WO2017094105A1 - Procédé permettant d'augmenter la quantité d'huile hydrocarbonée et dispositif associé - Google Patents

Procédé permettant d'augmenter la quantité d'huile hydrocarbonée et dispositif associé Download PDF

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WO2017094105A1
WO2017094105A1 PCT/JP2015/083739 JP2015083739W WO2017094105A1 WO 2017094105 A1 WO2017094105 A1 WO 2017094105A1 JP 2015083739 W JP2015083739 W JP 2015083739W WO 2017094105 A1 WO2017094105 A1 WO 2017094105A1
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water
catalyst suspension
oil
mixing
zeolite
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PCT/JP2015/083739
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English (en)
Japanese (ja)
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馨 中村
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株式会社ロイヤルコーポレーション
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Priority to PCT/JP2015/083739 priority Critical patent/WO2017094105A1/fr
Publication of WO2017094105A1 publication Critical patent/WO2017094105A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels

Definitions

  • This invention relates to a method for increasing the amount of hydrocarbon oil and its apparatus.
  • Patent Document 1 As an invention for improving the fuel efficiency of fuel hydrocarbons, there is one described in Patent Document 1 by the present inventor.
  • the invention disclosed in Patent Document 1 provides a fuel production method and apparatus for producing fuel oil by reacting an enzyme water prepared by mixing a natural plant complex enzyme with water with oil.
  • active water prepared by mixing natural plant complex enzyme with water is reacted with oil, and the reacted water also functions as fuel by hydrolysis reaction of the raw material oil by the enzyme.
  • Patent Document 2 active water produced by stirring and mixing water and enzyme by bubbling air is mixed with raw material oil and methanol to produce an emulsion, and the emulsion is brought into contact with carbon dioxide.
  • An invention for increasing the amount of hydrocarbon oil is disclosed.
  • the present invention provides a method and apparatus for increasing the amount of hydrocarbon oil according to the following embodiment.
  • [1] Stirring and mixing zeolite or zeolite-like substance and water by bubbling air to produce a catalyst suspension; Filtering the catalyst suspension with a filter having an aperture of 10 ⁇ m or less to generate active water; A method of increasing the amount of hydrocarbon oil, the method comprising contacting the mixture of active water, alcohol, and hydrocarbon oil with a gas or an aqueous solution containing carbon dioxide.
  • a catalyst mixing tank that stirs and mixes zeolite or a zeolite-like substance and water by bubbling air to form a catalyst suspension;
  • a filter having an opening of 10 ⁇ m or less for filtering the catalyst suspension to generate active water;
  • An apparatus for increasing the amount of hydrocarbon oil comprising: an oil mixing tank in which the mixture of the active water, alcohol, and hydrocarbon oil is brought into contact with a gas containing carbon dioxide or an aqueous solution.
  • the amount of hydrocarbon oil can be increased more efficiently using carbon dioxide, which is one of the causes of global warming, as a raw material.
  • a catalyst suspension is prepared by stirring and mixing water and zeolite or a zeolite-like substance, and the catalyst suspension is filtered through a filter having an opening of 10 ⁇ m or less to generate active water.
  • the amount of active oxygen species contributing to the generation of carbon radical species from carbon dioxide, which is the carbon source of the hydrocarbon oil, is greater in the active water after filtration than in the catalyst suspension.
  • hydrocarbon oil is increased by making the mixed solution of activated water, alcohol, and the raw material hydrocarbon oil contact the gas containing carbon dioxide, or aqueous solution (carbonated water).
  • the metal contained in the pores of the zeolite or the zeolite-like substance acts as a catalyst and contributes to activating air or oxygen and generating reactive oxygen species (ROS) in water.
  • the reactive oxygen species include at least one of superoxide anion radical (O 2 ⁇ ), hydroxy radical, hydrogen peroxide (H 2 O 2 ), and singlet oxygen.
  • a known synthetic zeolite can be used as the zeolite-like substance, such as CDS-1 (cylindrically double saw-edged zeolite) (for example, JP-A Nos. 2004-339044 and 2005-145773), PLS-1 Synthetic zeolite such as (pentagonal-cylinder layered silicate) (for example, JP-A-2008-162878) may be used.
  • any kind of zeolite such as borohydrite, mordenite, clinoptilolite, ZSM-5 may be used, and ferrierites are preferably used.
  • Natural ferrierites are cationic minerals with an orthorhombic structure. When the main cation species are magnesium, sodium or potassium, ferrierite-Mg, ferrierite-Na, ferrierite-K, etc. Is done. Natural ferrierite often contains calcium and other minerals as cations, and any cation can be mounted by substitution.
  • some ferrilites of natural zeolite exhibit CO 2 adsorption ability (for example, sodium-substituted ferrilite) and are used for CO 2 concentration (Reference Document 1 below).
  • the method for increasing the amount of hydrocarbon oil according to the present invention comprises: (i) a step of stirring and mixing soot zeolite or zeolite-like substance and water by bubbling air; and (ii) opening the catalyst suspension. (Or pore diameter) a step of producing active water by filtering with a filter of 10 ⁇ m or less; and (iii) a mixture of active water, alcohol, and raw material hydrocarbon oil into a gas containing carbon dioxide or an aqueous solution (carbonated water) A step of contacting.
  • reaction formulas in the steps (i) to (iii) are represented by the following formulas (1) and (2).
