KR20210089967A - A Process for Producing Heavy Hydrocarbon Oils Having Less Odor Vapors and Harzardous Substances Using Used Oils' Distillation Residues - Google Patents

Abstract

The present invention relates to a method for removing substances causing hazardous components including a plurality of types of odors, fine dust and the like in the heavy oil fractions so as to prevent generation of hazardous components including odor, fine dust and the like, which can be generated in a process of using heated heavy oil fractions as a raw material. In addition, in removing vapor, including odor-causing and hazardous components, from heavy oil fractions, the present invention improves heavy oil fractions and provides a use place for used oil by using distillation residues generated during a used oil purification process. Heavy oil fractions treated according to the present invention can improve working conditions in industries of using heavy oil fractions as a raw material and can greatly reduce hazardous substance generation in the industries. In addition, heavy oil fractions improved according to the improving method do not largely affect the characteristics thereof as a heavy oil raw material since a small amount of low boiling point component is only separated and pyrolysis or chemical reaction of molecular structures in oil fractions does not dominantly occur. Furthermore, since refuse-derived fuel which is a low cost separated material generated in a used oil purification process is used as a dispersing agent for removing hazardous components of the heavy oil fractions, the present invention can improve economic feasibility of a heavy oil fraction improvement process and save costs for treating used oil.

Description

Technology for manufacturing heavy oil with reduced odor and harmful vapors using waste oil distillation residues {A Process for Producing Heavy Hydrocarbon Oils Having Less Odor Vapors and Harzardous Substances Using Used Oils' Distillation Residues}

The present invention relates to a method for reducing odor-causing and harmful components of heavy oil, and more specifically, after separating impurities such as solids and moisture from waste oil, hydrocarbon oil from the top stream of the distillation process The present invention relates to a method for reducing odor-causing substances and inhibitory substances in a heavy fraction by adding a distillation residue obtained by separation into a predetermined fraction to a heavy fraction and performing a reforming reaction.

Heavy oil refers to residual oil that is mainly composed of high-boiling hydrocarbons with an API level of 29 or less, which are obtained from nature or obtained from downstream processes in refining, petrochemical, and steel industries. The components in the heavy oil are located in the center in the form of an agglomerated form of highly polar asphaltenes, and the resin surrounds them to form a boundary layer from non-polar hydrocarbons to form a colloidal state of a core-shell structure, and the core- It is known that not only macromolecules such as high polarity resins and asphaltenes, but also a large number of various low-boiling-point chemicals are trapped in the shell-structured colloid.

Because of this structure, when the heavy oil is heated as in the subsequent process for utilizing the heavy oil, for example, in the heating process for producing asphalt, one of the heavy oil components, into asphalt, the low boiling point chemical trapped in the colloid of the core-shell structure As water is discharged at a limited rate, it causes environmental pollution such as odor, which is a major factor in causing environmental and social conflicts around industries where heavy oil is used.

Therefore, there is a need for a technical solution capable of fundamentally reducing the emission of air pollutants in a process using heavy oil as a raw material by removing environmental pollutants such as the odor from the heavy oil.

In relation to the technology for removing the odor-causing substances, US Patent No. 5271767 (published on February 21, 1993) discloses vegetable oil and D-limonene on asphalt to remove odors generated in the process of heating asphalt, which is a type of heavy oil. of the mixture, and silicone oil is introduced to disperse the vegetable oil and D-limonene.

In addition, Chinese Patent Laid-Open Patent No. CN 109651831 (published on April 19, 2019) discloses a technical configuration for removing odors by injecting odor removers including ethyoxyl steamide and tactifiers as dispersants and air cleaning agents into asphalt. have.

However, in the preceding documents, it is not a method of separating and removing odor-causing substances in advance, but a technique for suppressing evaporation of odor-causing substances by masking or adsorbing odors, and there is a point in removing harmful components including odors.

The present invention is a method of removing environmental pollutants from the heavy oil fraction, removing impurities of low utility value from waste oil, and performing a separation process such as distillation in a boiling point range similar to that of base oil corresponding to the majority of oil before use. It is intended to provide a technology that takes a fraction of the hydrocarbon fraction through the process and utilizes the residue concentrated at the bottom of the tower.

Waste oil usually does not contain food by-products such as waste cooking oil, oil containing high polychlorinated biphenyl, and other oil that is difficult to regenerate or recover into fuel oil through refining. Although there are differences by country, waste lubricating oil is generally discharged as more than 75% of the waste oil, and may include abrasive oil, cutting oil, fuel oil, asphalt oil, electrical insulating oil, grease, and rust preventive oil.

Since the waste oil is too environmentally harmful to be disposed of as it is, it is common to recover as much as possible a portion that can be recovered as fuel oil through a separation method such as distillation and then dispose of the waste oil.

In relation to the waste oil refining, in European Patent No. 0708174 (published on April 24, 1996), the waste oil from which moisture has been removed at 240 ° C. or less is distilled and the distillation residue is further separated by solvent extraction, followed by hydrotreating located at the rear end. ), an example of improving the yield and the quality of the recovered oil through the process is presented. U.S. Patent No. 9932530 (published on December 17, 2015) presents an example of a process for producing high-quality base oil from waste lubricating oil through one or a plurality of hydrogenation pretreatment reaction processes for waste oil from which moisture has been removed.

In the distillation residue remaining after recovering fuel oil and the like from the waste oil, most organic compounds or organometallic additives that are not thermally decomposed as well as high-boiling solid hydrocarbons and inorganic substances may be accumulated in the air stream at the bottom of the tower. Their boiling point distribution has a high boiling point characteristic similar to that of the reduced pressure residual oil generated at the downstream of the oil refining process, and since a high concentration of asphaltene dispersant remains, it is quantified and used as an additive for asphaltene dispersion. The present invention has been completed by focusing on the fact that it can be efficiently applied to the reforming process for reducing the odor of the powder and harmful substances.

U.S. Patent No. 5271767 (published on December 21, 1993) Chinese Patent Publication No. 109651831 (published on April 19, 2019) European Patent Registration No. 0708174 (published on April 24, 1996) US Registered Patent No. 9932530 (published on December 17, 2015)

In order to prevent the generation of harmful components including odors and fine dust that may occur in a process using heated heavy oil as a raw material, harmful components including a large number of odors and fine dust present in the heavy oil component are removed. It is intended to provide a method to remove the causative substances in advance.

In addition, the present invention provides a useful application of waste oil while reforming the heavy oil by using the distillation residue generated in the refining process of waste oil in removing odor-causing and harmful components from the heavy oil. would like to provide

In order to solve the above problems, the present invention comprises the steps of: (a) mixing a heavy oil with a waste oil-derived asphaltene dispersant to increase the dispersibility of asphaltene structures in the heavy oil; and (b) dispersing and supplying a carrier gas to the heavy oil of step (a), and then separating and degassing the odor-causing and harmful components in the heavy oil together with the carrier gas from the heavy oil to remove odor-causing and harmful components. It provides a method for producing a heavy oil having reduced odor inducing and harmful components, comprising:

In one embodiment of the present invention, the asphaltene dispersant derived from the waste oil is a distillation column residue after removing solids and moisture from the waste oil and recovering renewable hydrocarbons.

In the present invention, the API of the distillation column residue may be 5 to 30, and a novel asphaltene dispersant may be added and used in addition to the asphaltene dispersant derived from the waste oil. In addition, the content of the asphaltene dispersant derived from the waste oil may be 0.1 to 5% by weight.

