanger 79 has a large number of radiating fins (not shown) fixed to a pipe through which the circulating air passes. The outside air is blown to the radiating fins by a forced blower fan 80, and the circulating air is added by the outside air. Warm up.

  The apparatus of FIG. 1 connects the discharge side of the atomization chamber 4, the air separator 50, and the supply side of the recovery chamber 5 with a circulation duct 30, so that the discharge side of the recovery chamber 5 and the supply side of the atomization chamber 4 Do not connect with a circulation duct. This apparatus circulates the air separated by the air separator 50 to the atomization chamber 4, and can efficiently atomize the oil into atomized particles in the atomization chamber 4. This is because air containing no oil is supplied to the atomization chamber 4. Furthermore, this apparatus can heat the circulating air with the outside air heat exchanger 79 to further efficiently atomize the oil. Moreover, this apparatus can also circulate through the atomization chamber 4 both the air which isolate | separated the oil with the air separator 50, and the air which isolate | separated the oil with the collection | recovery chamber 5, as shown with the dashed line of a figure.

  The recovery chamber 5 shown in FIGS. 1 to 4 incorporates a cooling heat exchanger 33 that cools and aggregates the atomized fine particles. The cooling heat exchanger 33 has fins (not shown) fixed to the heat exchange pipe 34. A cooling refrigerant or cooling water is circulated through the heat exchange pipe 34 to cool the cooling heat exchanger 33. A part of the atomized fine particles atomized in the atomizing chamber 4 is vaporized to become a gas, but the gas is cooled by the cooling heat exchanger 33 in the recovery chamber 5 and condensed to be condensed and recovered. . The atomized fine particles flowing into the recovery chamber 5 collide with the cooling heat exchanger 33 or collide with each other and greatly agglomerate, or collide with the fins of the cooling heat exchanger 33 and greatly agglomerate and recover. Is done. The air collected by agglomerating the atomized fine particles and the gas by the cooling heat exchanger 33 is circulated again to the atomization chamber 4 through the circulation duct 30.

  In the collection chamber 5, the collection chamber 5 of FIG. 16 includes a nozzle 6 for injecting oil in order to collect the atomized fine particles more quickly. The nozzle 6 is connected to the bottom of the recovery chamber 5 via a circulation pump 15. The circulation pump 15 sucks the oil collected in the collection chamber 5 and sprays it from the nozzle 6.

  In the illustrated desulfurization apparatus, a nozzle 6 is disposed in the upper part of the recovery chamber 5. The upper nozzle 6 sprays oil downward. Petroleum sprayed from the nozzle 6 is sufficiently large water droplets compared to the atomized fine particles atomized by the atomizer 1, and quickly falls inside the collection chamber 5 and is collected when it falls. It collides with the atomized fine particles floating inside the chamber 5 and falls while collecting the atomized fine particles. Therefore, the atomized fine particles floating in the collection chamber 5 can be collected efficiently and promptly.

  In the illustrated desulfurization apparatus, the nozzle 6 is disposed at the upper portion, but the nozzle can be disposed at the lower portion of the recovery chamber 5. The lower nozzle sprays oil upward. The nozzle sprays the oil at a speed at which the oil collides with the ceiling of the recovery chamber 5 or at a speed rising to the vicinity of the ceiling. Oil that is sprayed so as to rise to the vicinity of the ceiling falls in a downward direction in the vicinity of the ceiling, so it falls in contact with the atomized fine particles when rising and descending, so that the atomized fine particles are efficiently removed. to recover.

  The collection chamber 5 of FIG. 17 has a plurality of baffle plates 7 disposed therein. The baffle plate 7 is arranged in a vertical posture with a gap through which the atomized fine particles can pass between adjacent baffle plates 7. The vertical baffle plate 7 can collect the oil adhering to the surface by causing the atomized fine particles to collide with the surface to flow down naturally. The baffle plate 7 shown in the figure has an uneven surface, so that the atomized fine particles can be brought into contact more efficiently and collected.

  Further, the collection chamber 5 in FIG. 17 is provided with a fan 9 for forcibly blowing and stirring the atomized fine particles. The fan 9 agitates the atomized fine particles in the collection chamber 5. The agitated fine particles collide with each other and aggregate, or collide with the surface of the baffle plate 7 and aggregate. Agglomerated fine particles that aggregate are quickly dropped and collected. The fan 9 shown in the drawing circulates the atomized fine particles in the collection chamber 5 by blowing downward.

