KR101726972B1 - Conversion method of rag layer using supercritical alcohols - Google Patents

Abstract

The present invention relates to a conversion method of a rag layer using supercritical alcohol and, more specifically, to an effective conversion method of a rag layer, which converts asphaltene which is a main ingredient of the rag layer into a saturated compound and an aromatic compound which are active ingredients by a cracking reaction, using supercritical alcohol as a solvent and a reactant, and reduces impurities such as lead acid, calcium lead acid, heavy metals (Ni/V), and sulfur to some extent.

Description

TECHNICAL FIELD [0001] The present invention relates to a method of converting a rag layer using supercritical alcohols,

The present invention relates to a method for converting a rag layer using supercritical alcohol, and more particularly, to a method for converting a rag layer using a rag layer generated from a desalter in a petroleum refining process, To maximize utilization of crude oil, which is a limited resource, by converting the lag layer to produce useful chemical components.

As the global crude oil heaviness accelerates, the reserve reserves of traditional crude oil from Middle East gradually decrease, and the reserves of non-traditional crude oil (ultra-fine crude oil, high-grade crude oil and oil sands) reach 30-40% of total crude oil, An efficient refining process of crude oil is attracting attention. Canada, which is most active in the development of non-traditional crude oil, is opening an oil sands development and introducing incentive programs to encourage investment companies. In addition, high-grade crude oil is mainly produced in West Africa, North Sea, China, and South America. As the production of high-grade crude oil is gradually increasing due to its profitability, especially in West Africa and South America, It is leading. In addition, due to the rapid economic development of emerging countries such as China, India and Southeast Asia, demand for crude oil and petroleum products is expected to surge in the near future. Accordingly, major countries in the country, including major crude oil, high-grade crude oil, bitumen, shale oil, We are actively promoting the policy of diversification of crude oil introduction and development of related technology through introduction.

Unlike conventional crude oil, unconventional crude oil contains a large amount of impurities of various components, which causes a lot of problems when it is added to a conventional refinery without any pretreatment. Among the unrecognized crude oil, high-grade crude oil has an API value of 22, and contains super-high quality components such as asphaltene. In addition, lead acid and calcium lead sulfate are contained in an amount of 2 to 4 wt% ) Is higher than 4 ㎎ KOH / g and calcium (Ca) content is higher than 250 ppm. Therefore, when it is supplied without proper pretreatment for the conventional purification process, it causes very severe corrosion of the apparatus and causes clogging.

On the other hand, crude oil has a very low API value of 12, a very high asphaltene content of 10 to 15% by weight, a heavy metal content such as vanadium (V) and nickel (Ni) of 200 ppm, a sulfur content of 6% It is difficult to separate the crude oil from the crude oil and water because it is difficult to separate oil and water between the crude oil and water. In addition, lead acid / calcium lead acid and asphaltene form a very stable water-in-oil (W / O) emulsion at the interface between crude oil and water at the base, and these emulsions coalesce into water and crude oil A rag layer existing at the interface between the first electrode and the second electrode is formed. The rag layer contains water, lead sulphate, calcium lead sulphate, asphaltene and crude oil. Once formed, the lag layer is very stable and contains too much crude oil, resulting in a loss of available crude oil, and if the removal or conversion is not done in a proper way, the inactivity of the catalyst in the up- Causing a lot of problems.

In order to solve the problem of this non-conventional crude oil refining process, a method of blending a small amount of untreated crude oil into a crude oil and introducing it into a refining process, and a method of reducing corrosion of a process equipment by using a sulfur or phosphorus corrosion inhibitor additive However, since there is a problem that the content of usable non-hydrocarbon crude oil is low and the miscibility between crude oil and non-conventional crude oil deteriorates, and since the process for separating and treating lead acid is not a process, There is a problem that the catalyst is inactivated or the like.