In one embodiment of the present invention, the novel asphaltene dispersant contains both a polar group and a non-polar group, the dipole moment of the polar group is 1.1 diby or more, and the dipole moment of the non-polar group is 0.5 diby or less. can be

In one embodiment of the present invention, the method for manufacturing a heavy oil having reduced odor-causing and harmful components comprises (c) removing the odor-causing and harmful components from a carrier gas containing the odor-causing and harmful components separated and degassed from the heavy oil. It further comprises a step of separating the odor-causing and harmful components to separate, and the separated carrier gas can be recycled back to step (b) and reused.

In one embodiment of the present invention, the heavy oil may be asphalt.

In addition, the present invention includes a heavy oil reforming reactor comprising a heating means for heating the heavy oil stored therein, the carrier gas supplied to the inside is discharged to the outside together with odor-causing and harmful components in the heated heavy oil; a carrier gas supply unit for supplying a carrier gas into the heavy oil reforming reactor; a carrier gas dispersing unit for dispersing the carrier gas supplied from the carrier gas supply unit into the heavy oil reforming reactor; and a odor-causing and harmful component separation unit that separates odor-causing and harmful components from the carrier gas discharged from the heavy oil reforming reactor. Provides a heavy oil production system with reduced odor-causing and harmful components, comprising: .

In another embodiment of the present invention, the carrier gas circulation unit for re-supplying the carrier gas from which the odor-causing and harmful components are separated in the odor-causing and harmful component separation unit to the heavy oil reforming reactor; may further include .

In addition, the heavy oil reforming reactor may further include a demister for filtering the heavy oil particles contained in the carrier gas before the carrier gas is discharged to the outside of the heavy oil reforming reactor, and the odor-causing and harmful components The separation unit may use at least one of an adsorbent, a scrubber, a separation membrane, and a cooler to separate odor-causing and harmful components from the carrier gas discharged from the heavy oil reforming reactor.

Since the heavy oil treated according to the reforming method of the present invention is in a state in which harmful components that can cause harmful substances such as odor and fine dust contained in the oil are removed, the working environment in the industry using heavy oil as a raw material improvement and the generation of harmful substances in the industry can be greatly reduced.

Since only a small amount of low-boiling components are separated from the heavy fraction reformed according to the method of the present invention, and thermal decomposition or chemical reaction of molecular structures in the fraction does not predominantly occur, it does not significantly affect the properties of the heavy oil raw material.

In addition, in the present invention, since Refuse-derived Fuel, a low-cost separated product generated in the refining process of waste oil, is used as a dispersant for removing harmful components of the heavy oil, economic efficiency of the heavy oil reforming process and treatment of waste oil You can save money.

1 is a view for explaining a process of manufacturing an additive in a reforming process for reducing odor-causing and harmful components in heavy oil from waste oil in the present invention.
2 is a schematic diagram of the dispersion behavior of the asphaltene structure in the heavy oil when the asphaltene additive according to the present invention is added.
3 is a view for explaining a heavy oil production system for performing a method for manufacturing a heavy oil for removing odor-causing and harmful components according to an embodiment of the present invention.
4 is a comparison of the gas chromatograms measured under the same analytical conditions of the asphalt raw material used in Example 3 of the present invention and the oil vapor containing the odor-causing and harmful components generated after heating the asphalt after reforming to 180 ° C. it has been shown

Hereinafter, the present invention will be described in detail through preferred embodiments. Prior to this, the terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor appropriately defines the concept of the term in order to best describe his invention. Based on the principle that it can be done, it should be interpreted as meaning and concept consistent with the technical idea of the present invention. Accordingly, since the configuration of the embodiments described in this specification are only the most preferred examples of the present invention and do not represent all the technical spirit of the present invention, there are various equivalents and modifications that can be substituted for them at the time of the present application. It should be understood that

In the present invention, the term 'odor-causing and harmful ingredients' refers to all odor-causing substances and substances that do not cause odor but are harmful, and direct fine/ultra-fine dust (PM2.5 and PM10) during the asphalt concrete manufacturing process. ) and substances that generate the fine/ultra-fine dust.

In the present invention, by paying attention to the fact that odors or harmful components generated in the process in which heated heavy oil is applied as a raw material are generated from a low molecular weight compound included in a complex of heavy molecules including asphaltene, It relates to a method for producing a heavy oil in which odor-causing and harmful components are greatly reduced, which effectively removes vapors containing harmful components in advance.

As a representative example, the heavy fraction is a vacuum residue that is the bottom fraction of a vacuum distillation column (for example, obtained at about 25 to 100 mmHg and has an atmospheric pressure equivalent boiling point of about 813.15 K or more) during the crude oil refining process; It is one of the substances that are generated or finally left in the downstream of various industries, such as pyrolysis fuel oil generated in the petrochemical industry and coal tar generated from the dry distillation of coal, or exists in nature. Examples include asphalt or natural bitumen, which exist in a semi-solid or liquid state.

In particular, asphalt is widely used for road pavement and roof waterproofing materials. For road pavement, it is used in the form of asphalt concrete (ascon) in which aggregates such as sand and gravel are mixed with asphalt. In order to produce such asphalt, the asphalt, which is a heavy oil component, is heated and mixed with aggregate in a flowable state. At this time, the heated heavy oil component, that is, the asphalt, generates odor and harmful vapor components.

The odor-causing and harmful vapor components are mainly volatile organic compounds (VOCs), and the volatile organic compounds generated in the asphalt storage tank include polycyclic aromatic hydrocarbons (PAHs) including BTX, sulfides (thioethers (RSR`) or alkyl mercaptans ( R-SH), hydrogen sulfide, sulfide, etc.), various oxides (aldehydes, acetates, ketones), and other nitrogen compounds. In the present invention, it is possible to fundamentally block the generation of odor-causing and harmful vapor components in a process using the heavy oil as a raw material by removing the odor-causing and harmful vapor components in the heavy oil in advance.

The method for producing a heavy oil having reduced odor and harmful components according to the present invention comprises the steps of: (a) increasing the dispersibility of asphaltene structures in the heavy oil by mixing an asphaltene dispersant derived from waste oil with the heavy oil; and (b) dispersing and supplying the carrier gas into the heavy oil of step (a) and then separating and degassing the odor-causing and harmful components in the heavy oil together with the carrier gas to remove odor-causing and harmful components. step; characterized in that it includes.

The method for producing a heavy oil having reduced odor-causing and harmful components of the present invention further comprises, after step (b), (c) a separation step of separating and degassing the odor-causing and harmful components from the heavy oil from the carrier gas; can do.

The carrier gas from which the odor-causing and harmful components are separated is reused as a carrier gas for separating and degassing the odor-causing and harmful components in the heavy oil.

Hereinafter, the above steps will be described in detail.

When the additive is added in step (a) and mixed with the heavy oil, the asphaltene dispersant derived from the waste oil may be mixed with the heavy oil component heated above the temperature at which flowability occurs, and the asphaltene dispersant derived from the waste oil. After mixing, the heavy oil may be heated. At this time, the temperature at which the flowability occurs means the temperature at which the heavy oil is melted and the flow of the liquid phase starts to occur in the solid phase. After mixing the heavy oil and the asphaltene dispersant derived from the waste oil, agitation is performed if necessary so that the asphaltene dispersant is evenly dispersed in the heavy oil. In this case, agitation may be performed by means known in the art.