  The collection chamber 5 in FIG. 18 is provided with a mist fine particle vibrator 8 that increases the probability that the mist fine particles vibrate and collide with each other. The atomized fine particle vibrator 8 includes an electric vibration-mechanical vibration converter that vibrates the gas in the collection chamber 5 and a vibration power source that drives the electric vibration-mechanical vibration converter. The electric vibration-mechanical vibration converter is a speaker that emits sound having an audible frequency, an ultrasonic vibrator that emits ultrasonic waves higher than the audible frequency, or the like. In order for the electric vibration-mechanical vibration converter to vibrate the atomized fine particles efficiently, the vibration radiated from the electric vibration-mechanical vibration converter is resonated in the collection chamber 5. In order to realize this, the electric vibration-mechanical vibration converter is vibrated at a frequency that resonates in the recovery chamber 5. In other words, the recovery chamber 5 is designed to resonate with the vibration radiated from the electric vibration-mechanical vibration converter.

  Ultrasound is a high frequency that exceeds the human audible frequency, so it cannot be heard by the ear. For this reason, the atomized fine particle vibrator 8 that radiates ultrasonic waves vibrates the gas in the recovery chamber 5 violently. In other words, the output of the electric vibration-mechanical vibration converter is greatly increased, and sound damage is caused to humans. Never give. For this reason, the ultrasonic wave has a feature that the atomized fine particles are vibrated vigorously and efficiently collided to be quickly recovered.

  Since the above desulfurization apparatus arrange | positions the apparatus which agglomerates atomized fine particles efficiently in the collection | recovery chamber 5, it can agglomerate atomized fine particles more rapidly. Furthermore, although not shown in the drawings, the desulfurization apparatus of the present invention has a recovery chamber with a built-in nozzle for spraying oil, a fan for stirring the atomized fine particles, and a vibrator for vibrating the atomized fine particles. It can agglomerate atomized fine particles well. In addition, two devices for aggregating the atomized fine particles can be incorporated to efficiently agglomerate the atomized fine particles.

  Petroleum can be atomized into atomized fine particles by ultrasonic vibration and separated into petroleum having different components. That is, petroleum with a low carbon number (n) and a large amount of petroleum is atomized more effectively into atomized fine particles by ultrasonic vibration, and petroleum with a high carbon number (n) is atomized by ultrasonic vibration. This is because the amount is small.

  FIG. 19 shows an apparatus for collecting the mixed fluid atomized into atomized fine particles in multiple stages. This apparatus atomizes oil into atomized fine particles by ultrasonic vibration while heating petroleum to 40 ° C. The air supplied to the atomization chamber 4 is heated by an outside air heat exchanger 79. The outside air heat exchanger 79 heats the air with the heat energy contained in the outside air and supplies it to the atomization chamber 4. The atomized fine particles are mixed with air by a carrier gas to become a mixed fluid. Petroleum contained in the mixed fluid is recovered by the demister 81 that is the first recovery device 200 </ b> A, which is left without being vaporized and has a large particle diameter. The demister 81 of the first recovery device 200A is one of chevron, punching plate, mesh, demister, cyclone, electrostatic field recovery device, filter, scrubber, atomized particle recovery device by ultrasonic vibration, bundle of capillaries, and honeycomb. Alternatively, a plurality of combinations may be used.

  Air, which is a carrier gas from which a part of oil is separated by the demister 81 of the first recovery device 200A, is supplied by the blower 82 to the second recovery device 200B, which is the next step. The blower 82 connects the suction side to the atomization chamber 4 and connects the discharge side to the second recovery device 200B in the next stage. In this apparatus, the atomizing chamber 4 is depressurized from the atmospheric pressure by the blower 82, and the second recovery device 200B is pressurized from the atmospheric pressure. The decompressed atomization chamber 4 promotes the vaporization and atomization of oil. The pressurized second recovery device 200B promotes condensation by reducing the relative vapor pressure of petroleum. The recovery device 200 cools the atomized vaporized or aerosolized gas phase to separate and recover the oil from the air. In the recovery device 200 in this figure, recovery heat exchangers 84 are connected in multiple stages on the inflow side and the discharge side of the main cooler 83. By circulating the refrigerant in order from the main cooler 83, the heat of the entering mixed fluid is moved to the outlet gas phase of the main cooler 83, and the cool heat at the outlet of the main cooler 83 is transferred to the atomizing section outlet. It can be moved to the gas phase at the inlet of the recovery unit. In this way, the oil separation process can be configured by the one-pass method. With this configuration, the heat of the air outside the apparatus can be used effectively. In addition, the collection | recovery apparatus 200 can collect | recover from the atomization chamber 4 to the main cooler 83 in an order from the oil with much content of petroleum with a large carbon number (n).