  • the above formulas (1) and (2) involving carbon dioxide are expressed by the following chain reaction.
  • water and zeolite are mixed with air for 24 to 72 hours at room temperature and normal pressure so that the reactions represented by the above formulas (1) and (2) are performed at normal temperature and normal pressure.
  • active water it is preferable to produce active water by stirring and mixing.
  • the stirring and mixing time may be appropriately changed depending on the state of the raw material water.
  • the bubbling of air is to generate a large amount of minute air bubbles having a diameter of several ⁇ m to several hundred ⁇ m and to stir and mix the solution by the bubbles.
  • oxygen may be used instead of air.
  • the hydrocarbon oil is mainly composed of hydrocarbons and is liquid under normal temperature and normal pressure (for example, temperature of 15 degrees and 1 atmosphere), and has the chemical formula C n H 2n + 2 or C n + 1 H 2n + 4 (Chain saturated hydrocarbon).
  • n is 1 to 40, preferably 1 to 20.
  • An apparatus for increasing the amount of hydrocarbon oil includes an active water generating apparatus 1 that generates active water from zeolite or a zeolite-like substance and water, and the active water, alcohol, and raw material hydrocarbon oil. And a fuel oil production apparatus 2 for producing fuel oil.
  • FIG. 1 is a schematic configuration diagram of an active water generator 1 that generates active water used for increasing the amount of hydrocarbon oil according to an embodiment of the present invention.
  • the active water generating apparatus 1 includes a blower pump that sends air to one or more catalyst mixing tanks 11 (11a to 11d), one or more filters 12 (12a to 12b), a stabilization tank 14, and a catalyst mixing tank 11. 15, a pump P for moving the liquid between the tanks, and a filter F for removing impurities and the like when the liquid moves.
  • generation apparatus 1 may further be provided with the ventilation
  • the catalyst mixing tanks 11a to 11d are provided in two lines at the top and bottom in the drawing, and both systems are connected by a pump P and a filter F in the order of the catalyst mixing tanks 11a, 11b, 11c, and 11d.
  • the number of the catalyst mixing tanks 11 may be one, or may be two or more.
  • the catalyst mixing tanks 11 may be provided in one system or in two systems or more instead of two systems.
  • the filters 12a and 12b may be one common to each system, or may be provided for each system.
  • water and zeolite or zeolite-like substance are supplied at a predetermined ratio (for example, 1000 liters of water, 500 g of zeolite, etc.), and these are 24 to 72 by bubbling of air supplied from the blower pump 15. Stir and mix for hours.
  • an enzyme powder for example, EP-10) may be further added.
  • tap water may be used as water, soft water, ion exchange water, or pure water is preferably used.
  • the ratio of water to zeolite or zeolite-like substance is 5% (weight ratio) of zeolite or zeolite-like substance to 95% (weight ratio) of water, preferably zeolite or zeolite-like substance to 99% (weight ratio) of water.
  • the zeolite or zeolite-like substance may be 0.05% (weight ratio) with respect to 1% (weight ratio) of the substance, more preferably 99.95% (weight ratio) of water.
  • the enzyme is preferably made of lipase as a main raw material, and is composed of lipase and cellulase, more preferably 98% (weight ratio) of lipase and 2% (weight ratio) of cellulase.
  • the mixed water (catalyst suspension) of water and zeolite or zeolite-like substance in the catalyst mixing tank 11a is moved to the next catalyst mixing tank 11b by the pump P after a predetermined time has elapsed. During this movement, impurities are removed by the filter F. And in the catalyst mixing tank 11b, it stirs and mixes by bubbling of the air supplied from the blower pump 15 again. This is repeated up to the catalyst mixing tank 11d.
  • the total stirring time in the catalyst mixing tanks 11a to 11d is about 24 to 72 hours.
  • the catalyst suspension stirred and mixed in the catalyst mixing tank 11d is sent to the filters 12a and 12b.
  • the filters 12a and 12b are filters having openings (pore diameters) of 10 ⁇ m or less, and filter the catalyst suspension sent from the catalyst mixing tank 11d.
  • the catalyst suspension filtered through the filter 12 is referred to as active water.
  • the catalyst suspension (that is, active water) filtered in the filters 12a and 12b is transferred to the stabilization tank 14, and alcohol is added to the active water in the stabilization tank 14.
  • the alcohol can be, for example, methanol or ethanol, and methanol is preferably used.
  • the mixing ratio of the alcohol is preferably about 5% to 20% (weight ratio) of methanol with respect to the active water.
  • the role of the alcohol added to the active water is mainly the role of helping to mix water and oil and the role of being consumed in the initial reaction of increasing hydrocarbon oil.
  • the active water to which alcohol has been added in the stabilization tank 14 is taken out from the stabilization tank 14 by the pump P. At that time, one or more filters F further remove impurities, zeolites or zeolite-like substances.
  • the extracted activated water is transferred to an appropriate container or stored in the activated water tank 22 of the fuel oil production apparatus 2 shown in FIG.
  • the water activated by the active water generator 1 undergoes reactions of reaction formulas (1) and (2) when raw material oil (hydrocarbon oil) is added in the reaction step even at room temperature. It has been activated. Further, as will be described in detail later, the amount of active oxygen species in the active water is increased by filtering with the filter 12 having an opening of 10 ⁇ m or less as compared with the case of not filtering with the filter 12.