When a heavy oil is produced according to the method of the present invention, odor-causing and harmful components are degassed from the heavy oil using a carrier gas in a state in which the dispersion of constituent substances in the heavy oil is improved by the asphaltene dispersant derived from the waste oil. Therefore, it is possible to more effectively remove odor-causing and harmful components.

Hereinafter, the process of removing odor-causing and harmful components from the heavy oil according to the present invention will be described using the case where the heavy oil is asphalt as an example.

Asphalt is an organic raw material constituting asphalt, has adhesiveness, and has fluidity when heated above 80℃, but is a black or blackish-brown semi-solid substance with very high viscosity at room temperature. It is obtained from natural or petroleum refining processes and contains a large amount of high boiling point compounds. It contains heavy oil.

The oil is a mixture composed of a wide variety of chemical species in addition to high boiling point compounds, and its components can be broadly classified into SARA (Saturates, Aromatics, Resins, Asphaltenes).

Among the components, asphaltenes have a large molecular weight, high polarity, and constitute most of heteroatoms (sulfur and nitrogen) that can directly induce odors. In addition, as shown in the left side of FIG. 2, the components in the asphalt are located in the center in the form of agglomerated asphaltenes with high polarity, and the resin is limitedly surrounding them to form a boundary layer from non-polar hydrocarbons ( It is known to have a colloidal state of a core-shell) structure.

As such, when asphaltenes or the like form a cluster, it may be difficult to separate and degas the asphalt with a simple heating furnace because odor-causing and harmful components may exist in the cluster.

However, when the asphaltene dispersant extracted from the waste oil is added to the asphalt, the polar functional groups are aligned toward the polar material, and high dispersion of asphaltene can be induced according to the offset of the vector value representing the dipole moment. If it is dispersed without being present in the cluster, the odor-causing and harmful components present in the cluster can be easily degassed.

The asphaltene dispersant in the present invention may be prepared from a high boiling point residue obtained through a process of separating water and hydrocarbon fractions from waste oil. A process for obtaining the asphaltene dispersant from waste oil is shown in FIG. 1 .

In FIG. 1 , the feed waste oil 10 is subjected to a process 100 for physically separating solids through a physical method such as centrifugation or filtration. The separated solid content 11 is a solid material formed by mechanical friction or oxidation of oil, and may include macromolecular polymers, salts, metals, and the like. The waste oil stream 20 from which the solids are removed is water removed through the low temperature distiller 101 maintained at 240° C. or less, and is supplied to the high temperature distiller 200 through the tower downstream. When continuous processing of raw materials is not required, the removal of water and the separation of hydrocarbon fractions are possible in a single distiller according to temperature ranges with different boiling points.

In the high-temperature distiller 200, it is preferable to separate the oil having a boiling point distribution of 240°C to 590°C, and it is efficient to perform distillation under reduced pressure in order to reduce energy. At this time, the hydrocarbon vapor stream 40 at the top of the high-temperature distiller 200 is recovered 41 as a liquid fraction through the condenser 300, which may be used as an alternative fuel oil, regenerated base oil, etc. according to the characteristics of the fraction. The stream 50 at the bottom of the tower is a residue component containing a hydrocarbon fraction having a high boiling point, and distillation is performed so as to be 5 to 50% by weight based on the inputted waste oil.

The obtained stream 50 at the bottom of the tower may be used as it is as the asphaltene dispersant of the present invention, but if necessary, a new asphaltene dispersant may be additionally supplied 51 to have flowability at a temperature of 30° C. to 200° C. After mixing in the heated stirring tank 400, it can be obtained (60) in the form of a well-dispersed mixed additive.

The novel asphaltene dispersant includes a polarity additive containing both polar groups and non-polar groups.

The polarity additive preferably has a polar group having a dipole moment of 1.1 Debye or more and a non-polar group having a dipole moment of 0.5 Debye or less in the same molecule, and these groups are structurally symmetrical to obtain a net dipole moment It is preferred that no offset occurs. The net superpole moment is preferably 0.6 diby or more. Since the raw material to which the additive is applied is a heavy oil having hydrophobic properties, it is preferable that the material itself has hydrophobicity or oil soluble properties.

More specifically, the dipole moment of the polar group may be, but is not limited to, 1.1 diby or more, or 1.1 diby to 10 diby, 1.1 diby to 7 dibi, 1.1 diby to 5 dibi, or 1.1 diby to 3 diby. The dipole moment of the non-polar group has a value close to zero by definition, but is not limited thereto, but may be 0.5 diby or less, 0.1 diby or less, or 0.01 diby or less, depending on the relative strength of the dipole moment of the polar group. The net dipole moment of the bipolar additive may be, but is not limited to, 0.6 diby or more, and may be 0.6 diby to 10 dibi, 0.6 diby to 5 dibi, or 0.6 diby to 2 diby.

The polar group of the polarity additive may be exemplified by a functional group derived from nitrogen or oxygen, and the non-polar group may have a linear or polydispersity index (PI; Mw/Mn) close to 1 in the form of a polymer chain hydrocarbon or An example of a structure derived from It is preferable that the bipolar additive does not affect the properties or functions of the heavy oil, and it is preferable that the dispersion effect of the polar molecules in the heavy oil is prominent even when a small amount is used compared to the raw material. It is a substance that is well dispersed throughout the heavy oil but does not have a strong mutual attraction to polar molecules (eg, a lipophilic dispersion catalyst), or a substance that has both hydrophilicity and hydrophobicity (eg, an interface). activators) can be distinguished. The polar functional group and the non-polar functional group may be in a form in which they are directly bonded, or may be in a form modified by a connecting group or link.

The bipolar additive is, for example, selected from a single molecule or a polymer consisting of single or multiple combinations of amines, imides, amides, alcohols, phenols, esters, methacrylates, and the like. A homo-polymer derived from at least one polar group and ethylene, propylene, isobutylene, diene, styrene and having a number average molecular weight of 100 to 500,000 Or it may be prepared in the form of a polymer consisting of a combination of one or more non-polar groups selected from among copolymers (co-polymer).

Specifically, the amphipathic additive may include polyalkylene succinic acid imide; alkyl phenolic dispersants; polyacrylic dispersant; Urea, imidazoline, imidazole, tetrazole, tetrazoline, tetrazolon, lactam, sultam, thiourea, triazole, triazoline, pyridone, pyrimidone, dihydropyrimidine, tetrahydropyrimidine, pyrazole, imidazoline, dihydropyrimidinone, triazine, dihydrotriazine, tetrahydrotriazine, oxadiazole, thiadiazole, dihydrooxadiazole, dihydrothiadiazole, salicylate, etc. A polymer comprising at least one of a prominent polar head group; It may include at least any one or more of.

The asphaltene dispersant derived from waste oil prepared according to the present invention is a bottom residue obtained from the distillation process of waste oil, and may correspond to 5 to 50% by weight based on the inputted waste oil, and the API degree may be 5 to 30. . The obtained bottom residue is used as an additive for high dispersion of asphaltenes by mixing with the heavy oil at a temperature range of 30° C. to 200° C. where the flowability of the heavy oil can be maintained after or without the pre-treatment. When the dispersing performance is insufficient only with the asphaltene dispersant derived from the waste oil, it is indicated in FIG. 1 that the additional novel asphaltene dispersant is mixed in the stirring tank 400 in advance, but in the reforming reactor of the heavy oil, the flowability of the heavy oil is The reforming reaction may be performed after mixing the waste oil-derived asphaltene dispersant and the new asphaltene dispersant together with the heavy oil in a temperature range of 30° C. to 200° C. that can be maintained. The asphaltene dispersant derived from the waste oil is mixed with the heavy oil, and the amount of the asphaltene dispersant may be 0.1 wt% to 5 wt% of the total mixture. If the content of the asphaltene dispersant is less than 0.1% by weight, the polar molecules in the raw material may not be sufficiently dispersed, and thus the effect may be insignificant. If the content of the asphaltene dispersant is present in excess of 5% by weight, the physical properties of the heavy oil raw material after reforming are largely As it is different, the specification characteristics of the raw material may be lost.

