KR102299697B1 - A process for producing asphalt having less odor vapors and hazardous substances using additives possessing both polar and non-polar functional groups - Google Patents

Abstract

The present invention relates to an asphalt manufacturing process from which odor-causing and harmful components are removed, comprising the steps of: (a) increasing the dispersibility of an asphaltene structure in asphalt by mixing an asphalt raw material and a bipolar additive; and (b) dispersing and supplying the carrier gas into the asphalt of step (a), and then separating and degassing the odor-causing and harmful components in the asphalt together with the carrier gas to remove the odor-causing and harmful components; It relates to an asphalt manufacturing process with reduced odor inducing and harmful components, characterized in that it comprises.

Description

Asphalt manufacturing process with reduced odor and harmful substances using bipolar additives

The present invention relates to a process for producing asphalt in which harmful substances such as odor and fine dust that may occur during the manufacture of asphalt concrete (hereinafter referred to as asphalt concrete) are greatly reduced.

In general, asphalt concrete is manufactured by heating and mixing aggregates such as gravel or crushed stone, additives, and low-grade asphalt generated in the downstream of the crude oil refining process under certain conditions, and is widely used as a road and construction material.

At this time, the substances discharged to the atmosphere in the asphalt concrete manufacturing process may include scattering dust generated from aggregates and some low-boiling-point components not separated during the crude oil refining process in asphalt, all of which fall under the category of fine dust.

The asphalt is an organic raw material constituting asphalt, has adhesiveness, and has fluidity when heated to 80° C. or higher, but is a black or dark brown semi-solid material having a very high viscosity at room temperature. It contains a large amount of high boiling point compounds obtained from natural or petroleum refining processes. Included.

In addition, asphalt is a mixture composed of a wide variety of chemical species in addition to high boiling point compounds, and impurities present in crude oil, such as sulfur, nitrogen, and heavy metals (nickel, vanadium, iron, etc.), are concentrated at a high concentration. Most of these exist in the form of heteroatoms or porphyrins in the molecular structure of hydrocarbons, and are known to form a colloidal phase with macromolecules such as asphaltenes and resins with high polarity.

Therefore, even if the boiling point of a specific component in the asphalt raw material is low, degassing may not easily occur from the oil having a high boiling point, and when the oil is heated to a high temperature as in the manufacturing process of asphalt, only a part of the composition is separated with a very limited speed.

Therefore, the amount of oil vapor or volatile organic compounds (VOCs) generated during the asphalt concrete manufacturing process can occur continuously and continuously. Oil vapors generated in the manufacturing process can be visually identified as they diffuse into the atmosphere, and are also called blue smoke because of their unique color. On the other hand, in the case of low molecular weight compounds containing sulfur or nitrogen content in the components, even a small amount causes a severe odor, and it is known that hydrocarbons in the form of polyaromatic hydrocarbons (PAHs) are very harmful.

In addition, the discharged oil vapor may contain a number of harmful substances having a characteristic of colorless and odorless, such as aromatic compounds or oxides such as aldehydes having a unique scent, and carbon monoxide. When these substances are continuously generated and diffused from the manufacturing process, they can cause direct or indirect air pollution, and can affect the quality of life and health of residents in neighboring residential areas other than the operation process workers. there is a need

On the other hand, the manufacturing process of asphalt concrete is divided into a batch type and a continuous type, and the continuous type is further divided into a forward and a reverse type. In both batch and continuous methods, the gravel is dried with a rotary dryer and then mixed with hot asphalt cement.

However, the batch type is different in that it is mixed in a hot bins and mixer, and the continuous type is mixed in a drum mixer. In the case of the batch-type asphalt concrete manufacturing process mainly used in Korea, oil vapor is mainly generated in the hot bins and mixer, a process in which gravel and asphalt raw materials are mixed with each other. It can occur both in the process of maintaining and moving as a road, and in the process of laying on the road.

In this series of processes, as the flow of materials progresses in the downstream direction, it becomes more difficult to control the diffusion of harmful substances such as odors and fine dust, and the range of diffusion can also be very wide. Methods other than reforming the raw material itself before the step cannot be a fundamental solution to block the diffusion problem of air pollutants.

Although air pollutants are discharged from a relatively narrow space at the asphalt concrete manufacturing facility, the rate of diffusion in the atmosphere is very fast, and if the asphalt concrete manufacturing process continues, the scope of pollution and the absolute diffusion amount of the pollutant will increase.