  • FIG. 2 shows a configuration diagram of the fuel oil production apparatus 2.
  • the fuel oil production apparatus 2 includes a raw material oil tank 21 as an oil storage unit that stores a raw material hydrocarbon oil, an active water tank 22 as an active water storage unit that stores active water, and one or a plurality of oil mixing tanks 23.
  • the raw material oil tank 21 is a tank for storing oil as a raw material, and the required amount of raw material hydrocarbon oil is poured into the oil mixing tank 23 through the pipe R in a necessary amount.
  • the hydrocarbon oil as the raw material can be, for example, A heavy oil, B heavy oil, C heavy oil, light oil, kerosene and the like.
  • the active water tank 22 is a tank for storing the active water purified by the active water generator 1, and the stored active water is poured into the oil mixing tank 23 through the pipe R in a necessary amount.
  • the carbon dioxide supply unit 31 includes a cylinder or tank filled with gaseous carbon dioxide or water in which carbon dioxide is dissolved (carbonated water), and supplies gaseous carbon dioxide or carbonated water to the oil mixing tank 23.
  • the concentration of carbon dioxide supplied to the oil mixing tank 23 exceeds the atmospheric carbon dioxide concentration (about 0.03 to 0.04%, 300 to 400 ppm). This is good because more carbon dioxide is used.
  • the concentration of gaseous carbon dioxide (or carbonated water) supplied from the carbon dioxide supply unit 31 is 90% or more, preferably 99% or more, and more preferably 99.5% or more.
  • the carbon dioxide supply unit 31 may be a cylinder filled with carbon dioxide, or recovers carbon dioxide from combustion gas generated at a large-scale source of carbon dioxide such as a power plant, a steel mill, or an oil plant.
  • the apparatus itself or an apparatus for supplying carbon dioxide recovered by the apparatus may be used.
  • the oil mixing tank 23 mixes and stirs the raw material hydrocarbon oil supplied from the raw material oil tank 21 and the active water supplied from the active water tank 22, and supplies the mixed liquid to the carbon dioxide supplied from the carbon dioxide supply unit 31.
  • This is a tank that produces an increased amount of hydrocarbon oil (referred to as “fuel oil”) by being brought into contact with a gas or an aqueous solution containing.
  • active oxygen species including at least one of O 2 ⁇ , hydroxy radicals, H 2 O 2 , and singlet oxygen
  • active water are mainly carbon dioxide (and bicarbonate ions).
  • Carbonate ions, and carbon dioxide-derived ions to generate carbon radical species, and the carbon radical species react with the hydrocarbon oil as a raw material to extend the carbon chain of the hydrocarbon oil.
  • the ratio (weight ratio) of the raw material hydrocarbon oil to the active water in the oil mixing tank 23 may be appropriately adjusted depending on the type of the raw material hydrocarbon oil. For example, A heavy oil 60%, active water 40%, light oil 70% The ratio is preferably 30% and 30% of active water, or 70% of kerosene and 30% of active water, but may be appropriately adjusted depending on the properties of the hydrocarbon oil as a raw material.
  • Carbon dioxide may be supplied to the oil mixing tank 23 after the hydrocarbon oil and the active water are sufficiently stirred and mixed to obtain an emulsified mixed liquid, or the hydrocarbon oil and the active water are stirred. Carbon dioxide may be supplied during mixing so that the reaction with carbon dioxide proceeds faster.
  • the control panel 24 is a control unit that controls each unit of the fuel oil production apparatus 2 and executes various controls such as ON / OFF of power supply.
  • the pulse applying unit 25 vibrates the fuel oil produced in the oil mixing tank 23 to make it easy to remove residues. Residues include water that has not reacted completely, impurities in heavy oil, and the like.
  • the Newton separation tank 26 stores the fuel oil, drops the residue downward by gravity, and extracts the fuel oil remaining above.
  • the separation tank 27 further separates residue from the fuel oil.
  • the precision filter unit 28 removes residue from the fuel oil with a filter.
  • the completed tank 29 stores the completed fuel oil.
  • the drainage tank 30 stores the drainage containing the residue generated in the pulse applying unit 25 and the Newton separation tank 26.
  • FIG. 3 is a configuration diagram showing the configuration of the oil mixing tank 23.
  • the oil mixing tank 23 is provided with a substantially cylindrical stirring space 40, and a stirrer 43 (43L, 43R) and a pump 44 (44L, 44R) are provided in the stirring space 40.
  • a stirrer 43 43L, 43R
  • a pump 44 44L, 44R
  • each stirrer 43 is connected to a pump 44 (44L, 44R), from which raw material hydrocarbon oil and activated water, or a mixture thereof is supplied.
  • a vent pipe (or pump) 45 is connected to each stirrer 43, and carbon dioxide (or carbonated water) is supplied from the carbon dioxide supply unit 31 into the stirrer 43.
  • the pump 44L is connected to a pipe with the suction port 41L disposed above, and the pump 44L sends the raw hydrocarbon oil and active water or a mixture thereof to the stirrer 43L, and the fuel in the stirring space 40 Hydrocarbon oil and activated water, and carbon dioxide (or carbonated water) or a mixture thereof are circulated substantially evenly.
  • the pump 44R is connected to a pipe having a suction port 41R disposed below, and the pump 44L sends the raw hydrocarbon oil and active water or a mixture thereof to the stirrer 43L.