Further, FIG. 20 shows a gas oil desulfurization device in which the atomization chamber 4 is decompressed and the recovery device 200 is pressurized. As in the apparatus shown in FIG. 19, this apparatus promotes the atomization of petroleum by reducing the pressure in the atomization chamber 4, and condenses efficiently in the recovery apparatus 200 to promote the recovery. The mixed fluid supplied to the recovery device 200 is adiabatically compressed and generates heat. The generated heat is recovered by a heat exchanger and supplied to the carrier gas air supplied to the atomization chamber 4 to raise the temperature. The air of the carrier gas supplied to the atomization chamber 4 can raise temperature, and can raise the atomization efficiency of petroleum. This is because in atomization by ultrasonic vibration, the temperature of the carrier gas can be increased to promote atomization itself. Since the air of the carrier gas supplied to the decompressed atomization chamber 4 is adiabatically expanded and the temperature is lowered, it is desirable to move the adiabatic compression heat of the recovery device 200 as a heat source for raising the temperature of the air. .

  The mixed fluid containing atomized petroleum atomized fine particles is passed through a demister 81 which is a first recovery device. The demister 81 is an apparatus that collects agglomerated fine particles having a relatively large particle size that have not been vaporized or aerosolized by mechanical contact with each other. As in the apparatus of FIG. 19, the apparatus of this figure is connected to a recovery apparatus 200 including a multistage heat exchanger 84 with the main cooler 83 sandwiched between the inflow side and the discharge side of the main cooler 83. The multi-stage heat exchanger 84 can save energy for operating the apparatus by heat transfer. That is, the cold heat of the gas phase at the outlet of the main cooler 83 is applied to the pressure recovery portion inlet. The output side of the collection device 200 is connected to the atomization chamber 4 via the adjustment valve 85. The regulating valves 85, 85 can be spring type, but are not limited thereto. The spring-type regulating valve opens when the pressure increases and reaches a set pressure. The pump for transferring the carrier gas is preferably a diaphragm type or a piston type, but is not limited thereto.

  Petroleum contained in the carrier gas finally leaving the recovery device can be recovered by an adsorption device (not shown). The adsorption device includes an adsorption tower filled with activated carbon, zeolite, silica, ceramic porous body and the like. The adsorption device adsorbs and collects the lean petroleum contained in the carrier gas. The adsorption device heats and adsorbs the adsorbed oil, and this device is preferably a swing type. The swing type adsorption apparatus is a two-column system, and desorbs and collects in the other adsorption tower while adsorbing in one adsorption tower. The adsorption device may be of a rotor type adsorption tower. Activated carbon, zeolite, silica, and a ceramic porous body are supported on a honeycomb, adsorbed and recovered on one side of the rotation center of the rotor, and heated and desorbed and recovered.

FIG. 21 shows a gas oil desulfurization apparatus of a type using a molecular sieve membrane using an air separation membrane of a zeolite membrane. The apparatus includes an air separator 50 that separates petroleum from the mixed fluid. The air separator 50 includes a zeolite membrane as the air permeable membrane 51. The zeolite membrane of the air permeable membrane 51 has pores that are smaller than the molecular diameter of the substance constituting petroleum and larger than the molecular diameter of nitrogen or oxygen constituting the air that is the carrier gas introduced into the atomization portion. That is, it is an air permeable membrane that allows the carrier gas to permeate and does not permeate petroleum. As the air permeable membrane, silica, a ceramic porous body, or the like can be used instead of the zeolite membrane.