As a prior art, Korean Patent Laid-Open No. 10-2007-0037310 discloses a method of removing dust and odors by installing an intake fan that sucks odors generated inside the mixer during asphalt concrete production in order to remove odors and dust during the asphalt concrete manufacturing process. A method is described. In particular, a technology related to a mixer of an asphalt concrete plant and a dust and odor removal device using a dryer of an asphalt concrete plant that sucks and removes odors and dust generated in the process of putting asphalt in the loading box of a truck through the mixer's outlet are described. .

In Korean Patent Laid-Open No. 10-2012-0055321, by removing or minimizing other harmful dust emitted from the asphalt concrete manufacturing unit with one device, odor and dust are removed or minimized in one unit to remove or minimize the dust and odor generated during asphalt concrete manufacturing. Techniques for removing

In addition, in Patent Registration No. 10-1273329, it is possible to remove volatile organic compounds (VOCs) such as hazardous substances generated in the process of mixing AP oil and heated aggregates and loading asphalt on trucks in the manufacture of asphalt concrete. In particular, there is described a technology that can prevent environmental pollution in advance by removing or minimizing odors and dust, which are air pollutants or other harmful dusts generated when loading on a truck, in a short time as much as possible collectively.

However, the above prior art documents indicate the technology to remove odors and harmful substances generated during asphalt concrete manufacturing, mixing, and storage, but the range of preventing air pollution is very limited or uneconomical, It does not provide a fundamental solution to the air pollution problem.

Accordingly, the present inventors pay attention to the fact that harmful components including odor-causing and fine dust are generated from asphalt in the asphalt concrete manufacturing process, and are generated from the complex of heavy molecules including asphaltene among the components of asphalt raw materials. Manufacture of asphalt that effectively removes odor-causing and harmful components in advance, but does not change the properties of asphaltene while improving the performance and effect of removing odor-causing and harmful components by applying an additive capable of highly dispersing asphaltenes A method was developed and led to the present invention.

Korean Patent Publication No. 10-2007-0037310 (published on November 28, 2007) Korean Patent Publication No. 10-2012-0055321 (published on October 2, 2012) Korean Patent Registration No. 10-1273329 (2013.06.11. Announcement)

The present invention was created to solve the above problems, and by removing in advance low-boiling-point substances containing harmful substances such as a large number of odor-causing substances and fine dust present in asphalt, which is a raw material for manufacturing asphalt, a process for manufacturing existing asphalt, For example, it relates to a technology for fundamentally preventing the vaporization and air diffusion of harmful components, including odor-causing and fine dust, that may occur in each unit process maintained at a high temperature, such as a preheating unit and a mixing unit.

In addition, the present invention effectively disperses asphaltenes in asphalt using an anode additive in removing vapors containing odor-causing and harmful components of asphalt itself, and using a carrier gas distributor in the asphalt reforming reactor By continuously distributing and supplying an inert carrier gas in the asphalt reforming reactor, the odor-causing and harmful components that can be discharged from the heated asphalt are vaporized and separated from the asphalt, and the vaporized and separated odor-causing and harmful components are separated from the carrier gas at a low temperature. The purpose of this method is to remove in advance the odor-causing and harmful components that may occur during asphalt concrete manufacturing and road laying.

In order to achieve the above object, in one embodiment of the present invention, in the asphalt manufacturing process with reduced odor induction and harmful components, (a) asphaltene structures in asphalt used as asphalt raw materials by mixing a bipolar additive with asphalt increasing dispersibility; and (b) dispersing and supplying the carrier gas into the asphalt of step (a), and then separating and degassing the odor-causing and harmful components in the asphalt together with the carrier gas to remove the odor-causing and harmful components; It provides an asphalt manufacturing process with reduced odor inducing and harmful components, characterized in that it comprises.

In a preferred embodiment of the present invention, the polarity additive includes both a polar group and a non-polar group, the dipole moment of the polar group may be 1.1 diby or more, and the dipole moment of the non-polar group may be 0.5 diby or less.

In a preferred embodiment of the present invention, the amphiphilic additive may be in the form of a polymer having a number average molecular weight of 100 to 500,000.

In a preferred embodiment of the present invention, the polar group includes at least one selected from amine, imide, amide, alcohol, phenol, ester, and methacrylate. , The non-polar group may include a polymer derived from any one or combination of ethylene, propylene, isobutylene, diene, and styrene.