On the other hand, methods for removing or converting impurities such as lead acid, calcium lead acid, asphaltene, heavy metal and sulfur contained in non-conventional crude oil include adsorption, extraction, catalyst-based decarboxylation / esterification, And how to use it. Adsorption has the advantage that it can deal with high acidity crude oil containing high concentration of tungsten acid. However, it has a limitation of the process for separating and treating lead acid which is harmful to the environment after adsorption. Extraction is mainly carried out at a liquid- Liquid extraction is not effective for removal of lead acid contained in crude oil, and there is a limit to the separation of lead acid from the w / o due to formation of a stable melt.

On the other hand, the decarboxylation and esterification reaction is a method using a metal supported catalyst, a Co-Mo based catalyst, a Ni-Mo based catalyst, or a metal oxide based catalyst under high temperature and high pressure conditions. The conversion of lead and asphaltene using catalysts and hydrogen is relatively effective for model compounds, but there is a problem in that an excess of expensive hydrogen is required, and the impurities contained in the lag layer (sulfur, minerals dissolved in water, Dissolution of inorganic substances, etc.), the activity of the catalyst is rapidly deteriorated. In fact, it is not effective to remove lead acid discharged from a practical base and to prepare a useful component from a rag layer.

On the other hand, lead acid, calcium lead, asphaltene, heavy metal and sulfur components contained in the non-conventional crude oil are adsorbed to a water-in-oil type (W / O) emulsion formed at the interface between water and crude oil So that a very stable lag layer is formed. Therefore, it is possible to remove the impurities contained in the non-conductive crude oil through formation of an appropriate lag layer, and when the useful component contained in the removed lag layer is converted or separated by an appropriate method, Can be maximized. However, the rag layer contains a high concentration of sulfur, heavy metals, lead acid / calcium lead acid and asphaltene which cause inactivation of the supported catalyst, and when the conventional catalyst and the dicarboxyl miscible / cracking technique utilizing hydrogen are applied, There is a disadvantage in that the inactivity of the catalyst rapidly progresses and excessive use of expensive hydrogen is required.

Therefore, it is possible to effectively remove various kinds of impurities (lead acid / calcium tarsate, asphaltene, heavy metal, sulfur, etc.) present in the rag layer without using a heterogeneous catalyst and hydrogen and then recovering the crude oil, There is a desperate need for a transition method of the rag layer that can be utilized.

Japanese Laid-Open Patent Publication No. 2009-067951 US Registration No. 9005432

The present invention uses a supercritical alcohol as a solvent and a reactant to lower the acidity of high acidity crude oil by converting lead acid and calcium lead acid and to improve the acidity of crude oil components such as asphaltene contained in ultra- It is another object of the present invention to provide a method of converting a rag layer capable of producing a useful component by switching to a low molecular weight by cracking.

In addition, the present invention effectively reacts a rag layer with an alcohol in a supercritical state, thereby reducing acidity of crude oil, reducing asphaltene content, heavy metals, and sulfur content without using expensive hydrogen and heterogeneous catalysts externally provided It is intended to provide reduced crude.

According to another aspect of the present invention, there is provided a method of converting a rag layer using a supercritical alcohol, comprising: mixing a rag layer and an alcohol solvent; And a reaction step in which the rag layer is reacted with the alcohol solvent in a supercritical alcohol state.

The method of switching the lag layer may further include a separation and recovery step of separating and recovering the reaction product after the reaction step.

The lag layer may be in the form of a water-in-oil (W / O) emulsion formed from untransformed crude oil or traditional crude oil and the untransformed crude oil may comprise at least one of high acidity crude oil, super crude oil, have.

In addition, the crude oil may include at least one of tungsten acid, calcium tungstate, asphaltene, heavy metal, and sulfur, and the heavy metal may be vanadium (V) and / or nickel (Ni).

The rag layer may have a moisture content of 20 to 80% by weight.

The alcohol solvent may be at least one selected from the group consisting of methanol, ethanol, propanol, isopropyl alcohol, butanol, isobutanol, 2-butanol, tert-butanol, n- pentanol, isopentyl alcohol, Methyl-1-pentanol, 3-methyl-1-pentanol, 2-methyl-1-pentanol, Methyl-2-pentanol, 4-methyl-2-pentanol, 2-methyl-3-pentanol, 3- Dimethyl-1-butanol, 2,3-dimethyl-1-butanol, 2-ethyl 1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, and 4-heptanol.