On the other hand, in the reforming method for separating odor-causing and harmful components, the step (b) comprises dispersing and supplying a carrier gas as the heavy oil of step (a), and then removing the odor-causing and harmful components in the heavy oil together with the carrier gas. It is a step to remove odor-causing and harmful components by separating and degassing from heavy oil.

The duration of step (b) is continued until the target removal amount of odor-causing and harmful components in the heavy oil is reached. The duration may vary depending on the amount of heavy oil and the amount of carrier gas supplied, but in general, it may last for 1 to 24 hours.

More specifically, the step (b) comprises the steps of (b-1) heating the heavy oil in which the asphaltene dispersant derived from the waste oil is mixed with the dispersant to a reforming set temperature; (b-2) a carrier gas supply step of dispersing and supplying the carrier gas into the heated heavy oil; and (b-3) discharging the odor-causing and harmful components in the heavy oil degassed by the carrier gas together with the carrier gas.

The reforming set temperature range in step (b-1) may be appropriately set according to the type of heavy oil used or the surrounding environment. The reforming set temperature is preferably in the range above the temperature at which the flowability of the heavy stream to be reformed occurs and below the temperature at which the components of the heavy stream begin to thermally decompose, and more preferably, a process using the heavy stream as a raw material. It is in the range above the process operating temperature and below the denaturation temperature of the heavy oil.

As the carrier gas of (b-2), an inert gas is usually used, but air may be used in a closed system.

The step (b-3) is a discharging step of discharging odor-causing and harmful components in the heavy oil together with the carrier gas to the outside of the reforming reactor in which the heavy oil is reformed. When the carrier gas is discharged to the outside of the reforming reactor in (b-3) above, if necessary, the fine particles of the heavy oil accompanying the carrier gas may be collected using a demister or the like.

Thereafter (c) separating the odor-causing and harmful components from the carrier gas containing the odor-causing and harmful components separated from the heavy oil and separating the odor-causing and harmful components from the carrier gas; may further include; The carrier gas from which the hazardous components are separated can be returned to step (b) and reused.

In addition, the present invention provides a manufacturing system for producing a heavy oil having reduced odor inducing and harmful components.

The manufacturing system of the present invention includes a heating means for heating the heavy oil stored therein, and a heavy oil reforming reactor in which the carrier gas supplied therein is discharged to the outside together with odor-causing and harmful components in the heated heavy oil; a carrier gas supply unit for supplying a carrier gas into the heavy oil reforming reactor; a carrier gas dispersing unit for dispersing the carrier gas supplied from the carrier gas supply unit into the heavy oil reforming reactor; and an odor-causing and harmful component separation unit for separating odor-causing and harmful components from the carrier gas discharged from the heavy oil reforming reactor; is comprised of

In addition, the production system of the present invention may further include a carrier gas circulation unit for re-supplying the carrier gas from which the odor-causing and harmful components are separated in the odor-causing and harmful component separation unit to the heavy oil reforming reactor; , The heavy oil reforming reactor may further include a demister for filtering the heavy oil particles contained in the carrier gas before the carrier gas is discharged to the outside of the heavy oil reforming reactor.

The odor-causing and harmful component separation unit is for separating odor-causing and harmful components from the carrier gas, and uses at least one of an adsorbent, a scrubber, a separation membrane, and a cooler from the carrier gas discharged from the heavy oil reforming reactor. It can separate odor-causing and harmful components.

3 is a view for explaining a system for manufacturing a heavy oil having reduced odor inducing and harmful components according to an embodiment of the present invention.

As shown in FIG. 3, the heavy oil production system with reduced odor and harmful components according to the present invention includes a heavy oil reforming reactor 100, a carrier gas supply unit 120, a carrier gas dispersion unit 110, It is configured to include a malodorous component and a harmful component separation unit 130 , and may further include a carrier gas circulation unit 140 .

In the heavy oil reforming reactor 100, a heavy oil raw material is located in an internal space, and a heating means 103, a carrier gas inlet 101 and It is configured to include a carrier gas outlet (102).

More specifically, in the heavy oil reforming reactor 100 , a mixed solution is added after quantifying and adding a waste oil-derived asphaltene dispersant to the heavy oil raw material in advance, or the heavy oil raw material and waste oil-derived asphaltenes are introduced into the reforming reactor 100 . After the dispersant is added together, the heavy oil mixture positioned therein is heated by the heating means 103 . In the heated heavy oil mixture, the separation and mass transfer of low-boiling components from the colloidal phase inside the heavy oil component are promoted by heat, which is again transferred in vapor phase by the carrier gas supplied into the reforming reactor 100 . Oil vapor containing odor-causing and harmful components degassed from the inside of the fluidized heavy oil is continuously discharged to the outside of the reactor by the carrier gas. At this time, since asphaltenes in the heavy oil are highly dispersed by the asphaltene dispersant derived from the waste oil, the separation of odor-causing and harmful components can be further accelerated. In addition, in the heavy oil reforming reactor 100 , in providing reforming conditions by the heating means 103 , while the heavy oil maintains flowability, the characteristic change of the heavy oil does not predominantly occur, and the heavy oil It is advantageous to keep it in a range below the maximum temperature that can function as a Preferably, by heating the reforming temperature of the heavy oil component to a temperature higher than a set required temperature in the process in which the heavy oil component is used as a raw material, oil vapor (odor-causing and harmful ingredients) can be removed in advance. If the reforming of the heavy oil is carried out at a high temperature, the degree and removal rate of odor-causing and harmful components may be increased, but since many hydrocarbons constituting the heavy oil may be decomposed and denatured, the dominant thermal decomposition does not occur, but odor-causing and It should be maintained at a temperature high enough to allow physical degassing of low-boiling-point components constituting harmful components.

The duration of the reforming reaction is continued until the target removal amount of odor inducing and harmful components is reached. The duration may vary depending on the amount of heavy oil to be reformed and the amount of carrier gas supplied, but in general, it may last for 1 to 24 hours.

The carrier gas supply unit 120 is a means for supplying a carrier gas into the heavy oil reforming reactor 100 , and may be configured using a conventional technique in the technical field to which the present invention pertains. When oxygen is included in the selection of the carrier gas, a characteristic change may occur due to a partial oxidation reaction of the heated raw material. Therefore, in order to prevent oxidation of the heavy oil, it is preferably an inert gas without activity, and may be mainly composed of helium, argon, nitrogen gas, etc., but before the reforming process is applied, rather than continuously supplying during the reforming process, or Air may be used if it is provided as a one-time supply at an early stage and is recirculated in a closed system. As the carrier gas supply unit 120, a device such as a pressure vessel capable of storing high-pressure gas may be used.