In a preferred embodiment of the present invention, the content of the bipolar additive may be 0.01 to 5% by weight.

In a preferred embodiment of the present invention, the amphipathic additive is 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, Any one or more of imidazoline, dihydropyrimidinone, triazine, dihydrotriazine, tetrahydrotriazine, oxadiazole, thiadiazole, dihydrooxadiazole, dihydrothiadiazole, and salicylate a polymer containing a polar head group; It may include at least any one or more of.

In a preferred embodiment of the present invention, the step (b) comprises the steps of: (b-1) heating the asphalt mixed with the bipolar additive to a reforming set temperature; (b-2) a carrier gas supply step of dispersing and supplying the carrier gas into the heated asphalt; (b-3) the odor-causing and harmful components in the asphalt are separated and degassed from the asphalt mixture together with the carrier gas;

In a preferred embodiment of the present invention, (c) separating the odor-causing and harmful components from the carrier gas containing the odor-causing and harmful components separated and degassed from the asphalt mixture; can do.

In a preferred embodiment of the present invention, the heating step may heat the asphalt to a temperature of 300° C. or less.

In a preferred embodiment of the present invention, the carrier gas may be an inert gas.

The present invention relates to an asphalt manufacturing process with significantly reduced odor and harmful components, and does not remove air pollutants in the mixing process of mixing asphalt with aggregate during the asphalt concrete manufacturing process or other downstream processes, but rather as a raw material of asphalt concrete. By remarkably reducing the amount of low-boiling vapors generated through the reforming of asphalt itself, it is possible to fundamentally block the emission and diffusion of harmful components including odor and fine dust or precursor compounds that can develop into them from the existing asphalt concrete manufacturing process. can have an effect.

In addition, the present invention effectively disperses asphaltenes in asphalt, which is an asphalt raw material, primarily by using an anode additive in removing vapors containing odor-causing and harmful components from asphalt raw materials, and secondarily in the reforming reaction tank. By supplying a carrier gas in a circulating method and continuously separating/removing only the oil vapor in the asphalt discharged together with the carrier gas, a process for producing asphalt with reduced odor and harmful components is provided.

In addition, the asphalt raw material modified according to the method of the present invention was separated from only a small amount of low-boiling component, and since thermal decomposition or chemical reaction of molecular structures in the oil did not predominantly occur, it has a characteristic that does not significantly affect the properties of asphalt raw material. have.

1 is a schematic diagram of the dispersion behavior of asphaltene structures in asphalt when the bipolar additive according to the present invention is added.
2 is a view for explaining an asphalt manufacturing system for performing an asphalt manufacturing process for removing odor-causing and harmful components according to an embodiment of the present invention.
3 is a graph observing the change in vapor pressure according to the reforming temperature of asphalt.
4 shows gas chromatograms of oil vapor containing odor-causing and harmful components before reforming the samples used in Comparative Examples 1 and 1 of the present invention.
5 shows a gas chromatogram of oil vapor containing odor-causing and harmful components after reforming the samples used in Comparative Examples 1 and 1 of the present invention.

Hereinafter, an asphalt manufacturing process from which harmful substances such as odors and fine dust are removed will be described in detail so that those of ordinary skill in the art can easily practice the present invention with reference to the accompanying drawings.

In each drawing of the present invention, the size or dimensions of the structures are enlarged or reduced than the actual size for clarity of the present invention, and well-known components are omitted to reveal the characteristic configuration, so it is not limited to the drawings. .

In the detailed description of the principle of the preferred embodiment of the present invention, if it is determined that a detailed description of a related well-known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted.

In the asphalt manufacturing process with reduced odor-causing and harmful components according to the present invention, odor-causing and harmful components are removed from asphalt, which is a raw material for ascon manufacturing, through reforming in the stage prior to manufacturing asphalt, so that the odor generated in the existing asphalt concrete manufacturing process The purpose is to fundamentally reduce substances containing causative and harmful components.

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 fine/ultra-fine dust (PM2.5 and PM10) in the asphalt concrete manufacturing process. also included.

The odor-causing and harmful vapor components in asphalt generated during the asphalt concrete manufacturing process are volatile organic compounds (VOCs). ), alkyl mercaptan (R-SH), hydrogen sulfide, sulfide, etc.), various oxides (aldehyde, acetate, ketones), and other nitrogen compounds.

