Manufacturing method of organic porous particle as treatment method of oil sludges, organic porous particle, and organic porous particle manufacturing system

Abstract

To provide a method and a system of converting high viscosity organic sludges derived from crude oil manufacturing by subcritical water treatment without adhering to an inside of a pressure vessel to organic porous particles such as soil improvement agents.SOLUTION: An organic porous particle manufacturing system 10 includes: a high viscosity organic sludge hopper 14 for storing high viscosity organic sludges derived from crude oil manufacturing; an adhering inhibitor hopper 18 for storing an adhering inhibitor such as resin sludge wastes; a subcritical water treatment apparatus 12 for agitation of a raw material charged from a raw material charging port 12B at 170-250°C and 2.0-3.5 MPa to convert it to lower molecular weight; a high viscosity screw pump 16 for sending the high viscosity organic sludges to a raw material charging pipe 41; an organic porous particle storage tank 20 for storing most of organic porous particles exhausted from the subcritical water treatment apparatus; a centrifugal separator 28 for separating components including residual organic porous particles into a light liquid and heavy components; a recovered light liquid storage tank 30; and a heavy component recharging pipe 44 for sending the heavy components to the raw material charging pipe.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a method for producing organic porous particles using highly viscous organic sludge as a starting material, which includes at least one of oil sludge discharged from the crude oil production, refining and transportation processes in the petroleum industry, including oils and fats and their solidified products, and highly viscous organic residues generated in pharmaceutical factories, as well as to organic porous particles and an organic porous particle production system. [Background technology]

[0002] Concerning crude oil sludge, for example, Patent Document 1 discloses a method for recovering oil from crude oil sludge. In the invention disclosed in Patent Document 1, even if oil is recovered from the crude oil sludge, this is only about half the mass of the crude oil sludge, and the remaining half is treated as waste, and no method or system for treating it has been proposed yet.

[0003] Furthermore, Patent Document 2 discloses a subcritical water treatment method and apparatus for heating and pressurizing a polymeric resin in a subcritical state to reduce the molecular weight of the resin.

[0004] Crude oil sludge, etc., has a very high viscosity, and even if it is put into a subcritical water treatment device, if it remains adhered to the inner wall of the pressure vessel and is heated and pressurized, it is very difficult to remove it from the inner wall. The crude oil sludge, etc., comes into contact with the inner wall while rotating in the subcritical water treatment device, receives heat from this and separates, and the next crude oil sludge comes into contact with the inner wall, and is heated one after another. However, if the crude oil sludge, etc., strongly adheres to the inner wall, it becomes impossible to transfer heat in sequence as described above, and it has sometimes been impossible to heat some of the crude oil sludge, etc., to the subcritical state temperature. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2018-2899 A [Patent Document 2] Patent No. 6327993 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a method for producing organic porous particles by reducing the molecular weight of highly viscous organic sludge by bringing it into a subcritical state at high temperature and high pressure without it sticking to the inside of a pressure vessel of a subcritical water treatment device, and to provide organic porous particles and an organic porous particle production system.

[0007] Furthermore, the present invention can convert highly viscous organic sludge, such as crude oil sludge, into organic porous particles or a porous soil conditioner without treating the entire sludge as untreatable waste.

[0008] This will be a practical and concrete method for treating oil sludge that is left abandoned and stored in various forms around the world because it cannot be treated. [Means for solving the problem]