  In this apparatus, an outside air heat exchanger 79 is connected to the inflow side of the atomization chamber 4. The outside air heat exchanger 79 heats the air of the carrier gas supplied to the atomization chamber 4 by effectively using the external surplus heat. Further, the apparatus shown in the figure has a surplus heat exchanger 86 connected to the outside air heat exchanger 79. The surplus heat exchanger 86 warms the outside air by effectively using surplus heat generated from other devices. The outside air heated by the surplus heat exchanger 86 heats the air of the carrier gas supplied to the atomization chamber 4 by the outside air heat exchanger 79. The carrier gas air heated by the outside air heat exchanger 79 is supplied to the atomization chamber 4, and the atomization chamber 4 atomizes the oil into atomized fine particles. The atomized fine particles are diffused into the carrier gas to become a mixed fluid. In this state, a part of the atomized fine particles is vaporized or aerosolized and transferred toward the recovery device 200. The atomized fine particles contained in the mixed fluid and having a relatively large particle diameter are mechanically contacted and recovered by the demister 81 which is the first recovery device 200A. In the illustrated apparatus, demisters 81 serving as the first recovery apparatus 200A are connected in two stages. The first-stage demister 81A collects oil having a larger content of petroleum having a larger carbon number (n) than the second-stage demister 81B. The mixed fluid that has passed through the demister 81 is supplied to the air separator 50 having the molecular sieving effect, which is the second recovery device 200B. The air separator 50 separates only air from the mixed fluid with the zeolite membrane of the air permeable membrane 51 and exhausts it to the outside. Petroleum that does not pass through the zeolite membrane of the air permeable membrane 51 is separated from the air by the air separator 50 and recovered. The air separator 50 may pressurize or cool the primary passage side.

  Further, the desulfurization apparatus shown in the figure uses a solar cell 87, a fuel cell, or electric power generated by wind power generation as a power source. Since this apparatus does not use a boiler for driving as in a conventional distillation apparatus, it is possible to eliminate the emission of nitrogen oxides, sulfur oxides, suspended particulate matter, and greenhouse gases. In addition, according to this apparatus, each refinery does not require a countermeasure facility for these harmful substances, which is effective in reducing costs when viewed in total in Japan. It is only necessary to take countermeasures for large-scale warming substances or harmful substances such as thermal power plants and nuclear power plants, and scale merit for environmental measures arises. In the ultrasonic oscillation circuit, heat is generated at a rate of several tens of percent. This heat can be recovered and used effectively by heating the carrier gas supplied to the atomization chamber 4 or by heating the oil in the atomization chamber 4.

The light oil desulfurization apparatus in FIG. 22 connects a plurality of atomizing chambers 4 in series. The apparatus of this figure has connected the atomization chamber 4 and the collection | recovery apparatus 200 in four steps in series. Oil is transferred to the first, second, third and fourth atomization chambers 4 in order. As the oil is transferred, the oil having a small carbon number (n) is sequentially separated from the oil in the atomization chamber 4 as atomized fine particles. Accordingly, the oil in the former atomizing chamber 4 is oil having a small amount of oil having a smaller carbon number (n) than the oil in the latter atomizing chamber 4. The oil temperature in the atomization chamber 4 is lower in the former stage than in the latter stage. The oil in the subsequent atomizing chamber 4 has a higher carbon content (n) than the oil in the preceding atomizing chamber 4, and therefore the oil temperature is gradually increased to increase the amount of oil. The efficiency of atomizing fine particles. Moreover, the temperature of the oil in the former stage atomization chamber 4 can be lowered, and in the former stage atomization chamber 4 and the recovery device 200, the oil having a small amount of carbon (n) and a large amount of petroleum can be separated. The recovery device 200 cools the mixed fluid and separates the petroleum contained in the mixed fluid from the air.