In addition, the carrier gas dispersion unit 110 disperses the carrier gas supplied into the reforming reactor 100 over a wide area, whereby the carrier gas dispersed into the heavy oil reforming reactor 100 is dispersed in the oil. As it is evenly dispersed and bubbled, it is possible to more effectively transport and discharge oil vapor including odor-causing and harmful components that vaporize inside the heavy oil to the outside of the reforming reactor.

As described above, the carrier gas transports and transports oil vapor containing odor-causing and harmful components that are vaporized from the inside of the heavy oil, thereby forming a colloidal phase with macromolecules such as asphaltenes and resins with high polarity, and degassing from the heavy oil. It is possible to remove the harmful components that do not occur easily and can be separated in a very limited rate and only a part of the composition even at high temperature in a process meaningful time.

To this end, the dispersing unit 110 has a form of a distributor having a plurality of perforated holes, and a form composed of a plurality of orifice nozzles from a single carrier gas supply coil (sparger). It may be configured using at least one or more means of dispersing means.

The flow rate of the carrier gas injected from the carrier gas dispersion unit 110 may vary depending on the type of heavy oil, but 0.05 to 90 sccm/(g of feedstock), preferably as a ratio of the standard state flow rate per unit mass of the heavy oil material can be 0.1 to 10 sccm / (g of feedstock).

On the other hand, the heavy oil reforming reactor 100 may additionally include a demister 104 therein, and using the demister 104, before the carrier gas is discharged to the outside of the heavy oil reforming reactor 100 . Excessive loss of high-boiling-point components can be prevented from filtering particulates that may be included in the carrier gas or from boiling of raw materials that may occur during the reforming process.

In addition, the odor-causing and harmful component separation unit 130 for separating the odor-causing and harmful components separates or decomposes and removes the odor-causing and harmful components from the carrier gas discharged from the reforming reactor 100, and the adsorbent , an oxidizer, a scrubber, a separation membrane, and at least one of conventional separation means such as a cooler to remove oil vapors containing odors and harmful components from the carrier gas discharged from the reforming reactor 100 .

More specifically, the odor-causing and harmful component separation unit 130 absorbs odor-causing and harmful components in the carrier gas using a scrubber, adsorbs them using a catalyst or an adsorbent, or liquefies them using a cooler. In this way, it is possible to separate and remove oil vapors containing odor-causing and harmful components in the carrier gas.

In the present invention, in adsorbing odor-causing and harmful components using an adsorbent among the separation means as described above, a spent catalyst may be used. As the spent catalyst used at this time, an alumina-based or zeolite-based catalyst discharged from the chemical industry may be used.

In addition, the odor-causing and harmful component separation unit 130 may include an outlet for continuously discharging the separated odor-causing and harmful components.

In addition, the carrier gas circulation unit 140 re-supply the carrier gas from which the oil vapor has been separated or removed in the odor-causing and harmful component separation unit 130 to the reforming reactor 100, and the transport through the configuration. Since the carrier gas supplied by the gas dispersing unit 110 is not discharged to the outside of the system, it is possible to circulate the reforming reactor 100 and the odor-causing and harmful component separation unit 130 by the carrier gas circulation unit 140 . There is no need to continuously receive a carrier gas from the outside, and even if air is used as a carrier gas, oxygen present in the air at the beginning of the carrier gas circulation process is consumed for the reaction with the raw material, and only nitrogen exists, so only air is applied as a carrier gas Even so, the performance and effect of the modification according to the present invention may be exhibited.

In the present invention, when the heavy oil is asphalt, and the asphalt is used as a raw material for asphalt, the heavy oil production method with reduced odor and harmful components of the present invention includes an asphalt concrete manufacturing process, for example, an asphalt concrete mixing part that mixes asphalt with aggregate. may be included.

Hereinafter, the present invention will be described in more detail through Experimental Examples, Examples and Comparative Examples.

<Experimental Example 1> Preparation of asphaltene dispersant from waste oil

From the waste oil purification process according to FIG. 1, the stream 30 in which impurities and moisture are separated was separated into a liquefied hydrocarbon fraction stream 41 and a distillation residue stream 50 through high-temperature distillation. Waste oil was separated by taking the products of three refiners with different recovery areas and different impurity removal processes.

Waste oil 1 was prepared according to the physical filtration method using a filter to remove solids before the distillation step, waste oil 2 was prepared through centrifugation, and waste oil 3 was prepared by adding sulfuric acid as a coagulant, followed by salt precipitation and using a decanter. It is prepared by removing the sludge containing the precipitated salt.

After removing the moisture through a low-temperature distiller maintained below 240 ° C again, the waste oil from which the impurities have been removed is heated from 240 ° C to 10 ° C per minute to reach a boiling point of up to 590 ° C, but the input mass of the refined waste oil is Separation was performed so that the liquefied hydrocarbon fraction and the distillation residue were 80-90% and 10-20% by weight, respectively, as a reference. Samples 1 to 3 were prepared by taking the residue obtained from the waste oil 1 to 3 as the bottom stream through the distillation process, and the distillate obtained from the top stream was taken and prepared as Samples 4 to 6. Elemental analysis (Model Name: Thermo Scientific Flash 2000, Detector: Thermal Conductivity Detector), X-ray fluorescence analysis (Model Name: Thermo/ARL QUANT'X) for these samples ), inductively coupled plasma-atomic emission spectrometry (ICP-AES; model name: Thermo Fisher Scientific iCAP 6500Duo) was used, and ASTM D7169 (GC-Simdis) method was used for specific distribution, and the amount of recalcitrant residual carbon (Conradson carbon residue) was used. ; CCR) was analyzed using ASTM D189 method, and the results are shown in Table 1 below.

element distillation residue
(Residue at the bottom of the tower) liquid hydrocarbon fraction
(top distillate) sample 1
(wt%) sample 2
(wt%) sample 3
(wt%) sample 4
(wt%) sample 5
(wt%) sample 6
(wt%) C 79.5 81 79.5 85.3 85.5 85.3 H 12.1 12.6 12.1 13.7 13.9 13.7 O 3.2 1.6 2.1 - - - N 0.47 0.19 0.27 - - - S 0.94 0.58 0.91 0.08 0.05 0.08 Others 3.79 4.03 5.12 0.92 0.55 0.92

Referring to Table 1, it was confirmed that when the waste oil purified from impurities was distilled, each separated product obtained from the upper part and the lower part had a similar distribution of organic elements (C, H, O, N, S). The boiling point distribution of each of the top distillate and the bottom residue obtained from Sample 1 was analyzed according to ASTM D7169, and the results are shown in Table 2.

In Table 2 below, mass% represents the cumulative mass of components volatilized below each boiling point.

sample 1 sample 4 Boiling Point (℃) cumulative mass
(wt%) Boiling Point (℃) cumulative mass
(wt%) 192.1 IBP 200.0 0.53 231.8 IBP 250.0 0.59 250.0 0.67 300.0 0.61 300.0 1.90 350.0 0.66 350.0 6.14 400.0 0.94 400.0 25.94 450.0 2.72 450.0 66.85 500.0 11.28 500.0 91.90 550.0 47.18 550.0 98.70 600.0 77.99 585.1 FBP 650.0 93.79 700.0 99.36 702.8 FBP

* IBP: initial boiling point

** FBP: final boiling point

Looking at the boiling point distribution shown in Table 2, the top distillate has a relatively narrow boiling point distribution (230-585° C.), while the bottom residue (190-700° C.) has a relatively high and wide boiling point distribution. It can be observed that there is In particular, it can be seen that the residue at the bottom of the tower is composed of a large amount of hydrocarbon compounds corresponding to a boiling point of 500° C. or higher, similar to asphalt.