[0009] The above problem is solved by a process of mixing highly viscous organic sludge, which includes at least one of oil sludge discharged from the crude oil production, refining, and transportation processes in the petroleum industry, including fats and oils and their solidified products, and highly viscous organic residue generated in pharmaceutical factories, with an adhesion inhibitor consisting of at least one of resin sludge scraps, crushed PET bottle scraps, resin scraps, and organic particles obtained by low molecular weight treatment of highly viscous organic sludge, and introducing the mixture into a subcritical water treatment environment with a weight ratio of the adhesion inhibitor of 5%-80%, and a process of treating the mixture at a temperature of 170℃-250℃ and a pressure of 2. The above-mentioned problems are solved by a method for producing organic porous particles, which comprises: a step of stirring and mixing the added highly viscous organic sludge and an adhesion inhibitor in a subcritical environment of 0 MPa to 3.5 MPa; and a step of maintaining the subcritical environment and stirring until, in the process of breaking down the resin contained in the added highly viscous organic sludge into smaller molecules, the hydrophobicity of the oil and fat content and the fluidity of high temperature suppress recombination and melting and solidification of the broken down resin, thereby producing a solid decomposition product in the form of organic porous particles containing micropores with a diameter of 2 mm or less.

[0010] The present invention also provides a method for treating a sludge containing at least one of oil sludge discharged from the crude oil production, refining and transportation processes in the petroleum industry, which contains fats and oils and their solidified products, and highly viscous organic sludge containing at least one of highly viscous organic residues generated in pharmaceutical factories, inorganic sludge containing silica components, and oil sludge containing fats and oils and their solidified products in the residue of a heat-resistant sheet containing silica components, and a process for introducing the mixture into a subcritical water treatment environment with a weight ratio of the adhesion inhibitor of 5%-80%; and The above-mentioned problem is solved by a method for producing organic porous particles containing an organic matter and a silica component, which comprises: a step of stirring and mixing the charged highly viscous organic sludge and an adhesion inhibitor in a subcritical environment; and a step of maintaining the subcritical environment and stirring until, in the process of breaking down the resin contained in the charged highly viscous organic sludge into smaller molecules, the hydrophobicity of the oil and fat content and the fluidity of high temperatures inhibit recombination and melting and solidification of the broken down resin, thereby producing a solid decomposition product containing organic matter and a porous particulate silica component and having a diameter of 2 mm or less.

[0011] The above-mentioned problem is further solved by providing a high-viscosity organic sludge hopper for storing and discharging high-viscosity organic sludge including at least one of oil sludge discharged from the processes of crude oil production, refining and transportation in the petroleum industry, including fats and oils and their solidified products, and high-viscosity organic residue generated in pharmaceutical factories; an adhesion inhibitor hopper for storing and discharging an adhesion inhibitor consisting of at least one of resin sludge scraps, crushed PET bottle scraps, resin scraps, and organic particles obtained by low-molecular-weight treatment of high-viscosity organic sludge; a subcritical water treatment device having a material inlet and stirring the input material in a subcritical environment at a temperature of 170°C-250°C and a pressure of 2.0MPa-3.5MPa to low-molecular-weight the material; and a material input pipe for inputting the adhesion inhibitor from the adhesion inhibitor hopper into the material inlet from above. The above-mentioned problems are solved by an organic porous particle production system comprising: a high-viscosity screw pump that sends out the highly viscous organic sludge discharged from the highly viscous organic sludge hopper to the material input pipe; an organic porous particle storage tank that stores the organic porous particles discharged from the subcritical water treatment device after resin contained in the highly viscous organic sludge is broken down into smaller molecules; a branch discharge pipe that branches off from a discharge pipe extending from a treated product discharge outlet of the subcritical water treatment device to the organic porous particle storage tank; a centrifuge that separates a light liquid and a heavy component from the treated product discharged from the branch discharge pipe by centrifugal force; a recovered light liquid storage tank that stores the separated light liquid; and a heavy component re-introduction pipe that returns the separated heavy component to the material input pipe. Effect of the Invention

[0012] According to the present invention, highly viscous organic sludge such as oil sludge is mixed with an adhesion inhibitor consisting of resin sludge scraps, crushed PET bottle scraps, resin scraps, etc., and the mixture is stirred in a subcritical environment, thereby preventing the highly viscous organic sludge from adhering to the inner wall of a pressure vessel in a subcritical water treatment device, and the mixture is treated with subcritical water to produce a solid decomposition product in the form of organic porous particles. This has the effect of producing a material that can be used as a soil conditioner or water retention agent without generating any residue from the mixed highly viscous organic sludge and adhesion inhibitor.