  • the raw material hydrocarbon oil and active water, or a mixture thereof are circulated substantially evenly.
  • the pumps 44L and 44R are preferably 30 to 40 pressure pumps.
  • FIG. 4 is an explanatory diagram for explaining the configuration of the stirrer 43.
  • the stirrer 43 is made of a hollow metal, and is mainly composed of a substantially cylindrical head 51, an inverted conical body 59 that follows the head 51, and a rear end 60 below the head 51. .
  • a cylindrical central shaft 53 is provided at the center of the upper surface of the head 51.
  • the central shaft 53 is provided with an inflow hole 53a (see FIG. 5) penetrating in the vertical direction, and raw material hydrocarbon oil and active water or a mixture thereof flows from the inflow hole 53a.
  • a part of the side surface of the head 51 is provided with an inlet 57 into which raw material hydrocarbon oil and active water or a mixture thereof flows.
  • the inflow port 57 is a hole penetrating from the outside to the inside, and is surrounded by a cylindrical connecting cover 55.
  • a thread groove 56 is provided on the inner surface of the connection cover 55 so that a pipe connected to the pump 44 is attached.
  • the position of the inlet 57 and the direction of the connecting cover 55 are, as shown in the AA cross-sectional view of FIG. 4B, eccentric from the center of the stirrer 43 toward the inner periphery, Active water or a mixture of active water and oil flows in. As a result, the hydrocarbon oil or the like of the raw material that has flowed in from the inlet 57 is efficiently rotated about the cylindrical central shaft 53.
  • a plurality of pins 63 are provided inside the stirrer 43 along the inner periphery. The plurality of pins 63 are arranged with a gap so as not to cross each other. For example, it is preferable to provide 55 to 80 0.03 mm pins with an interval of about 10 mm.
  • a discharge hole 61 is provided in the rear end portion 60 of the stirrer 43.
  • the stirrer 43 configured as described above can efficiently stir oil and active water to cause a decomposition reaction. More specifically, the raw material hydrocarbon oil and active water flowing in from the inlet 57, or a mixture thereof, rotates around the central shaft 53 and gradually decreases in radius of rotation toward the discharge hole 61. Move to. In that case, it agitates with the some pin 63 provided in the inside. Further, by rotating in a tornado shape, a negative pressure is generated in the vicinity of the lower portion of the central shaft 53, whereby the raw material hydrocarbon oil and active water or a mixture thereof flows from the inflow hole 53a. That is, the stirrer 43L shown in FIG.
  • the stirrer 43R mainly takes in active water sucked from the suction port 41R from the inlet 57 by the pump 44R and takes in oil mainly from the inlet hole 53a and stirs. With this stirrer 43, the active water and oil collide with each other in a strong water pressure, and the mixture is stirred to promote the reaction of the reaction formula (1).
  • the oil mixing tank 23 equipped with the stirrer 43 is stirred for a predetermined time (for example, about 15 to 20 minutes)
  • the oil and the enzyme that are moved in a stirrer shape in the stirrer 43 and stirred are 300 to 500 times.
  • the contact is repeated, the hydrolysis reaction is promoted, the molecular structure is reduced, and the specific gravity is also reduced.
  • FIG. 6A is a perspective view of the pulse filter 70 provided in the pulse applying unit 25.
  • the pulse filter 70 is provided between the two line mixers, and allows the fuel oil to pass through holes formed between the grid-like partitions 71.
  • the pulse applying unit 25 (particularly the partition 71) is formed of a ceramic fired body.
  • the partition 71 is gently twisted in a screw shape inside, and vibrates the fuel oil that has flowed in, thereby promoting the reaction. As a result, it is possible to easily remove impurities.
  • FIG. 6B is a perspective view of the precision filter 80 provided in the precision filter section 28.
  • This precision filter 80 is provided with a filter 81 extending radially from the center around a cylindrical tube portion 82 formed of a mesh-like material. Impurities can be removed by allowing the fuel oil to pass through the filter 81 from the outer periphery toward the cylindrical portion 82.
  • the filters 81 are provided radially, the fuel oil can pass through the entire plate-like surface 81b from the base side 81a to the tip side 81c, as shown in the partially enlarged plan view of FIG. . For this reason, even if impurities accumulate on the base portion side 81a and become difficult to pass, the fuel oil can be passed through the plate-like surface 81b without any problem and removed.
  • FIG. 7 shows a longitudinal sectional view of a Newton separation tank 26 as a contact tank according to the present invention.
  • the Newton separation tank 26 is mainly composed of an inclined plate 96 provided in the vicinity of the bottom, and a plurality of high-level plates 92 and low-level plates 93 provided alternately above the upper plate, and a liquid inlet 91 is provided at the front stage and the rear stage. Is provided with a liquid discharge port 95.
  • the high plate 92 is provided with a space between the lower end and the inclined plate 96, and is configured so that the fuel oil can move back and forth.
  • the lower plate 93 has an upper end formed lower than the high plate 92 and can overflow the upper portion of the stored fuel oil and move it to the adjacent storage section.
  • the lower plate 93 is provided with a movable plate 94 at the lower end, and is configured such that the lower end of the movable plate 94 contacts the inclined plate 96.
  • the high level plate 92 and the low level plate 93 are alternately arranged in this order, and are configured such that the lower ends are successively shortened in accordance with the inclination of the inclined plate 96.