Most of the hydrocarbon compounds in the waste oil start from the base oil component of the oil before use, and the change in boiling point distribution may not be large because the hydrocarbon structure is maintained as a physicochemically stable hydrocarbon structure during the use process. Base oil is a high-boiling oil (reduced gas oil) obtained from crude oil. It is a colorless and transparent mineral oil or PAO (poly-α-olefin) obtained by isomerization after removing unsaturated double bonds or cyclic compounds through a refining process such as hydroprocessing. ), polyol esters, and synthetic oils such as wax cracking hydrocarbons are used. Therefore, in the distillation residue, the lower part of the column contains high-boiling hydrocarbons as a major component and the boiling point distribution is very similar to the boiling point distribution of heavy oils, so even if it is mixed as an additive, it does not significantly affect the change in the properties of the raw material. may not be

On the other hand, when using the lower portion of the tower as an asphaltene dispersant, if solid hydrocarbons such as coke are present in the residue at the lower portion of the tower, the viscosity or flowability of the heavy oil may be affected, and the lower portion of the residue may be affected. When measured by ASTM D189, if the residual carbon content is 50% or more, it may be difficult to use as an additive because the carbon content that can be solidified during heating is too high.

Table 3 shows the results of measuring the amount of hard-to-decompose residual carbon for the distillation residue in Experimental Example 1.

sample 1 sample 2 sample 3 CCR (wt%) 9.8 7.1 13.4

Referring to Table 3, it can be seen that the amount of hard-to-decompose residual carbon in the lower portion of the top obtained in Experimental Example 1 is only 13.4% even in the largest case, so that it can be used as an additive.

Meanwhile, X-ray fluorescence analysis was performed on the distillation residue to observe the types of inorganic components including transition metals active in the hydrocracking reaction, and the relative contents of the detected components are shown in Table 4.

element sample 1
(wt%) sample 2
(wt%) sample 3
(wt%) Na 17.2 22.6 0.0 Mg 1.5 0.0 0.0 Al 0.4 0.0 0.0 P 7.7 7.9 2.1 S 20.2 18.2 6.3 Cl 1.6 4.9 9.1 K 2.9 2.0 3.8 Ca 27.2 26.0 38.8 Fe 2.5 2.2 4.4 Cu 0.6 0.5 1.8 Zn 16.7 14.6 30.4 Br 0.3 0.2 0.2 Mo 1.4 1.1 3.0

Referring to Table 4, various cations (Na, Mg, K, Ca) resulting from additives of lubricants such as dispersants are included in large amounts. On the other hand, molybdenum, copper, iron, zinc, etc. corresponding to transition metals exist, and may be uniformly dispersed in the form of sulfides, phosphides, and halides that are effective for hydrocracking reactions as those derived from organometallic additives. These metals concentrated in the residue were quantified by ICP-AES analysis, and the determined contents are shown in Table 5.

element sample 1
(wppm) sample 2
(wppm) sample 3
(wppm) Mo 480 130 650 Cu 183 570 460 Fe 902 310 1,100 Zn 5,300 3,500 6,800

Each of the distillation residues quantified by the above analysis method was prepared as an asphaltene dispersant derived from waste oil, that is, an additive in the heavy oil reforming method for reducing odor and harmful vapors.

<Experimental Example 2> Measurement of asphaltene dispersion effect of asphaltene dispersant derived from waste oil

According to Experimental Example 1, the dispersion degree of asphaltenes was measured using Turbiscan (manufacturer: Formulation, model name MA2000) according to ASTM D7061-04 for each of the samples. ASTM D7061-04 is based on optically measuring the relative dispersion due to asphaltene precipitation or phase separation by adding n-heptane, a non-polar solvent, to a heavy oil dissolved in a polar solvent, and then converting it into a separability number for dynamic stability of the oil. It is a standardization method to evaluate stability. Separation water can be calculated as a standard deviation value for the change in average permeability measured every minute up to 15 minutes of stabilization time. As the raw material, AP-5 grade heavy oil supplied from Hyundai Oilbank was used, and in Experimental Example 1, the distillation residue (the residue at the bottom of the tower) was added to the heavy oil to 5,000 wppm, and the dispersion effect was observed. The measured values of separated water using the results are shown in Table 6.

additive-free sample 1 sample 2 sample 3 separated water 8.5 0.7 1.5 1.4

Referring to Table 6, in the case of AP-5 without the addition of additives, the stability of asphaltene is very low (dispersibility of asphaltene molecules is very low and sedimentation occurs), but 5,000 wppm of asphaltene dispersant derived from waste is used. When added, it can be seen that the stability of asphaltenes is greatly improved.

added concentration
(wppm) 0 1,000 2,000 3,000 4,000 5,000 8,000 10,000 separated water 8.5 7.0 6.4. 5.1 2.8 0.7 0.1 0.0

Table 7 shows the results of measuring the asphaltene dispersion of the heavy oil according to the added concentration of Sample 1 among the waste oil-derived additives of Experimental Example 1. Even when the additive was diluted to a concentration of 1,000 wppm or less, there was a partial effect of asphaltene dispersion, but when the concentration of the additive was 5,000 wppm or more, a very extreme asphaltene dispersion effect was observed.

<Experimental Example 3> Preparation and characterization of heavy oil raw materials

The heavy oil used in the evaluation of the reforming performance according to the present invention is an AP-5 grade asphalt supplied from SKE or Hyundai Oilbank and used as a raw material for asphalt concrete. The asphalt is in a solid state at room temperature. When analyzing the characteristics of the asphalt, measuring the amount of odor-inducing and harmful components, supplying it as a raw material for a reforming reaction, or adding an anode additive, put the asphalt in a previously sealed container and place it in an oven preheated to 80°C or higher. It was used after leaving it to stand for 3 hours or more to maintain flowability.

<Experimental Example 4> Analysis of odor-causing and harmful components generated from heated heavy oil (equilibrium composition method)

The collection and analysis of odor-causing and harmful components generated from heavy oil were carried out in a heated environment, such as the environment of the asphalt concrete manufacturing process, and 100 g of heavy oil was measured before or after reforming and placed in a 250ml flask maintained at 180°C. left for up to 5 hours. In the upper gas phase space (headspace) of the flask, there is oil vapor in a liquid state and equilibrium state, and after allowing the oil vapor to stay in a sample loop (1 ml) mounted on a 6-port valve heated to 180° C. or higher to prevent condensation, The flow path was changed at the time of measurement, and the retention characteristics of the components were analyzed by injecting it into gas chromatography (GC-MS; gas chromatography w/ mass spectrum detector and HP 50+ column) connected to a mass spectrum detector, and a flame ionization detector (FID) Quantitative analysis of each component was performed under the same analysis conditions (HP 50+ column) using a separate gas chromatography equipped with The concentration of gaseous components was calibrated using a Refinery Gas Analyzer (RGA; Agilent 5184-3538, 5184-3543) standard gas.