  The desulfurization apparatus of this figure supplies the petroleum raw material of normal temperature to the 1st atomization chamber 4A. The first atomizing chamber 4 </ b> A atomizes into atomized fine particles by ultrasonic vibration, with the oil temperature being the lowest temperature compared to the oil temperature of the other atomizing chamber 4. The mixed fluid containing atomized atomized fine particles has a high content of petroleum having a small carbon number (n). Petroleum with a large amount of petroleum having a small carbon number (n) is recovered by being separated from air by the first recovery device 200A. The residual oil from which the oil having a small amount of carbon having a small carbon number (n) is separated in the first atomizing chamber 4A is supplied to the second atomizing chamber 4B. Since the oil in the second atomization chamber 4B has a higher content of oil having a carbon number (n) than the oil in the first atomization chamber 4A, the oil in the second atomization chamber 4B Heating is performed so that the oil temperature is higher than that of the oil in the atomizing chamber 4A. The second atomization chamber 4B raises the oil temperature and generates atomized fine particles by ultrasonic vibration. The atomized fine particles generated in the second atomizing chamber 4B have a higher content of petroleum having a larger carbon number (n) than the atomized fine particles generated in the first atomizing chamber 4A. The mixed fluid that has passed through the first recovery device 200A is supplied to the second atomizing chamber 4B. The mixed fluid generated in the second atomizing chamber 4B is supplied to the second recovery device 200B. The second recovery device 200B recovers the atomized fine particles generated in the second atomization chamber 4B. However, a part of the atomized fine particles generated in the first atomization chamber 4A passes through the first recovery device 200A and is recovered by the second recovery device 200B. The oil recovered by the second recovery apparatus 200B is oil having a large content of petroleum having a larger carbon number (n) than the oil recovered by the first recovery apparatus 200A. The residual oil separated in the second atomization chamber 4B is supplied to the third atomization chamber 4C. In the same manner, the residual oil separated in the third atomization chamber 4C is supplied to the fourth atomization chamber 4D. The mixed fluid passes through the first recovery device 200A, the second recovery device 200B, the third recovery device 200C, and the fourth recovery device 200D, and gradually increases in the number of carbon atoms ( Oil with a high content of n) is separated and recovered. As described above, the oil temperature is gradually increased in order, and the oil having a large content of oil having a large carbon number (n) can be separated.

  In the illustrated apparatus, the heat of the remaining residual oil is recovered by the residual oil heat exchanger 88. Although the above example does not heat the oil in the first atomizing chamber 4A, the oil can also be heated. In addition, the outside of the atomization chamber 4 can be insulated to reduce the energy use in the entire apparatus as much as possible. The above apparatus is suitable for separating crude oil into light oil, kerosene, naphtha, etc., because it separates petroleum by the content of petroleum having a different carbon number (n).

It is a schematic block diagram which shows the desulfurization apparatus of the light oil concerning one Example of this invention. It is a schematic block diagram which shows the desulfurization apparatus of the light oil concerning the other Example of this invention. It is a schematic block diagram which shows the desulfurization apparatus of the light oil concerning the other Example of this invention. It is a schematic block diagram which shows the desulfurization apparatus of the light oil concerning the other Example of this invention. It is a schematic sectional drawing which shows an example of an atomization chamber and an atomizer. It is an expanded sectional view which shows an example of the connection structure of an ultrasonic transducer | vibrator and a desorption plate. It is a top view of the desorption plate shown in FIG. It is sectional drawing which shows the state with which the desorption plate was mounted | worn in the atomization chamber. It is an expanded sectional view which shows the connection structure of the desorption plate and atomization chamber which are shown in FIG. It is an expanded sectional perspective view which shows another example of the connection structure of an ultrasonic transducer | vibrator and a desorption plate. It is an expanded sectional view which shows another example of the connection structure of an ultrasonic transducer | vibrator and a desorption plate. It is an expanded sectional view which shows another example of the connection structure of an ultrasonic transducer | vibrator and a desorption plate. It is sectional drawing which shows another example which arrange | positions a desorption plate in an atomization chamber. It is a graph which shows the absolute ethanol amount in the air under pressure. It is a schematic block diagram which shows the desulfurization apparatus of the light oil concerning the other Example of this invention. It is a schematic sectional drawing which shows an example of a collection chamber. It is a schematic sectional drawing which shows another example of a collection chamber. It is a schematic sectional drawing which shows another example of a collection chamber. It is a schematic block diagram which shows the desulfurization apparatus of the light oil concerning the other Example of this invention. It is a schematic block diagram which shows the desulfurization apparatus of the light oil concerning the other Example of this invention. It is a schematic block diagram which shows the desulfurization apparatus of the light oil concerning the other Example of this invention. It is a schematic block diagram which shows the desulfurization apparatus of the light oil concerning the other Example of this invention. It is a figure which shows the separation ratio of each component density | concentration of each carbon chain length in the atomization part gaseous phase with respect to the atomization process.