  • the fuel oil that has flowed into the first reservoir 90a from the liquid inlet 91 is refined with impurities accumulated downward, and the fuel oil is generated according to the reaction formulas (1) and (2). It overflows to the next second reservoir 90b.
  • the fuel oil that has been cleaned by repeating this from the first reservoir 90 a to the fourth reservoir 90 d is discharged from the liquid outlet 95.
  • Impurities precipitated in the reservoirs 90a to 90d move downward along the inclined plate 96.
  • the movable plate 94 is opened to allow impurities to move downward. Since the movable plate 94 does not open in the reverse direction, impurities do not flow backward.
  • Impurities that have moved downward along the inclined plate 96 move from the collection opening 97 to the collection unit 98 via the valve 99a and are collected in the collection unit 98.
  • the valve 99a is opened / closed intermittently, and is opened and collected in the collection unit 98 and closed when a certain amount of residue is accumulated. At this time, the gas is exhausted from an exhaust valve 99c provided near the upper portion of the recovery unit 98.
  • the impurities collected in the collection unit 98 may be taken out from the collection valve 99b and discarded.
  • the stirrer 43 may be a different type of stirrer 43A as shown in FIG.
  • the stirrer 43A is not provided with a discharge hole at the rear end portion 60.
  • a central pipe 54 is provided instead of the central shaft 53 of the above-described embodiment.
  • the center pipe 54 has a cylindrical shape having a hollow portion 67 therein, and its upper end 67a functions as a fuel oil discharge port.
  • the stirrer 43A configured in this manner rotates the active water and oil flowing in from the inlet 57, moves downward in a tornado shape while reducing the rotation radius, and moves from the lower end to the upper end of the center pipe 54. It is discharged from the upper end.
  • This stirrer 43A can also exhibit the same effects as the stirrer 43 of the above-described embodiment.
  • reaction according to the reaction formulas (1) and (2) can be performed to generate fuel oil.
  • a catalyst suspension was prepared in which natural zeolite and ion-exchanged water were bubbled with air for 2 days (48 hours) and mixed by stirring.
  • natural zeolite mainly containing ferrierites natural zeolite was used.
  • catalase to remove hydrogen peroxide (CAT) O 2 - superoxide dismutase to remove (SOD), and is the removal reagent 1 O 2 1,4-diazabicyclo [2.2.2]
  • Samples to which octane (1,2-diazabicyclo [2.2.2] octane: DABCO) was added were prepared.
  • the integrated value of CLA chemiluminescence (CLA-CL) integrated time: 3 minutes, unit: rlu was measured for each sample (FIG. 9).
  • “2 day bubbling” represents a sample of a catalyst suspension obtained by mixing natural zeolite and ion exchange water for 2 days
  • “DDW” represents a sample of only ion exchange water
  • “CAT” represents a sample obtained by adding 4 kU / ml of CAT to the catalyst suspension
  • “20 kU / ml CAT” represents a sample obtained by adding 20 kU / ml of CAT to the catalyst suspension
  • “DABCO” represents a sample with DABCO added to the catalyst suspension.
  • the CLA-CL integrated value of the “2-day bubbling” sample was four times or more larger than the value of the “DDW” sample containing only ion-exchanged water. From this, it was found that O 2 ⁇ active oxygen species were generated in the catalyst suspension obtained by bubbling natural zeolite and ion-exchanged water for 2 days.
  • CLA-CL of samples “4 kU / ml CAT” and “20 kU / ml CAT” added with CAT for removing hydrogen peroxide to the catalyst suspension and sample “DABCO” added with DABCO for removing 1 O 2 were added.
  • CLA especially O 2 - show high selectivity for
  • CLA-CL is O 2 - to indicate that it is the specific detection, is effective utilization of 1 O 2 removal reagent such as DABCO
  • the system is long if CLA-CL of 1 O 2 is generated Can be quenched with DABCO (Reference 8 below). Therefore, as shown in FIG. 9, since there was no significant difference between the CLA-CL integrated value of the sample “2 day bubbling” and the CLA-CL integrated value of the sample “DABCO”, the observed CLA-CL is O 2 - has been suggested to be specific for.
  • H 2 O 2 is required as an O 2 ⁇ precursor (upstream). It is known to be inhibited (Reference 9 below). However, this does not deny that H 2 O 2 and its downstream hydroxy radical are produced from O 2 ⁇ .
  • Reference 7 Nakano M, Sugioka K, Ushijima Y, Goto T. Chemiluminescence probe with Cypridina luciferin analog, 2-methyl-6-phenyl-3,7-dihydroimidazo [1,2-a] pyrazin-3-one, for reducing the ability of human granulocytes to generate O2-. Anal Biochem 1986; 159: 363-9.
  • Example 1 natural zeolite and ion-exchanged water were stirred and mixed for 2 days (48 hours) to prepare a catalyst suspension sample.
  • the stirring and mixing was performed in two patterns: stirring and mixing by air bubbling and stirring and mixing by a stirrer regardless of bubbling.
  • Tyron which is an O 2 ⁇ removal reagent
  • dimethyl which is a hydroxyl radical removal reagent.
  • Air0.2 represents a sample of the catalyst suspension prepared by stirring and mixing by air bubbling
  • Air0.2 Tiron2.5 mM represents the catalyst suspension prepared by stirring and mixing by air bubbling.