The asphalt manufacturing process with reduced odor inducing and harmful components according to the present invention comprises the steps of: (a) increasing the dispersibility of asphaltene structures in asphalt, which is an asphalt raw material, by mixing a bipolar additive with asphalt; and (b) dispersing and supplying the carrier gas into the asphalt of step (a), and then separating and degassing the odor-causing and harmful components in the asphalt together with the carrier gas to remove the odor-causing and harmful components; characterized by including.

The process for producing asphalt with reduced odor-causing and harmful components of the present invention may further include, after step (b), (c) a separation step of separating and degassing the odor-causing and harmful components from the asphalt from the carrier gas; have.

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 from the asphalt.

Hereinafter, the above steps will be described in detail.

When the bipolar additive is mixed with the asphalt in step (a), the bipolar additive may be mixed while the asphalt is heated above the temperature at which flowability occurs, or the asphalt may be heated after mixing the bipolar additive. At this time, the temperature at which the flow property occurs means the temperature at which the asphalt is melted and the flow of the liquid phase starts to occur in the solid phase. In general, when the flow property is 80° C. or higher, the flow property occurs.

After mixing the asphalt and the bipolar additive, if necessary, stirring may be performed so that the bipolar additive is evenly dispersed in the asphalt. The stirring may be performed by means known in the art.

When asphalt is manufactured according to the process of the present invention, odor-causing and harmful components are degassed from the asphalt using carrier gas, etc. in a state in which the dispersion of constituent materials in the asphalt raw material, which is the asphalt raw material, is improved by the bipolar additive. , It is possible to more effectively remove odor-causing and harmful components from asphalt, a raw material for producing asphalt.

Ascon, the raw material of asphalt, is an organic raw material constituting asphalt, has adhesiveness, and has fluidity when heated to 80° C. or higher, but is a black or blackish-brown semi-solid material having a very high viscosity at room temperature. It is obtained from the refining process of natural or petroleum It is a heavy oil containing a large amount of point compounds.

The oil is a mixture composed of a wide variety of chemical species in addition to high boiling point compounds.

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 on the left side of FIG. 1, the components in the asphalt are located in the center in the form of agglomerated asphaltenes with high polarity, and the resin restrictively surrounds 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 by simple heating or the like because odor-causing and harmful components may exist in the cluster.

However, when the bipolar additive is added to the asphalt, the polar functional groups are aligned toward the material having polarity, and high dispersion of asphaltenes can be induced as shown on the right side of FIG. 1 according to the offset of the vector value representing the dipole moment. In addition, when asphaltenes are dispersed without being present in a cluster, odor-causing and harmful components present in the cluster can be easily degassed.

The polarity additive in the present invention means a material containing both a polar group and a non-polar group. 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 asphalt having hydrophobic properties, it is preferable that the material itself has hydrophobicity or oil soluble properties.

In more detail, the dipole moment of the polar group may be, but is not limited to, 1.1 diby to 10 diby, 1.1 diby to 7 diby, 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 0.01 diby or less, 0.1 diby or less, or 0.5 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 asphalt, and it is preferable that the dispersion effect of the polar molecules in the asphalt is prominent even when a small amount is used compared to the raw material. It is a material that is well dispersed throughout the asphalt but does not have a strong mutual attraction to polar molecules (e.g., a lipophilic dispersion catalyst), or a substance that has both hydrophilicity and hydrophobicity (e.g., surfactant). ) can be distinguished from 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 bipolar additive may be mixed with asphalt and used, but the amount of the bipolar additive may be 0.01% to 5% by weight relative to the mixture. If the content of the polarity additive is less than 0.01% by weight, the polar molecules in the raw material may not be sufficiently dispersed, and thus the effect may be insignificant.

On the other hand, in step (b), after dispersing and supplying the carrier gas into the asphalt of step (a), the odor-causing and harmful components in the asphalt are separated and degassed together with the carrier gas from the asphalt to remove the odor-causing and harmful components. is a step

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

More specifically, the step (b) comprises the steps of (b-1) heating the bipolar additive to a reforming set temperature; (b-2) a carrier gas supply step of dispersing and supplying the carrier gas into the heated asphalt; and (b-3) discharging odor-causing and harmful components in which the odor-causing and harmful components in the asphalt are separated and degassed from the asphalt mixture together with the carrier gas.

The reforming set temperature range in step (b-1) may be appropriately set according to the type of asphalt used or the surrounding environment. The reforming set temperature is preferably in the range above the temperature at which the flowability of the asphalt to be reformed occurs, and below the asphalt transformation temperature at which the components of the asphalt begin to thermally decompose, more preferably above the production temperature of conventional asphalt, asphalt It is below the denaturation temperature.