[0013] In detail, the inventors' field tests have confirmed that this material improves the soil to an effective organic state by decomposing the oil sludge and resin-derived organic matter that composes the pores in the soil, using it as a nutrient source, while releasing the microbial organic matter into the ground.

[0014] Oil sludge and the like are difficult to treat, and so they have been left abandoned around the world for many years or simply dumped and accumulated in storage ponds. The present invention treats oil sludge and the like and returns it to the natural environment as organic materials, thus forming an organic material cycle. [Brief description of the drawings]

[0015] [Figure 1] FIG. 1 is a block diagram showing a system for producing organic porous particles according to an embodiment of the present invention. [Diagram 2] A 400x microscope photograph of organic porous particles (diameter 2 mm) produced by the system of this embodiment cut into 1 mm slices using a cutter, with the pores visible due to light transmitted from behind. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] An embodiment of the present invention will now be described with reference to FIG.

[0017] [Example 1] Example 1 is a system for producing organic porous particles for carrying out the method of the present invention.

[0018] First, the organic porous particle production system 10 will be described with reference to the drawings.

[0019] As shown in FIG. 1 , this organic porous particle production system 10 comprises a subcritical water treatment device 12, a highly viscous organic sludge hopper 14 equipped with a heating device 14A for storing highly viscous organic sludge, an adhesion inhibitor hopper 18 for storing an adhesion inhibitor, and a material feeding pipe 41 for feeding the highly viscous organic sludge from the highly viscous organic sludge hopper 14 and the adhesion inhibitor from the adhesion inhibitor hopper 18 into a material feeding port 12B of the subcritical water treatment device 12. While stirring with a stirring screw 12C in the subcritical water treatment device 12, high-temperature, high-pressure steam is added to bring the mixture into a subcritical state, and the highly viscous organic sludge and the adhesion inhibitor are reduced in molecular weight, discharged from a treated material discharge port 12A, stored in an organic porous particle storage tank 20, and transported to the outside from there.

[0020] The heating device 14A heats the crude oil sludge and the like in the highly viscous organic sludge hopper 14 using heat sources such as system exhaust heat such as boiler exhaust and compressed air exhaust heat in the subcritical water treatment device 12, boiler-generated steam, electricity, and the like.

[0021] In the organic porous particle production system 10 of Example 1, highly viscous organic sludge is mixed with an adhesion inhibitor, and the mixture is charged into a subcritical water treatment environment with the weight ratio of the adhesion inhibitor being 5%-80%, and then batch-treated in fixed amounts.

[0022] More specifically, the highly viscous organic sludge stored in the highly viscous organic sludge hopper 14 includes at least one of oil sludge discharged from the crude oil production, refining and transportation processes in the petroleum industry, including fats and oils and their solidified products, and highly viscous organic residues generated in pharmaceutical factories. In this embodiment, the crude oil sludge lumps excavated from the crude oil sludge storage pond 22 by the excavation heavy machinery transport device 24 are stored in the highly viscous organic sludge hopper 14 and heated by the heating device 14A, and then sent to the material input pipe 41 by the high-viscosity screw pump 16.

[0023] The adhesion inhibitor hopper 18 stores an adhesion inhibitor consisting of at least one of resin sludge scraps, crushed PET bottle scraps, and resin scraps, and is configured to be fed from here to the material feeding pipe 41 and then fed into the subcritical water treatment device 12 together with the highly viscous organic sludge fed by the high-viscosity screw pump 16.

[0024] In this example, the adhesion inhibitor was a resin filament made by processing a sheet-like PET resin into a filament shape.

[0025] The subcritical water treatment device 12 converts the materials fed through the material feeding port 12B into smaller molecules while stirring them with a stirring screw 12C in a subcritical environment of a temperature of 170°C-250°C and a pressure of 2.0 MPa-3.5 MPa.