  • Air0.2 Bipy1 mM represents the sample added with 1 mM 2,2′-bipyridine to the catalyst suspension prepared by stirring and mixing by air bubbling
  • Air0.2 Dabco2 .5 mM represents a sample obtained by adding 2.5 mM of DABCO to a catalyst suspension prepared by stirring and mixing by air bubbling
  • Air0.2 to DMTU1 mM represents a catalyst suspension prepared by stirring and mixing by air bubbling.
  • DMTU represents a sample added with 1 mM
  • Air0.2 o-Phe1 mM (1% EtOH) represents a sample obtained by adding orthophenanthroline to a catalyst suspension prepared by stirring and mixing by bubbling air.
  • w / o Air0.2 represents a sample of the catalyst suspension prepared without bubbling
  • w / o Air0.2 Tiron2.5 mM represents the catalyst suspension prepared without bubbling
  • W / o Air0.2 Bipy1 mM represents a sample in which 1 mM of 2,2′-bipyridine was added to a catalyst suspension prepared without bubbling.
  • Air0.2 Dabco2.5mM represents a sample prepared by adding 2.5mM DABCO to a catalyst suspension prepared without bubbling
  • w / o Air0.2 DMTU1mM represents a catalyst suspension prepared without bubbling. Represents a sample added with 1 mM DMTU
  • w / o Air0.2 o-Phe1mM (1% EtOH) represents a sample obtained by adding orthophenanthroline to a catalyst suspension prepared without bubbling.
  • DMTU inhibits the generation of hydroxy radicals.
  • high concentrations of DMTU were used in this example, various intermediates of reactive oxygen species related to the generation of O 2 ⁇ may be removed.
  • CLA-CL integrated values of the samples “Air0.2 DMTU1 mM” and “w / o Air0.2 DMTU1 mM” to which DMTU was added were reduced.
  • Example 1 natural zeolite and ion-exchanged water were stirred and mixed by air bubbling for 2 days (48 hours) to prepare a catalyst suspension, and a sample filtered through a filter having an opening of 0.2 ⁇ m was prepared. Got ready. The filtered sample was aerated with oxygen (O 2 ), carbon dioxide (CO 2 ), and nitrogen (N 2 ) gas for 10 seconds, and then the CLA-CL integrated value (integrated time 3 minutes) for each sample. , Unit: rlu) was measured (FIG. 11). In the aeration treatment, the catalyst suspension filtered through a filter was stirred and mixed by bubbling oxygen, carbon dioxide, and nitrogen, respectively. The purity of oxygen (O 2 ), carbon dioxide (CO 2 ), and nitrogen (N 2 ) gases used for the aeration treatment is 99.9% or more.
  • “2 day bubbling” is a sample not subjected to aeration treatment
  • “2 day bubbling + O 2 10 sec” is a sample aerated with oxygen
  • “2 day bubbling + CO 2 10 sec” is a sample aerated with carbon dioxide
  • “2 day bubbling + N 2 10 sec” represents a sample that has been aerated with nitrogen.
  • the value of the sample “2 day bubbling + O 2 10 sec” aerated with oxygen is more significant (7-8) than the CLA-CL integrated value of the sample “2 day bubbling” that has not been aerated (7-8). Doubled). From this, it was found that the amount of O 2 ⁇ produced can be significantly improved by subjecting the catalyst suspension to aeration treatment with oxygen, compared to the case where the catalyst suspension is not subjected to aeration treatment with oxygen. Since it is considered that other active oxygen species are generated along with the generation of O 2 ⁇ , the amount of other active oxygen species produced (the amount of active oxygen species per unit volume) by oxygen aeration treatment is also aerated with oxygen. It is considered that the amount is significantly higher than the amount of the catalyst suspension before treatment (the amount of active oxygen species per unit volume).
  • the CLA-CL integrated value of the sample “2 day bubbling + CO 2 10 sec” aerated with carbon dioxide is small, and the O 2 ⁇ production activity is significantly inhibited by aeration treatment of the catalyst suspension with carbon dioxide. I understood it. This is considered to be due to the fact that the carbon component derived from carbon dioxide used for the aeration treatment reacted with O 2 ⁇ in the catalyst suspension.
  • the amount of active oxygen species produced can be significantly increased (7 to 8 times) by aeration treatment with oxygen after the catalyst suspension is produced, so that active water rich in active oxygen species can be obtained.
  • active water, alcohol, and raw material hydrocarbon oil are mixed to produce an emulsion, and the emulsion is brought into contact with a gas containing carbon dioxide or an aqueous solution (carbonated water).
  • Carbon radical species are generated from carbon dioxide according to the amount of oxygen species, and the amount of hydrocarbon oil is increased according to the amount of carbon radical species produced. Note that the higher the concentration of carbon dioxide that is brought into contact with the emulsion, the more carbon dioxide molecules are present at the interface between the emulsion and the gas (or aqueous solution) containing carbon dioxide. It is considered that the number of carbon dioxide molecules that react with the active oxygen species increases, and as a result, the amount of carbon radical species generated also increases.
  • Example 1 natural zeolite and ion-exchanged water were stirred and mixed for 2 days (48 hours) to prepare a catalyst suspension, and samples filtered through filters with various openings were prepared.
  • the stirring and mixing was performed in two patterns: stirring and mixing by air bubbling and stirring and mixing by a stirrer regardless of bubbling.
  • the filter used for filtration used what has an opening of 0.2 micrometers, 5 micrometers, 10 micrometers, and 40 micrometers.