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

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

2 is a view for explaining a system for producing asphalt with reduced odor inducing and harmful components according to an embodiment of the present invention.

As shown in FIG. 2 , the asphalt manufacturing system according to the present invention includes an asphalt reforming reactor 100 , a carrier gas supply unit 120 , a carrier gas dispersion unit 110 , and a odor component and harmful component separation unit 130 . Is configured to include, and may be configured to further include a carrier gas circulation unit (140).

In the asphalt reforming reactor 100, an asphalt raw material is located in an internal space, and a heating means 103, a carrier gas inlet 101, and a carrier gas outlet in order to degas substances containing odor-causing and harmful components from the positioned asphalt. (102) is included.

More specifically, in the asphalt reforming reaction tank 100, the bipolar additive is pre-quantified and added to the asphalt raw material, or the asphalt mixture is added to the reaction tank together with the raw material, and then positioned inside by the heating means 103. The asphalt mixture is heated. The heated asphalt mixture promotes the separation and mass transfer of low-boiling components from the colloidal phase inside the raw material, which is then transferred to the vapor phase by the carrier gas supplied therein. Oil vapor containing odor-causing and harmful components from the inside of the fluidized asphalt raw material is continuously discharged to the outside of the reactor by the carrier gas. At this time, since asphaltenes in asphalt, which are raw materials for asphalt, are highly dispersed by the bipolar additive, the separation of odor-causing and harmful components is further accelerated.

In addition, in the asphalt reforming reactor 100, in providing the reforming conditions by the heating means 103, while the asphalt maintains flowability, the characteristic change of the asphalt does not predominantly occur, and asphalt for asphalt It should be maintained in a range below the maximum reforming temperature that can function as a Preferably, by heating the asphalt reforming temperature above the set temperature of asphalt during asphalt concrete production, oil vapors that may be generated in the asphalt concrete manufacturing process or the site utilizing the same are removed in advance.

If the reforming is carried out at high temperature, the removal degree and removal rate of oil vapor can be increased, but since many hydrocarbons constituting the asphalt raw material are decomposed and modified and cannot be applied as a raw material for the asphalt concrete manufacturing process, the dominant thermal decomposition does not occur, but the physical The temperature should be maintained high enough to allow degassing.

The duration of the reforming reaction is continued until the target removal amount of oil vapor is reached. The duration may vary depending on the amount of asphalt to be reformed and the amount of carrier gas supplied, but may generally last for 1 to 24 hours.

The carrier gas supply unit 120 supplies a carrier gas to the inside of the asphalt reforming reactor 100, and when oxygen is included in selecting the carrier gas, the characteristics change due to partial oxidation of the heated raw material. can happen Therefore, it is preferable to use an inert gas with no activity in order to prevent asphalt oxidation, and may be mainly composed of helium, argon, nitrogen gas, etc. It is okay to use the air in the form of recirculation in a closed system by providing it once to the air conditioner.

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 dispersing unit 110 is to disperse the carrier gas supplied from the carrier gas supply unit 120 into the asphalt reforming reactor 100 over a wide area, whereby the asphalt reforming reactor 100 As the carrier gas dispersed inside the oil is evenly dispersed and bubbled, the oil vapor including harmful components and causing odors vaporized from the inside of the asphalt is transported and discharged to the outside of the reforming reactor at a faster speed by the carrier gas. It can improve the removal effect of causative and harmful substances.

As such, the carrier gas transports and transports oil vapor including odor-causing and harmful components that are vaporized from the inside of the asphalt, so that it forms a colloidal phase with macromolecules such as asphaltene or resin with high polarity, so that degassing from the oil does not occur easily. And even at high temperature, it is possible to remove the harmful components in a very limited rate and only a part of the composition in a fair and 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 is 0.05 to 90 sccm/(g of feedstock), preferably 0.1 to 10 sccm/(g of feedstock) as a ratio of the standard state flow rate per unit mass of the raw material. .

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

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 asphalt reforming reactor 100, By using at least one or more of the conventional separation means such as an adsorbent, an oxidizing agent, a scrubber, a separation membrane, and a cooler, oil vapors containing odors and harmful components are removed from the carrier gas discharged from the asphalt 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, in addition to separating and removing odor-causing and harmful components, applies an oxidation catalyst to induce odor generated from the carrier gas discharged from the asphalt reforming reactor 100 and It may also be configured to directly chemically convert substances containing hazardous components into substances with less hazardous or higher boiling points.