In the mixing step, the rag layer may be mixed in an amount of 10 to 90% by weight based on the total amount of the alcohol solvent and the rag layer.

The reaction step may remove and / or convert impurities contained in the lag layer, and the impurities may include at least one of: lead acid, calcium lead acid, asphaltene, heavy metal, and sulfur.

The reaction may be carried out in a supercritical alcohol state at a reaction temperature of 200 to 600 ° C and a reaction pressure of 30 to 700 bar.

The present invention can provide the crude oil from which the impurities have been removed, recovered from the lag layer through the method of switching the lag layer.

The method for converting a rag layer using a supercritical alcohol according to the present invention is a method for converting a rag layer into a rag layer without using expensive hydrogen and a heterogeneous catalyst provided externally, By converting and / or eliminating the sulfur component, there is an advantage that the useful component of the crude oil contained in the rag layer can be utilized.

In addition, the impurities contained in the non-conventional crude oil are removed by formation of a lag layer, the collected rag layer is treated with supercritical alcohol, and impurities are removed, and the useful components are added to the existing petrochemical refinery process, There is an advantage that it can be maximized.

Figure 1 shows an optical microscope image of a rag layer produced in an embodiment of the present invention.
FIG. 2 is a graph showing the relationship between the content of saturated compounds, aromatic compounds, resins, asphaltene content, and the amount of asphaltenes in the liquid material prepared by reacting the liquid phase with methanol in supercritical state using a lag layer as a raw material according to Example 3 of the present invention The results are shown in Fig.
FIG. 3 shows the result of analyzing the liquid material prepared in Example 3 by a time-of-flight mass spectrometer-gas chromatography.

Advantages and features of the present invention and methods of achieving them will become apparent with reference to the embodiments described in detail below. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. To fully disclose the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims.

Unless defined otherwise, all terms (including technical and scientific terms) used herein may be used in a sense commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, commonly used predefined terms are not ideally or excessively interpreted unless explicitly defined otherwise.

The present invention relates to a method for converting a rag layer using a supercritical alcohol, wherein a rag layer containing an impurity is used as a raw material to remove impurities contained in the rag layer from a supercritical alcohol-supercritical water mixed supercritical fluid And recovering the rag layer from which the impurities have been removed, crude oil containing useful components can be provided.

The lag layer switching method of the present invention may include a mixing step (S10), a reaction step (S20), and optionally a separation and recovery step (S30).

Each step of the impurity removal and crude oil recovery method of the lag layer according to an embodiment of the present invention will be described in detail.

First, in the mixing step (S10), a rag layer and an alcohol solvent are charged into a reactor and mixed. The rag layer that can be used in the present invention is not particularly limited, but may be in the form of a water-in-oil type (W / O) emulsion formed from untransformed crude oil or conventional crude oil, and the untransformed crude oil is a high acidity crude oil, , And bitten. ≪ / RTI >

Specifically, the rag layer that can be used in the present invention is an oil-in-water emulsion which is formed at an interface where water in the lower layer of the base and oil in the upper layer are separated from each other when various kinds of non- In the form of a water-in-oil type water-in-oil type emulsion, it may be a raw material in which impurities contained in crude oil, such as lead acid, calcium lead acid, asphaltene, heavy metal and sulfur, are transferred in a certain lag layer. The heavy metal may be vanadium (V) and / or nickel (Ni).

In addition, the water content in the lag layer may vary depending on the temperature, pressure, and chemical use of the demineralizer such as the demineralizer operating conditions, but may be 20 to 80% by weight.