[0026] In addition, in the subcritical water treatment device 12, the organic porous particles, which have been solidified from the input material after the subcritical water treatment, are discharged from the treated material discharge outlet 12A through the discharge pipe 42 to the organic porous particle storage tank 20.

[0027] Here, a large amount of low molecular weight oil may be discharged together with the generated organic porous particles, and in this case, the oil is sent to the centrifuge 28 from the branch discharge pipe 43.

[0028] The centrifuge 28 separates the liquid sent from the branch discharge pipe 43 into a light liquid and a heavy liquid.

[0029] The light liquid discharged from the centrifuge 28 is stored in a recovered light liquid storage tank 30 and, depending on its properties, is used for fuel oil or fractionation.

[0030] The heavy fraction discharged from the bottom of the centrifuge 28 passes through the heavy fraction re-introduction pipe 44 and is circulated again from the material introduction pipe 41 to the subcritical water treatment device 12 .

[0031] Here, before being discharged by the high-viscosity screw pump 16, the high-viscosity organic sludge is heated in the high-viscosity organic sludge hopper 14 equipped with a heating device 14A, causing oil (mostly light liquid) to be generated. This oil is then stored in the recovered oil storage tank 26 via the separated oil recovery pipeline 32, and from there it is transported according to its properties.

[0032] The organic porous particles stored in the organic porous particle storage tank 20 are discharged, or, if the decomposition into smaller molecules is insufficient, are circulated to the material input pipe 41 via the insufficient decomposition re-introduction pipe 46.

[0033] Experiments have shown that, in addition to resin filaments, resin sludge scraps, crushed PET bottle scraps, resin scraps, and organic porous particles that have been once depolymerized by the subcritical water treatment device 12 can also be used as adhesion inhibitors to prevent highly viscous organic sludge from sticking to the inner wall of the pressure vessel in the subcritical water treatment device 12.

[0034] As a result, the highly viscous organic sludge and the adhesion inhibitor were broken down into smaller molecules in a mixed state, and all of them became organic porous particles, with no residue being generated.

[0035] When the highly viscous organic sludge is a phenol-containing grease sludge and the adhesion inhibitor is a resin filament containing filament-like crushed PET bottle chips and resin chips, and when the phenol-containing grease sludge and the resin filament are mixed, the phenol-containing grease sludge is sprinkled with at least one of coal ash and fly ash before being mixed, the resin filament efficiently winds around the phenol-containing grease sludge, and the coal ash and fly ash do not adhere to the filaments but adhere to the parts of the phenol-containing grease sludge to which the filaments are not adhered, thereby efficiently achieving adhesion inhibition.

[0036] FIG. 2 shows a 400x microscope photograph of organic porous particles (diameter 2 mm) produced by the system of this embodiment, cut into 1 mm slices by a cutter, with the pores visible due to light transmitted from behind.

[0037] In this photo, we can see countless pores around the area that look like feathers, scattered light, and light transmitted through slightly larger holes.

[0038] When the organic porous particles once produced as described above are to be supplied as an adhesion inhibitor to an adhesion inhibitor hopper 18 from an organic porous particle recycling pipe 45, as shown in the lower part of Figure 1, the discharge outlet of the organic porous particle storage tank 20 can be connected to the organic porous particle recycling pipe 45, and the organic porous particles can be used in the adhesion inhibitor hopper 18 from here.

[0039] For example, when treating crude oil sludge in an oil field in the desert, it is difficult to transport resin sludge waste, crushed PET bottles, resin waste, etc. from far away, and the amount is large, so in such cases, it is advisable to use organic porous particles that have already been produced as all or part of the adhesion inhibitor.

[0040] In addition, crude oil sludge that settles in tanks of tankers, in addition to crude oil tanks, is usually disposed of near the port of discharge, so it is effective to use crushed plastic bottles, etc. as an adhesion inhibitor to also serve as a means of disposing of urban garbage.