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-supplying 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 asphalt reforming reactor 100, the carrier gas dispersing unit The carrier gas supplied by 110 is not discharged and circulates through the asphalt reforming reactor 100 and the odor-causing and harmful component separation unit 130 by the carrier gas circulation unit 140 .

As such, the carrier gas is not consumed and may be used while being continuously recirculated by the circulation unit 140 . When the carrier gas circulation unit 140 is used in the asphalt manufacturing system from which the odor-causing and harmful components are removed according to the present invention, the carrier gas does not need to be continuously supplied from the outside by the carrier gas circulation structure as described above, and the carrier gas Even if air other than an inert gas is used as a gas, the amount of oxygen present in the air at the beginning of the carrier gas circulation process is very limited. Since it is supplied in a form having

In addition, the oil vapor and inert gas of low boiling point components that can occur in the asphalt concrete process exist only in the closed flow, and the oil vapor is separated and induced in the form of a concentrated phase from the phase change according to the equilibrium temperature. and generation of harmful components does not occur.

In addition, the asphalt manufacturing process with reduced odor inducing and harmful components according to another embodiment of the present invention may include an asphalt concrete manufacturing process, for example, an asphalt concrete mixing unit for mixing asphalt with aggregate.

Hereinafter, details of the process of the present invention will be described through experimental examples, examples and comparative examples.

< Experimental example 1> Asphalt raw material preparation and characterization

As the asphalt raw material used to evaluate the reforming performance, AP-5 grade heavy oil supplied from SKE was used. Asphalt raw materials are in a solid state at room temperature, and when quantitatively analyzing raw materials, measuring the amount of odor-causing and harmful components, supplying them as raw materials for reforming reactions, or adding bipolar additives, put them in a sealed container at 80 ° C. It was used after leaving it in the oven preheated above for 3 hours or more to maintain the flowability.

< Experimental example 2> Analysis ( equilibrium method )

For the collection and analysis of odor-causing and harmful components generated during asphalt concrete production, 100 g of asphalt raw material before or after reforming was placed in a 250 ml flask maintained at 180° C. and exposed 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 5 ml of the oil vapor is collected at 1 hour intervals using a gas-tight syringe and a gas chromatography connected to a mass spectrum detector. The retention characteristics of each component were analyzed with a graph (GC-MS; gas chromatography w/ mass spectrum detector and HP 50+ column), and the same analysis conditions ( Quantitative analysis was performed for each component under HP 50+ column). The concentration of gaseous components was calibrated using a Refinery Gas Analyzer (RGA; Agilent 5184-3538, 5184-3543) standard gas.

<Experimental Example 3> Determination of asphalt reforming temperature

In order to measure the reforming temperature at which asphalt does not lose its physical properties as a raw material of asphalt in the reforming stage to remove harmful components such as odor-causing and fine dust, the experiment was constructed as follows.

As asphalt, 100 g of AP-5 grade heavy oil supplied from S-OIL was filled in 250 ml of high-temperature and high-pressure autoclave (Parr 4576A), maintained at a set constant temperature, and the increase in pressure was observed after 8 hours compared to the initial pressure. The results of the experiment are shown in FIG. 3 .

As shown in FIG. 3, no pressure change was observed when the temperature applied to the raw material was 300° C. or less, and in this temperature range, chemical reactions such as thermal decomposition did not proceed even if heating and cooling of the raw material were repeated. Asphalt raw material recovery is possible. On the other hand, under the condition maintained at 315°C, a pressure change of 0.1 bar begins to occur, and a sharp increase in pressure is observed as the temperature is increased to a higher temperature of 315°C or higher. This pressure change is a result of the thermal decomposition of the side-chain of the polyaromatic compound, and the decomposed saturated hydrocarbon fragments produce gaseous compounds, and exist in a phase-separated form from the raw material in liquid or solid form. As a result, some of the components have irreversible properties. Since the partial thermal decomposition of the raw material brings about chemical change of the raw material, it can be seen that it is advantageous to set the reforming temperature to 300° C. or less in order to maintain the raw material properties.