The alcohol solvent may be used for an alcohol containing at least one hydroxyl group in the main chain having 1 to 10 carbon atoms. An alcohol in which at least one hydroxyl group is bonded to the main chain having 1 to 7 carbon atoms can be used, but the present invention is not limited thereto. The alcohol solvent is methanol (critical temperature = 239 DEG C, critical pressure = 81 bar), ethanol (critical temperature = 241 DEG C; critical pressure = 63 bar), propanol (critical temperature = Isobutanol (critical temperature = 275 deg. C; critical pressure = 45 bar), isopropyl alcohol (critical temperature = 307 DEG C, critical pressure = 41 bar), butanol (critical temperature = 289 DEG C, critical pressure = (Critical pressure = 42 bar), tert-butanol (critical temperature = 233 캜, critical pressure = 40 bar), n-pentanol (critical temperature = 307 캜, critical pressure = 39 bar) (Critical pressure = 39 bar), 2-methyl-1-butanol (critical temperature = 302 캜, critical pressure = 39 bar), neopentyl alcohol (critical temperature = (Critical pressure = 37 bar), methyl isopropyl < RTI ID = 0.0 > (Critical pressure = 39 bar), dimethylethylquinol (critical temperature = 271 캜, critical pressure = 37 bar), 1-hexanol (critical temperature = 337 캜, critical pressure = 34 bar), 2 3-hexanol (critical temperature = 309 占 폚, critical pressure = 34 bar), 2-methyl-1-pentanol (critical temperature = 331 占 폚; (Critical pressure = 30 bar), 3-methyl-1-pentanol (critical temperature = 387 캜, critical pressure = (Critical pressure = 36 bar), 3-methyl-2-pentanol (critical temperature = 333 ° C, critical pressure = 36 bar), 2-methyl- - pentanol (critical temperature = 301 < 0 >C; (Critical pressure = 35 bar), 2-methyl-3-pentanol (critical temperature = 303 캜, critical pressure = 35 bar) (Critical pressure = 35 bar), 2,3-dimethyl-1-butanol (critical temperature = 331 캜, critical pressure = 35 bar), 2,3-dimethyl- (Critical pressure = 35 bar), 3-dimethyl-1-butanol (critical temperature = 331 캜, (Critical temperature = 307 DEG C, critical pressure = 34 bar), 1-heptanol (critical temperature = 360 DEG C, critical pressure = 31 bar), 2-heptanol (critical temperature = 335 DEG C, Heptanol (critical temperature = 332 DEG C, critical pressure = 30 bar), and 4-heptanol (critical temperature = 329 DEG C; critical pressure = 30 bar).

The configuration of the reactor used in the mixing step (S10) is not particularly limited, but a batch type or continuous type reactor may be used.

Also, in the mixing step (S10), the concentration of the rag layer in the mixture of the alcohol solvent and the rag layer may be 10 to 90 wt%, and preferably 20 to 80 wt%. If the concentration of the rag layer is less than 10% by weight, the concentration is too lean and the amount of the rag layer in which impurities are removed in a unit time is too small to be economical. If the concentration exceeds 90% by weight, The elimination reaction can not be carried out.

Next, the reaction step S20 is a step of removing and / or changing impurities contained in the rag layer in a mixed supercritical fluid state of water contained in the alcohol solvent and the rag layer, Is increased above the critical temperature and critical pressure of the alcohol and water to remove and / or convert impurities contained in the lag layer in the supercritical fluid state. The advantage of the impurity removal and / or conversion method included in the rag layer using the mixed supercritical fluid is that the acid reduction reaction, the hydrogenation reaction and the cracking reaction can be effectively performed without using hydrogen and heterogeneous catalysts provided from the outside . It is contained in the salts of lead acid and calcium lead, which increase the acidity of the crude oil by the esterification, alkylation and alkoxylation, which are the unique chemical reactivity of supercritical alcohols. The acidity of the crude oil can be reduced by converting the carboxylic acid into another substance without using an externally provided catalyst, and it is possible to fundamentally remove the factors causing corrosion in the subsequent step. In addition, the highly active hydrogen generated in the supercritical alcohol can produce saturated hydrocarbons and aromatic components having a low molecular weight useful as a cracking reaction of asphaltenes having a high molecular weight. The asphaltene component is a very complex compound, which is a structure in which an aromatic compound and a heterogeneous ring compound are connected to each other. In the cracking in a supercritical fluid, hydrogen and catalyst provided externally are not used, and supercritical alcohol is generated by itself Stabilization of the active intermediate produced during the cracking reaction can inhibit coke formation. In addition, heavy metal ions released by cracking a compound having a porphyrin structure in which a heavy metal such as V and Ni are bonded can be converted into VO _x and NiO _x materials through oxidation reaction and removed from the produced liquid phase. It is also possible to crack the heterogeneous ring compound containing sulfur to convert the sulfur to a gas such as H ₂ S and remove it from the liquid phase to be produced.