[0041] The highly viscous organic sludge is mixed with an adhesion inhibitor, and the weight ratio of the adhesion inhibitor in the mixture is set to 5%-80% before being introduced into the subcritical water treatment environment, but as the properties vary greatly depending on the source, the actual ratio is determined by trial and error. However, if the ratio of highly viscous organic sludge exceeds 80%, it is difficult to make the sludge porous, and if it is less than 5%, the amount of adhesion inhibitor added is too small and it is not possible to prevent the adhesion of the highly viscous organic sludge.

[0042] The present invention is a manufacturing method that is good for the natural environment, as it returns to the circulation of organic matter such as oil sludge. In addition, the adhesion inhibitor itself is made of waste that is difficult to process, and by processing it, it becomes part of the natural circulation of organic matter to the natural environment, and is an effective solution to the problem of large amounts of waste that are currently causing blockages in the industrial sector. [Industrial Applicability]

[0043] It can be used in industries that process oil sludge and crude oil sludge to produce useful organic porous particles. That is, it can be used not only for waste treatment but also for industries that convert by-products as part of a plant for crude oil, etc. to produce useful organic porous particles.

[0044] The organic porous particles of the present invention can easily secure a large amount of growth space for microorganisms, and can be spread over a large area of ​​land to disperse and settle in the ground due to rainfall, etc. Even in areas with very poor rainfall, such as deserts, the pores and the microorganisms growing there can effectively retain moisture, allowing a system to be constructed that can appropriately supply plants with the moisture and organic matter they need. In this respect, there is a great advantage in that it can effectively re-introduce persistent oil sludge into the environmental organic matter circulation system. Because of its versatility and the fact that oil sludge is available as a material all over the world, it can also be expected to be used in climate change countermeasures systems. [Explanation of symbols]

[0045] 10...Organic porous particle manufacturing system 12...Subcritical water treatment equipment 12A…Processed material discharge port 12B…Material input port 12C...Mixing screw 14...Highly viscous organic sludge hopper with steam heating device (sludge hopper) 14A…Heating device 16…High viscosity screw pump 18…Adhesion inhibitor hopper 20...Organic porous particle storage tank 22...Crude oil sludge storage pond 24...Excavation heavy machinery transport device 26…Recovered oil storage tank 28…Centrifuge 30…Recovered light liquid storage tank 32…Separated oil recovery pipe 41…Material input pipe 42...Discharge pipe 43...Branch exhaust pipe 44... Heavy content re-injection pipe 45…Organic porous particle recycling pipe 46…Re-injection pipe for insufficient disassembly

Claims

1. A process of mixing a highly viscous organic sludge containing at least one of oil sludge discharged from the crude oil production, refining and transportation processes in the petroleum industry, including fats and oils and their solidified products, and a highly viscous organic residue generated in a pharmaceutical factory, with an adhesion inhibitor consisting of at least one of resin sludge scraps, crushed PET bottle scraps, resin scraps, and organic particles obtained by low molecular weight treatment of the highly viscous organic sludge, and introducing the mixture into a subcritical water treatment environment with the weight ratio of the adhesion inhibitor being 5% to 80%; Stirring and mixing the charged highly viscous organic sludge and the adhesion inhibitor in a subcritical environment at a temperature of 170°C to 250°C and a pressure of 2.0MPa to 3.5MPa; A step of maintaining the subcritical environment and stirring until the hydrophobicity of the oil and fat content and the fluidity of high temperature during the process of decomposing the resin contained in the high viscosity organic sludge into smaller molecules inhibits recombination and melting and solidification of the decomposed resin, and produces an organic porous particulate solid decomposition product having micropores with a diameter of 2 mm or less; A method for producing organic porous particles, comprising the steps of:

2. A process of mixing highly viscous organic sludge containing at least one of oil sludge discharged from the crude oil production, refining and transportation processes in the petroleum industry, which contains fats and oils and their solidified products, and highly viscous organic residue generated in pharmaceutical factories, with an adhesion inhibitor consisting of at least one of inorganic sludge containing silica components and oil sludge containing fats and oils and their solidified products in the residue of a heat-resistant sheet containing silica components, and introducing the adhesion inhibitor in the mixture into a subcritical water treatment environment at a weight ratio of 5% to 80%; Stirring and mixing the charged highly viscous organic sludge and the adhesion inhibitor in a subcritical environment at a temperature of 170°C to 250°C and a pressure of 2.0MPa to 3.5MPa; a step of maintaining the subcritical environment and stirring until, during the process of decomposing the resin contained in the charged highly viscous organic sludge into smaller molecules, the hydrophobicity of the oil and fat content and the fluidity of the high temperature suppress recombination and melting and solidification of the decomposed resin, and a solid decomposition product having a diameter of 2 mm or less containing organic matter and porous particulate silica components is produced; A method for producing organic porous particles comprising an organic substance and a silica component, comprising:

3. In claim 1, The highly viscous organic sludge comprises inorganic sludge containing silica components, and the organic porous particles comprise silica components and organic matter.

4. In claim 1, The highly viscous organic sludge is a phenol-containing oil and fat sludge, and the adhesion inhibitor is a filament-like resin filament containing crushed PET bottles and resin waste. When the phenol-containing oil and fat sludge and the resin filament are mixed, A method for producing organic porous particles, comprising the steps of: sprinkling at least one of coal ash and fly ash on the phenol-containing fat and oil sludge and then mixing the sprinkled at least one of coal ash and fly ash.

5. 5. An organic porous particle produced by the method for producing an organic porous particle according to claim 1, wherein the micropores have a diameter of 1 to 2000 Å, and at least a portion of the numerous micropores are densely distributed.

6. In claim 5, The organic porous particles are characterized in that, when the diameter exceeds 0.5 mm, the organic porous particles have a compressive strength such that they can be crushed by a human fingertip into fine powder having a diameter of 0.5 mm or less.

7. A high-viscosity organic sludge hopper for storing and discharging high-viscosity organic sludge including at least one of oil sludge discharged from the crude oil production, refining, and transportation processes in the petroleum industry, including fats and oils and their solidified products, and high-viscosity organic sludge generated in pharmaceutical factories; an adhesion inhibitor hopper for storing and discharging an adhesion inhibitor comprising at least one of resin sludge scraps, crushed PET bottle scraps, resin scraps, and organic particles obtained by subjecting highly viscous organic sludge to a low molecular weight treatment; A subcritical water treatment device having a material inlet for reducing molecular weight of the input material while stirring the input material in a subcritical environment at a temperature of 170°C to 250°C and a pressure of 2.0MPa to 3.5MPa; a material supply pipe for supplying the adhesion inhibitor from the adhesion inhibitor hopper to the material supply port from above; a high-viscosity screw pump that delivers the high-viscosity organic sludge discharged from the high-viscosity organic sludge hopper to the material input pipe; an organic porous particle storage tank for storing organic porous particles discharged from the subcritical water treatment device after resin contained in the high-viscosity organic sludge is broken down into smaller molecules; a branched discharge pipe branched from a discharge pipe extending from a treated product discharge port of the subcritical water treatment device to the organic porous particle storage tank; and a centrifuge that separates a light liquid and a heavy liquid from the treated material discharged from the branch discharge pipe by centrifugal force; a recovered light liquid storage tank for storing the separated light liquid; a heavy fraction reintroduction pipe for returning the separated heavy fraction to the material input pipe; A system for producing organic porous particles, comprising:

8. In claim 7, The organic porous particle production system is characterized by comprising: a separated oil recovery pipe connected to the middle of the material introduction pipe for discharging recovered oil separated from the introduced highly viscous organic sludge; and a recovered light liquid storage tank for storing liquid oil from the separated oil recovery pipe.

9. In claim 7 or 8, An organic porous particle manufacturing system characterized by having an organic porous particle recycling pipeline that sends the organic porous particles discharged from the organic porous particle storage tank to the adhesion inhibitor hopper as part or all of the adhesion inhibitor.

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