<Experimental Example 4> Asphalt reforming reaction

For the reforming reaction of asphalt, a high-temperature, high-pressure reactor (manufacturer: Ari Instrument, model: SCH reactor 500 w/ data gathering tool) that can be equipped with a 500ml SUS liner was used 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 (100° C.), and reforming was carried out by supplying a carrier gas from the time when the target temperature was reached. As the carrier gas, nitrogen gas was supplied from the outside, or 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. It 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. Gas phase was discharged in a mixed form of oil vapor and carrier gas from the upper part of the reactor, and a demister made of glass fiber or SUS316 was placed to prevent the loss of high boiling point oil. The mixed gas passes through the double-jacketed gas-phase condenser and the collection container designed so that the cooling liquid below -10°C continuously flows from the outside through the external pipe to concentrate and collect only the liquefied oil vapor. The carrier gas was configured to be re-supplied into the reactor through a gas transfer pump. 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.

Example 1

To 150 g of AP-5 grade asphalt supplied from SKE, 1000 wppm of a bipolar additive (manufacturer: Emac Solution, model name: ESCA) containing polyisobutenyl succinimide as a component was added, and this was the method of <Experimental Example 4> In carrying out the reforming reaction according to was performed. 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.

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 as in <Experimental Example 2>, and the results of the concentration of oil vapor measured by time are shown in Table 1, and raw materials before reforming The gas phase chromatogram of the oil vapor collected after continuously heating for 5 hours is shown in FIG.

Comparative Example 1

The same procedure as in Example 1 was carried out except that the bipolar additive was not added in Example 1.

In order to analyze the effect of the reforming reaction, the samples before and after the reforming reaction were analyzed by the same measurement method as in <Experimental Example 2>, and the results of the concentration of oil vapor measured by time are shown in Table 1, and the raw materials before reforming were continuously The gas phase chromatogram of the oil vapor collected after heating for 5 hours is shown in FIG.

Equilibration time in Table 1 below means the time the flask was heated at 180° C. in <Experimental Example 2>, 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.

<Table 1> Oil vapor generation concentration (wppm) of Example 1 and Comparative Example 1

<Hazardous steam generation in raw materials before and after reforming by adding additives reduction Effect>

<Table 1> is a table comparing the amount of harmful vapors generated for raw materials before and after reforming according to the introduction of additives. First, when the raw material to which no additives were added (Comparative Example 1) and the raw material to which the bipolar material was added (Example 1) to the AP-5 raw material to which the reforming process was not applied (Example 1) was heated and maintained at 180° C., which is the heating temperature when manufacturing asphalt , the differences in the degassing behavior of oil vapors (rate and amount of oil vapor generation) were compared and observed. In the raw material in which the bipolar material exists, it can be seen that the low boiling point components expected to be trapped in the asphaltene structure are vaporized very quickly in the initial stage (within 2 hours), and the mass to be degassed is also observed in a very high amount. When a simple raw material without additives is exposed to the asphalt manufacturing temperature for a long time, the concentration of oil vapor is maintained at a high concentration, whereas when a bipolar material is present in the raw material, the concentration of hydrocarbons in the vapor tends to decrease, and the discharge rate is also lowered. it can be seen that This is because the oil vapor component existing in the closed gaseous space continuously transfers mass with the heated asphalt raw material liquid phase, but maintains thermodynamic equilibrium conditions with a composition different from the component form in the asphaltene structure of the initial raw material. can be inferred. On the other hand, it can be confirmed that the addition of the bipolar material has a very dramatic effect in manufacturing an asphalt reforming raw material with reduced odor and harmful substances through the reforming process. As shown in the chromatograms of FIGS. 4 and 5 , the amount of oil vapor generated after reforming in both Examples and Comparative Examples was reduced by the reforming process at 300° C., but when the positive electrode additive was added as in Example 1 of the present invention, it was not added. It can be seen that the amount of oil vapor generated after reforming is reduced to about 1/60 compared to Comparative Example 1. This is about 1/300 of the amount of oil vapor generated by the asphalt raw material itself (compare the amount of oil vapor generated before the reforming of Comparative Example 1 and the raw material after reforming of Example 1), and the concentration of the heated closed gaseous space is also at a level of 100wppm or less. It can be seen that the amount of generated oil vapor is significantly reduced. In fact, it was found that even when the raw material heated to a high temperature of 180° C. or more is opened to the atmosphere, there is no detectable odor. When the raw material was applied to the reforming process after the addition of the bipolar additive, it was possible to produce a heavy raw material from which the low boiling point vapor that causes odor and harmful substances was removed very effectively. On the other hand, under the same reforming conditions, the amount of harmful vapor components separated through reforming (mass of separated oil vapor per unit mass of raw material; m _vap ) was 0.0152 (g/g feed) obtained when the additive was applied (Example 1), When no additive was applied (Comparative Example 1), the obtained amount was separated at a higher level than 0.0127 (g/g feed), but the relative mass deviation with respect to the raw material did not occur significantly. It can be seen that an environment in which only low boiling point vapor components can be selectively separated from macromolecular aggregates is provided by controlling the dispersion of asphaltenes, that is, the structure of the colloidal phase of the heavy macromolecules. That is, it is a result that explains that harmful components that may be continuously generated in the manufacturing process of asphalt concrete can be effectively removed in advance by applying a combination of the bipolar additive and the modifying conditions that promote mass transfer.