  • CLA-CL integrated value integrated time: 3 minutes, unit: rlu
  • the filter used in this example is a filter for syringes (Mirex Mille (registered trademark) for HPLC (Mirex LG / LH)) manufactured by Merck Millipore, with a filter having an opening of 0.2 ⁇ m, and has an opening of 5 ⁇ m, 10 ⁇ m, and 40 ⁇ m.
  • the filter is a nylon mesh (mesh cloth) filter.
  • the catalyst suspension prepared by stirring and mixing natural zeolite and ion-exchanged water for 2 days (48 hours) with air bubbling is used for various aperture filters. Then, the absorbance (turbidity) of light having a wavelength of 600 nm was measured in the air for each sample, and the difference in turbidity was examined (FIG. 13). As in the above, filters having a mesh size of 0.2 ⁇ m, 5 ⁇ m, 10 ⁇ m, and 40 ⁇ m were used.
  • “DDW” is a sample containing only ion-exchanged water
  • “Air0.2” is a sample obtained by filtering a catalyst suspension prepared by stirring and mixing by bubbling air with a filter having an opening of 0.2 ⁇ m
  • “Air5” is a sample obtained by filtering the catalyst suspension prepared by stirring and mixing by air bubbling with a filter having a mesh opening of 5 ⁇ m
  • “Air10” is filtering the catalyst suspension prepared by stirring and mixing by air bubbling through a filter having a mesh of 10 ⁇ m
  • the sample “Air40” represents a sample obtained by filtering a catalyst suspension prepared by stirring and mixing by bubbling air through a filter having an opening of 40 ⁇ m.
  • w / o ⁇ Air0.2 is a sample obtained by filtering a catalyst suspension prepared without bubbling with a filter having a mesh opening of 0.2 ⁇ m
  • “ w / o Air5 ” is prepared without bubbling.
  • “w / o Air10” is a sample obtained by filtering the prepared catalyst suspension through a filter having a mesh opening of 10 ⁇ m without bubbling
  • w / o Air40 Represents a sample obtained by filtering a catalyst suspension prepared without bubbling through a filter having an opening of 40 ⁇ m.
  • the largest integrated value of CLA-CL was the sample “Air0.2” that was stirred and mixed by bubbling air for two days and filtered through a filter with an opening of 0.2 ⁇ m. It was. Further, as shown in FIG. 13, the absorbance (suspension) of the sample filtered with a filter opening of 10 ⁇ m and 40 ⁇ m hardly changed. From this, it can be seen that the size of the natural zeolite used for the sample of this measurement is approximately 10 ⁇ m or less. Then, in FIG.
  • the samples “Air10” and “w / o Air10” filtered through 10 ⁇ m, and the samples “Air40” and “w / o Air40” filtered through a filter with 40 ⁇ m openings are not filtered. It can also be said to be a suspension.
  • the CLA-CL integrated values of the samples “Air0.2” and “Air5” are CLA-CL integrated values of the samples “Air10” and “Air40” which can be regarded as unfiltered catalyst suspensions. Further, the CLA-CL integrated value of the sample “Air0.2” was larger than the CLA-CL integrated value of the sample “Air5”. Similar results were obtained for samples “w / o Air0.2” to “w / o Air40” prepared without bubbling.
  • a filter having a small opening (preferably an opening of 10 ⁇ m or less, more preferably 0.2 ⁇ m or less) is used for a catalyst suspension prepared by stirring and mixing natural zeolite and ion-exchanged water. It has been found that the amount of active oxygen species in the catalyst suspension can be improved as the amount of filtration increases. In other words, the more natural zeolite with a smaller outer diameter (preferably the outer diameter is 10 ⁇ m or less, more preferably the outer diameter is 0.2 ⁇ m or less), the more active oxygen species in the catalyst suspension. It was found that can be improved. The reason for this is thought to be that zeolite or zeolite-like material having a particle size of a certain size (especially a size exceeding 10 ⁇ m) partially inhibits the reaction that generates active oxygen species in the catalyst suspension. It is done.
  • a sample was prepared by filtering a catalyst suspension prepared by stirring and mixing natural zeolite and ion-exchanged water for 2 days (48 hours) in the same manner as in Example 1 with a filter having an opening of 0.2 ⁇ m.
  • the stirring and mixing was performed in two patterns: stirring and mixing by air bubbling and stirring and mixing by a stirrer regardless of bubbling. Further, 50 ⁇ M of divalent iron ions (Fe 2+ ) or 50 ⁇ M of trivalent iron ions (Fe 3+ ) were added to the filtered samples, and the CLA-CL integrated value was measured for each (FIG. 14).
  • Air0.2 represents a sample obtained by filtering a catalyst suspension prepared by stirring and mixing by bubbling
  • Air0.2 (Fe 2+ ) 50 ⁇ M represents a catalyst prepared by stirring and mixing by air bubbling. The suspension is filtered and a sample to which 50 ⁇ M of divalent iron ions (Fe 2+ ) is added is represented.
  • Air0.2 (Fe 3+ ) 50 ⁇ M is a filtered catalyst suspension prepared by stirring and mixing by bubbling air.
  • 3 represents a sample to which 50 ⁇ M of trivalent iron ions (Fe 3+ ) is added.
  • w / o Air0.2 represents a sample obtained by filtering the prepared catalyst suspension without bubbling, and “w / o Air0.2 (Fe 2+ ) 50 ⁇ M” does not bubbling.