<Experimental Example 5> Heavy oil reforming reaction to induce odor and reduce harmful components

The asphalt of Experimental Example 4 was subjected to a reforming reaction using a high-temperature, high-pressure reactor (manufacturer: Ari Instrument, model: SCH reactor 500 w/ data gathering tool) that can be equipped with a 500 ml capacity SUS liner as a reforming reactor. . The reforming temperature was sensed using a thermocouple and was measured by inserting it into a thermowell to probe the temperature of the internal reforming reactor in close proximity. As for the internal reforming temperature, the heat source was supplied through a heating furnace where heat transfer can occur through the outer wall, and the temperature was maintained within ±1℃ during the reforming stage of the raw material using a multi-loop PID control program. It took up to 20 minutes to reach the reforming temperature from the initial temperature (80° C.), and reforming was performed by supplying a carrier gas from the time the target temperature was reached. The asphalt raw material used for the reforming reaction was heated to 80° C. or higher, 150 g was put into the reaction tank, the raw material was initially stirred at a speed of 50 rpm by a magnetic drive, and the stirring speed was changed to 300 rpm when the desired reforming temperature was reached. did.

As the carrier gas, nitrogen gas is initially provided from the outside, and after that, a gas transfer pump (model name: KNF N022ATE) was installed so that the initial gas could be continuously recirculated and supplied within a closed loop. The flow rate was controlled using a mass flow controller (mfc). The gas introduced into the reforming reactor was distributed and supplied using a porous gas dispersing pipe (sparger) located at the bottom.

Oil vapor and carrier gas are mixed from the upper part of the reactor and discharged in a mixed gas state. At this time, to prevent the loss of high boiling point oil in the reforming reactor, it was discharged through a demister made of SUS316.

The mixed gas discharged from the reforming reactor passes through the double-jacketed gas-phase condenser and the collection container designed to allow the cooling liquid of -10°C or lower to flow as an external pipe to liquefy only the oil vapor in the mixed gas, thereby concentrating and collecting the oil vapor. The separated inert carrier gas was configured to be re-supplied into the reactor through a gas transfer pump.

<Experimental Example 6> Modification of Daeyongrang asphalt

Using the reforming reactor constructed in the same principle as in Experimental Example 5, 15 kg of asphalt with reduced odor and harmful components in a large capacity was manufactured. A 50L Hastelloy-C high-temperature and high-pressure reactor (manufacturer Buchi Pilot Plant) was used as the reforming tank, and the heat source was supplied through thermal oil (Dowtherm RP) flowing through the outer wall of the reactor, and a gas transfer pump was used to control the flow rate. A large-capacity reforming reaction was performed in the same manner as in Experimental Example 6, except that an air compressor equipped with an air compressor (maximum flow rate of 20 L/min) was used, and the condenser was a shell & tube type heat exchanger. was carried out.

<Effect of reducing harmful vapors in raw materials before and after reforming by adding additives>

<Example 1>

5,000 wppm of asphaltene dispersant (sample 1 of Experimental Example 1) extracted from waste oil was added to 150 g of AP-5 grade asphalt supplied from SKE, and this was subjected to a reforming reaction according to the method of <Experimental Example 5> , The temperature of the reforming reactor was maintained at 230° C., nitrogen was used as a gaseous carrier gas, and reforming was performed for 6 hours while maintaining the flow rate of the gas at 200 sccm. Thereafter, the circulation of the carrier gas was stopped, and the temperature in the reforming reactor was brought to room temperature while the system was sealed.

<Example 2>

The same procedure as in Example 1 was performed except that 10,000 wppm of the asphaltene dispersant (sample 1 of Experimental Example 1) extracted from the waste oil in Example 1 was added.

<Comparative Example 1>

The same procedure as in Example 1 was performed except that no additives were added in Example 1.

In order to quantify the relative amount of oil vapor generated by the reforming reaction, samples before and after the reforming reaction were analyzed by the same measurement method according to <Experimental Example 4>, and the results of the concentration of oil vapor measured over time are shown in Table 8.

Equilibration time in Table 8 below means the time the flask was heated at 180° C. in <Experimental Example 5>, and the value measured for each equilibrium time is the total concentration of the oil vapor formed in the gaseous space in a mass ratio in parts per million It is converted in (wppm) units.

division before reform After reforming at 230℃ equilibrium time Raw material Example 1 Example 2 Comparative Example 1 0.0 0 0 0 0 0.5 61,338 1,124 1,216 12,157 1.0 75,574 4,230 2,978 12,713 1.5 75,466 4,900 3,466 13,107 2.0 75,398 5,123 3,383 13,392 2.5 76,634 5,739 3,629 13,016 3.0 81,649 5,953 3,690 13,810 3.5 79,481 5,892 3,708 13,897 4.0 75,980 6,105 3,700 14,038 4.5 78,591 5,864 3,693 14,373 5.0 77,313 5,793 3,733 14,481

Table 8 is a table comparing the amount of harmful vapors generated for raw materials before and after reforming according to the introduction of additives. In the case of the AP-5 raw material to which the reforming process was not applied, a high oil vapor concentration of 70,000 to 80,000 wppm was formed in the gas phase under the condition that the equilibrium composition was reached after 1 hour, but the heavy oil that went through the reforming process according to Experimental Example 5 It can be seen that the amount of oil vapor generated from the raw material is greatly reduced. When comparing the amount of oil vapor generated in the heavy oil reformed by adding 5,000 wppm (Example 1) and 10,000 wppm (Example 2) to the raw material to which no additives were added (Comparative Example 1) and the asphaltene dispersant extracted from waste oil, respectively, the additive It can be seen that the addition of is much more effective in reducing the amount of oil vapor generated. In particular, Example 2, in which the asphaltene dispersant extracted from the waste oil was added at a concentration of 10,000 wppm (Turbiscan measurement result according to ASTM D7061-04 of Experimental Example 2) so that the separated water value of the heavy oil was close to 0, and then reformed Example 2 It can be seen that the amount of oil vapor generated is reduced by about 1/20 compared to the raw material. This result is believed to be because an environment in which the low boiling point vapor components trapped in the aggregates of macromolecules can be selectively separated as the asphaltenes are highly dispersed is provided.

<Changes in properties of asphalt raw materials due to reforming>

Table 9 below is a table showing the difference in the element ratio composition of the asphalt raw material before reforming and the asphalt after reforming according to Comparative Example 1 and Examples 1 and 2. The constituent organic elements and their contents were analyzed using an elemental analyzer (model name: Thermo Scientific Flash EA-2000 Organic Elemental Analyzer, detector: Thermal Conductivity Detector). According to Table 9, it can be seen that the asphalts modified according to <Example 1>, <Example 2> and <Comparative Example 1> exhibit almost the same compositional ratio in element ratio as compared to that before reforming. In view of this, it can be predicted that the properties of the asphalt will not change significantly even by the modification according to the method of the present invention.

asphalt
Raw material classification Elemental Analysis N (wt%) C (wt%) H (wt%) S (wt%) O(wt%) H/C O/C before reform 0.6 84.1 10.1 5.1 0.4 0.121 0.005 Comparative Example 1 0.6 84.3 10.1 5.2 0.5 0.120 0.006 Example 1 0.6 83.8 10.0 5.3 0.5 0.120 0.006 Example 2 0.6 83.8 10.1 5.3 0.5 0.120 0.006

<Effect of reducing harmful steam generation due to large-capacity reforming>

In order to verify that the effect of reducing odor and oil vapor containing harmful components is the same in the large-capacity reforming process, an asphaltene dispersant extracted from waste oil was applied and large-capacity reforming was performed, and then the amount of oil vapor generation was compared and analyzed using similar analysis conditions. . In this experiment, AP-5 grade heavy oil with relatively high oil vapor generation was applied as a raw material, and the amount of oil vapor generated from heavy oil that had undergone a large-capacity reforming process was compared and analyzed based on the relative oil vapor generation amount with the raw material before reforming.