DESCRIPTION OF SYMBOLS 1 ... Atomizer 2 ... Ultrasonic vibrator 2A ... Vibration surface 3 ... Ultrasonic power source 4 ... Atomization chamber 4A ... 1st atomization chamber
4B ... Second atomization chamber
4C ... Third atomization chamber
4D ... 4th atomization chamber 5 ... Collection chamber 6 ... Nozzle 7 ... Baffle plate 8 ... Mist vibrator 9 ... Fan 10 ... Pump 11 ... Stock solution tank 12 ... Desorption plate 12A ... Surface plate 12B ... Back plate
12a ... through hole 12b ... concave
12c ... through hole 13 ... casing 13A ... opening 15 ... circulation pump 16 ... packing 17 ... hinge 18 ... ring plate 19 ... lead wire 20 ... caulking material 21 ... fixing tool 21A ... through hole 22 ... fixing screw 23 ... packing 24 ... Fixing bracket 25 ... Set screw 27 ... Blower mechanism 29 ... Fan 30 ... Circulating duct 33 ... Cooling heat exchanger 34 ... Heat exchange pipe 35 ... Forced transfer machine 35A ... Compressor 36 ... Throttle valve 37 ... Exhaust heat heat exchanger 38 ... circulation pipe 39 ... second heat exchanger for exhaust heat 40 ... condenser 50 ... air separator 51 ... air permeable membrane 52 ... primary side passage 53 ... secondary side exhaust passage 54 ... forced exhaust machine 55 ... compressor 60 ... Previous collection chamber 75 ... Temperature control mechanism 76 ... Warming device 77 ... Temperature sensor 78 ... Suction fan 79 ... Outside air heat exchanger 80 ... Forced air fan 81 ... Demister 1A ... 1 stage of the demister
81B ... Second stage demister 82 ... Blower 83 ... Main cooler 84 ... Heat exchanger 85 ... Regulating valve 86 ... Surplus heat exchanger 87 ... Solar battery 88 ... Residual oil heat exchanger 100 ... Atomizer 200 ... Recovery device 200A ... First recovery device
200B ... Second recovery device
200C ... Third recovery device
200D ... Fourth recovery device W ... Petroleum surface P ... Liquid column

Claims (6)

A desulfurization method for separating petroleum containing less sulfur from petroleum containing sulfur,
Oil containing sulfur is ultrasonically vibrated and released in the form of atomized fine particles floating in the carrier gas, atomized, mixed fluid of atomized atomized fine particles and carrier gas, and residual oil that is not atomized And a recovery step of separating and recovering petroleum from the mixed fluid obtained in the atomization step,
In the atomization process, petroleum is separated into residual oil and mixed fluid, and in the recovery process, oil is recovered from the mixed fluid to produce desulfurized oil. A gas oil desulfurization method that uses sulfur as gas oil to remove sulfur from gas oil . The gas oil desulfurization method according to claim 1, wherein the carrier gas is air. A desulfurization device that separates petroleum containing less sulfur from petroleum containing sulfur,
Oil containing sulfur is ultrasonically vibrated and released in the form of atomized fine particles floating in the carrier gas, atomized, mixed fluid of atomized atomized fine particles and carrier gas, and residual oil that is not atomized The oil is separated from the mixed fluid obtained by the atomizer (100), the heater (76) for heating the oil in the atomization chamber (4), and the atomizer (100). A recovery device (200) for recovery,
The oil to be desulfurized is light oil, and light oil with less sulfur is separated from light oil.
The oil is a light oil is separated into a residual oil mixed fluid atomizing device (100), a mixed fluid was recovered by the recovery device (200), desulfurization of the gas oil to produce a desulfurized gas oil. The atomization device (100) includes an atomization chamber (4) for supplying oil, and an atomizer (1) for atomizing the oil in the atomization chamber (4) into atomized fine particles by ultrasonic vibration. The diesel oil desulfurization apparatus according to claim 3 . The light oil desulfurization apparatus according to claim 3 , wherein the atomizer (100) includes an ultrasonic vibrator (2), and the ultrasonic vibrator (2) ultrasonically vibrates petroleum to atomize the oil into atomized fine particles. . The light oil desulfurization device according to claim 3 , wherein the recovery device (200) recovers the oil by cooling the fluid mixture of the atomized fine particles and the carrier gas.

Images