  • the sample is obtained by filtering the suspension and adding 50 ⁇ M of trivalent iron ions (Fe 3+ ).
  • an iron content removal unit may be provided in the road to remove iron ions from the active water generated by the filters 12a and 12b.
  • An iron removing unit may be provided to remove iron ions from the catalyst suspension before being sent to the filters 12a and 12b.
  • an ion exchange resin or a reverse osmosis (RO) membrane may be used, or a device that is precipitated by a chelating agent or an oxidant and precipitated or filtered may be used.
  • a sample was prepared by filtering a catalyst suspension prepared by stirring and mixing natural zeolite and ion-exchanged water for 2 days (48 hours) with a filter having an opening of 0.2 ⁇ m.
  • the stirring and mixing was performed in two patterns: stirring and mixing by air bubbling and stirring and mixing by a stirrer regardless of bubbling. Further, 50 ⁇ M of monovalent copper ions (Cu + ) or 50 ⁇ M of divalent copper ions (Cu 2+ ) were added to the filtered samples, and CLA-CL integrated values were measured for each (FIG. 15).
  • Air0.2 represents a sample obtained by filtering the catalyst suspension prepared by stirring and mixing by air bubbling
  • Air0.2 (Cu + ) 50 ⁇ M was prepared by stirring and mixing by air bubbling. This represents a sample in which the catalyst suspension was filtered and monovalent copper ions (Cu + ) 50 ⁇ M were added.
  • Air0.2 (Cu 2+ ) 50 ⁇ M represents the catalyst suspension prepared by stirring and mixing by bubbling air. The sample which filtered and added 50 micromol of divalent copper ion (Cu2 + ) is represented.
  • w / o Air0.2 represents a sample obtained by filtering the prepared catalyst suspension without bubbling
  • “w / o Air0.2 (Cu + ) 50 ⁇ M” does not bubbling.
  • the prepared catalyst suspension is filtered and a sample to which 50 ⁇ M monovalent copper ion (Cu + ) is added is represented.
  • “W / o Air0.2 (Cu 2+ ) 50 ⁇ M” is a catalyst suspension prepared without bubbling.
  • the sample which filtered the liquid and added 50 micromol of bivalent copper ion (Cu2 + ) is represented.
  • the CLA-CL integrated values of the samples “Air0.2 (Cu + ) 50 ⁇ M” and “Air0.2 (Cu 2+ ) 50 ⁇ M” added with copper ions were not added with copper ions. There was no significant difference from the value of sample “Air0.2”.
  • the CLA-CL integrated values of the samples “w / o Air0.2 (Cu + ) 50 ⁇ M” and “w / o Air0.2 (Cu 2+ ) 50 ⁇ M” with copper ions added do not contain copper ions.
  • the value of the sample “w / o Air0.2” was not significantly different. Therefore, the effect of O 2 of copper ions - reduction of production activity (i.e.
  • the amount of active oxygen species has little, if adding metal ions to the reaction solution, rather than iron ions, copper ions is desirable I understood.
  • the active water generating device homogeneous mixing device, mixing device, oil mixing tank, stirrer, pulse filter, precision filter, and Newton separation tank shown in FIGS. It is preferable that the portion that comes into contact with the emulsified liquid, which is a mixed solution of active water, alcohol, and raw material hydrocarbon oil, be made of a copper member and not an iron member as much as possible.
  • the present invention can be used for increasing the amount of various hydrocarbon oils.

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Abstract

L'invention concerne un procédé mettant en oeuvre du dioxyde de carbone et permettant d'augmenter la quantité d'huile hydrocarbonée, ainsi qu'un dispositif associé. Dans un mode de réalisation de cette invention, le procédé permettant d'augmenter la quantité d'huile hydrocarbonée comporte: une étape consistant à agiter et mélanger un zéolite ou une substance de type zéolite avec de l'eau par barbotage d'air pour produire une suspension catalytique; une étape consistant à faire passer la suspension catalytique dans un filtre dont l'ouverture de maille est égale ou inférieure à 10μｍ pour produire une eau corrosive; et une étape de mise en contact de cette eau corrosive, d'alcool et d'un mélange d'huile hydrocarbonée avec une solution aqueuse ou un gaz contenant du dioxyde de carbone. L'invention concerne en outre un dispositif associé.
PCT/JP2015/083739 2015-12-01 2015-12-01 Procédé permettant d'augmenter la quantité d'huile hydrocarbonée et dispositif associé WO2017094105A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0592192A (ja) * 1991-10-01 1993-04-16 Nippondenso Co Ltd 水質浄化装置
JP2010029812A (ja) * 2008-07-30 2010-02-12 Noritz Corp 水処理装置及び潜熱回収熱源機
WO2015147322A1 (fr) * 2014-03-28 2015-10-01 株式会社ロイヤルコーポレーション Procédé et dispositif de production d'huile hydrocarbonée combustible

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0592192A (ja) * 1991-10-01 1993-04-16 Nippondenso Co Ltd 水質浄化装置
JP2010029812A (ja) * 2008-07-30 2010-02-12 Noritz Corp 水処理装置及び潜熱回収熱源機
WO2015147322A1 (fr) * 2014-03-28 2015-10-01 株式会社ロイヤルコーポレーション Procédé et dispositif de production d'huile hydrocarbonée combustible

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