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

Table 2 below is a table showing the difference in the element ratio composition of the asphalt before reforming and the asphalt after reforming according to Comparative Example 1 and Example 1. 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 2, it can be seen that the asphalts modified according to <Example 1> and <Comparative Example 1> exhibit almost the same compositional ratio in element ratio as compared to 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.

<Table 2> Changes in boiling point and element composition ratio of raw materials according to reforming

As such, the asphalt manufacturing process according to the present invention can effectively separate odor-causing and harmful components that may occur in the asphalt concrete manufacturing process, whereas the manufactured reformed raw material does not significantly change physical properties, resulting in odor-inducing and harmful substances. It can be inferred that it can be used as a raw material for asphalt that does not do.

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 determined by the following claims.

100: asphalt reforming reactor
101: carrier gas inlet
102: carrier gas outlet
103: heating means
104: demister
110: carrier gas dispersion unit
120: carrier gas supply unit
130: odor inducing and harmful component separation part
140: carrier gas circulation unit

Claims (10)

In the asphalt manufacturing process with reduced odor and harmful components,
(a) increasing the dispersibility of asphaltene structures in asphalt used as an asphalt raw material by mixing the anodic additive to asphalt; and
(b) After supplying the asphalt with increased dispersibility in step (a), while maintaining the flowability of the asphalt, the carrier gas is dispersed into the asphalt, and then the odor-causing and harmful components in the asphalt are added together with the carrier gas. Separation and degassing from the degassing step to remove odor-causing and harmful components;
The method of claim 1,
The polarity additive includes 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. Asphalt production with reduced odor and harmful components process.
The method of claim 1,
The bipolar additive is an asphalt manufacturing process with reduced odor and harmful components, characterized in that it is in the form of a polymer having a number average molecular weight of 100 to 500,000.
3. The method of claim 2,
The polar group includes at least one selected from amine, imide, amide, alcohol, phenol, ester, and methacrylate,
The non-polar group comprises a polymer derived from any one or a combination of ethylene, propylene, isobutylene, diene, and styrene.
The method of claim 1,
The content of the bipolar additive is 0.01 to 5% by weight of the asphalt manufacturing process with reduced odor inducing and harmful components.
The method of claim 1,
polyalkylene succinic acid imide as the amphipathic additive; alkyl phenolic dispersants; polyacrylic dispersant; Urea, imidazoline, imidazole, tetrazole, tetrazoline, tetrazolon, lactam, sultam, thiourea, triazole, triazoline, pyridone, pyrimidone, dihydropyrimidine, tetrahydropyrimidine, pyrazole, Any one or more of imidazoline, dihydropyrimidinone, triazine, dihydrotriazine, tetrahydrotriazine, oxadiazole, thiadiazole, dihydrooxadiazole, dihydrothiadiazole, and salicylate a polymer containing a polar head group; Asphalt manufacturing process with reduced odor inducing and harmful components, characterized in that it comprises at least one of at least one.
The method of claim 1,
Step (b) is,
(b-1) heating the asphalt mixed with the bipolar additive to a reforming set temperature;
(b-2) a carrier gas supply step of dispersing and supplying the carrier gas into the heated asphalt;
(b-3) odor-causing and harmful components in the asphalt are separated and degassed from the asphalt mixture together with the carrier gas; .
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 asphalt mixture; Asphalt manufacturing process with reduced composition.
8. The method of claim 7,
The heating step is an asphalt manufacturing process with reduced odor inducing and harmful components, characterized in that heating the asphalt to a temperature of 300° C. or less.
The method of claim 1,
Asphalt manufacturing process with reduced odor inducing and harmful components, characterized in that the carrier gas is an inert gas.

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