<Example 3>

The asphaltene dispersant derived from waste oil (Sample 1 of Experimental Example 1) was added to about 15.3 kg of AP-5 grade asphalt supplied from Hyundai Oilbank so as to be 5,000 wppm, and at the same time a similar asphaltene dispersion effect (when used alone in the same environment) After adding a small amount (500 wppm) of the organic additive ESCA (manufacturer: Emac Solution), which is known to have a separated water value measured by Experimental Example 2 is 1.0 or more), it is added to the method of <Experimental Example 6> According to the mass reforming reaction, the temperature of the reforming reactor was maintained at 230°C. As a gaseous carrier gas, the initial gas trapped inside the reforming tank was continuously supplied and used, and the recirculated flow into the reforming tank was supplied by concentrating and separating odors and harmful components at a low temperature by an external condenser. The raw material reforming was carried out for 6 hours while maintaining the flow rate of the gas at 5-20 slm. Thereafter, the circulation of the carrier gas was stopped, and the temperature in the reforming reactor was lowered to 120° C. or less in a closed system, and then the reformed heavy oil raw material was taken.

In order to quantify the relative amount of oil vapor generated by the reforming reaction, samples before and after the reforming reaction were analyzed by the same measurement method according to <Experimental Example 4>, and the results of the concentration of oil vapor measured by time are shown in Table 10, and before reforming The gas phase chromatogram of the oil vapor collected after continuously heating the raw material for 5 hours is shown in FIG. 4(a), and the gas phase chromatogram of the oil vapor collected under the same measurement conditions for the sample after reforming is shown in FIG. 4(b). .

Equilibration time in Table 10 below means the time the flask was heated at 180° C. in <Experimental Example 5>, and the value measured for each equilibrium time is the total concentration of the oil vapor formed in the gaseous space in the mass ratio in parts per million It is converted in (wppm) units.

division before reform
(wppm) after reforming
(wppm) equilibrium time Raw material Example 3 0 0 0 0.5 118,700 1,022 1.0 126,067 2,340 1.5 124,403 2,919 2.0 120,508 3,142 2.5 117,726 3,227 3.0 117,967 3,507 3.5 116,133 3,590 4.0 114,685 3,338 4.5 113,001 3,591 5.0 112,383 3,628

There was a big difference in the amount of oil vapor generated for heavy oil before and after reforming, and when the amount of oil vapor generated using mixed additives (asphaltene dispersant extracted from waste oil and asphaltene dispersant prepared by organic synthesis), the amount of oil vapor generated was modified It can be seen that it is reduced by about 1/30 compared to all raw materials. From this, it can be seen that the results explain that even the partial introduction of asphaltene dispersants derived from waste oil is effective in reducing odors and harmful substances.

Meanwhile, Table 11 shows the results of measuring the composition ratio of elements before and after large-capacity reforming. According to Table 11, the asphalt raw material modified in large quantities according to <Example 3> showed almost the same compositional ratio in element ratio as compared to before reforming, and the properties of the asphalt did not change significantly by the reforming according to the method of the present invention. It can be inferred that it will not.

Sample classification Elemental Analysis N (wt%) C (wt%) H (wt%) S (wt%) O(wt%) H/C O/C before reform 0.5 82.9 9.9 4.7 0.4 0.120 0.005 Example 3 0.5 83.1 9.9 4.8 0.5 0.120 0.006

As a result, it can be seen that the heavy oil reformed by the method according to the present invention has significantly reduced odor-causing and harmful components, and the properties of the heavy oil are hardly changed even by reforming.

Therefore, the process using the heavy oil produced according to the present invention as a raw material, for example, the asphalt concrete manufacturing process effectively suppresses odor-causing and harmful components that may occur in the asphalt concrete manufacturing process, while maintaining the same physical properties of the prepared asphalt concrete. it can be seen that

As described above, the present invention has been described with reference to Examples and Comparative Examples, which are merely exemplary, and those of ordinary skill in the art will understand that various modifications and equivalent other examples are possible therefrom. will be. Therefore, the technical protection scope of the present invention should be defined by the following claims.

Claims (12)

A method for reducing odor-causing and harmful components in heavy oil, the method comprising:
(a) increasing the dispersibility of asphaltene structures in the heavy oil by mixing a waste oil-derived asphaltene dispersant with the heavy oil; and
(b) removing odor-causing and harmful components by dispersing and supplying a carrier gas to the heavy oil of step (a) and then separating and degassing the odor-causing and harmful components in the heavy oil together with the carrier gas; A method for producing heavy oil with reduced odor and harmful components, comprising:
The method of claim 1,
The waste oil-derived asphaltene dispersant is a distillation column residue after removing solids and moisture from waste oil and recovering renewable hydrocarbons.
3. The method of claim 2,
The method for producing a heavy oil having reduced odor and harmful components, characterized in that the API of the distillation column residue is 5 to 30.
The method of claim 1,
A method for producing heavy oil with reduced odor and harmful components, characterized in that a novel asphaltene dispersant is added in addition to the asphaltene dispersant derived from the waste oil.
The method of claim 1,
The method for producing a heavy oil having reduced odor and harmful components, characterized in that the content of the asphaltene dispersant derived from the waste oil is 0.1 to 5% by weight.
5. The method of claim 4,
The novel asphaltene dispersant contains both a polar group and a non-polar group, the dipole moment of the polar group is 1.1 diby or more, and the dipole moment of the non-polar group is 0.5 diby or less. A method for manufacturing a heavy oil with reduced components.
The method of claim 1,
(c) separating the odor-causing and harmful components from the carrier gas containing the odor-causing and harmful components separated and degassed from the heavy oil; (b) A method for producing a heavy oil having reduced odor and harmful components, characterized in that it is recycled and reused in step (b).
The method of claim 1,
The heavy oil production method with reduced odor inducing and harmful components, characterized in that the heavy oil is asphalt.
a heavy oil reforming reactor comprising a heating means for heating the heavy oil stored therein, wherein the carrier gas supplied therein is discharged to the outside together with odor-causing and harmful components in the heated heavy oil;
a carrier gas supply unit for supplying a carrier gas into the heavy oil reforming reactor;
a carrier gas dispersing unit for dispersing the carrier gas supplied from the carrier gas supply unit into the heavy oil reforming reactor; and
an odor-causing and harmful component separation unit for separating odor-causing and harmful components from the carrier gas discharged from the heavy oil reforming reactor;
A heavy oil production system with reduced odor and harmful components comprising a.
10. The method of claim 9,
A carrier gas circulation unit for re-supplying the carrier gas from which the odor-causing and harmful components are separated in the odor-causing and harmful component separation unit to the heavy oil reforming reactor; Heavy Oil Manufacturing System.
10. The method of claim 9,
The heavy oil reforming reactor,
A heavy oil production system from which odor-causing and harmful components are removed, characterized in that it additionally includes a demister that filters the heavy oil particles contained in the carrier gas before the carrier gas is discharged to the outside of the heavy oil reforming reactor.
10. The method of claim 9,
The odor-causing and harmful component separation unit,
Manufacturing heavy oil with reduced odor and harmful components, characterized in that the odor-causing and harmful components are separated from the carrier gas discharged from the heavy oil reforming reactor using at least one means of an adsorbent, a scrubber, a separation membrane, and a cooler system.

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