The supercritical alcohols can provide highly active hydrogen that is generated by itself according to temperature and pressure. As an example, supercritical propanol can provide hydrogen with high activity, such as proton, high-dry, etc., by at least three mechanisms (Nakagawa et al., J Supercrit Fluids 2003, 27, 255-261; Ross et al. Fuel 1979, 58, 438-442; Brand et al., Energy, 2013, 59, 173-182).

In the reaction step (S20), the reaction temperature may be 200 to 600 ° C, preferably 300 to 500 ° C. When the reaction temperature is lower than 200 ° C, there is a problem that the hydrogen generation reaction, the cracking reaction and the acidity reduction reaction of the supercritical alcohol are hard to occur, and the impurities contained in the rag layer can not be effectively removed. There is a possibility that the cracking reaction occurs actively and the crude oil component may be gasified, so that the yield of the liquid phase due to the conversion of the lag layer is lowered and the economical efficiency is reduced.

Also, in the reaction step S20, the reaction pressure may be 30 to 700 bar, preferably 100 to 500 bar. When the reaction pressure is less than 30 bar, hydrogen generation reaction, cracking reaction, and acidity reduction reaction ability of the supercritical alcohol are lowered, and it is difficult to effectively remove impurities from the rag layer. When the reaction pressure exceeds 700 bar, There is a problem in that the process cost is increased.

The reaction time in the reaction step S20 is not particularly limited, but may be 10 seconds to 6 hours, preferably 1 minute to 3 hours. When the reaction time is less than 10 seconds, there is a problem that the reaction for eliminating impurities from the rag layer due to the hydrogen generation reaction, the cracking reaction and the acidity reduction reaction of the supercritical alcohol proceeds too short and effective impurity removal can not be achieved. If the reaction time exceeds 6 hours, the high temperature and high pressure must be maintained for a long time, which raises a problem that the process cost increases.

Next, the separation and recovery step S30 is a step of separating and recovering the reaction products by lowering the temperature and the pressure after the reaction step S20. The reaction product may be discharged through a decompression device located at the outlet of the reactor. The reaction product may be gaseous carbon dioxide, carbon monoxide, methane, ethane, ethylene, propylene, propane, butane, etc., and the liquid material may be in the form of a reacted rag layer, crude oil, alcohol, An organic compound converted from an alcohol, and the solid residue may include zeolite, tar, and an inorganic substance. At this time, the separation of the gaseous products can be performed by separating the gas and liquid by lowering the temperature and the pressure, and the solid residue can be separated through the solid-liquid separation using a filter, a cyclone or the like. A method for separating the useful component from the liquid state material may be a method such as oil / water separation, distillation or the like.

The present invention can provide the crude oil from which the impurities have been removed from the lag layer through the above-mentioned method of switching the lag layer.

Hereinafter, the present invention will be described in detail with reference to the following examples and comparative examples, which should not be construed as limiting the scope of protection defined by the appended claims.

Example  - Supercritical  Alcohol-based Lag Of the layer  transform

Experimental Example  - Analysis method

The total acid number (TAN) of the crude oil and the total acid number of the lag layer before and after the reaction were measured using Metrohm 848 Titrino plus according to the ASTM D664 method with the amount of KOH required to neutralize the acid contained in the lag layer 1g. Analysis of saturated compounds, aromatic compounds, resins, and asphaltenes in crude oil and in the rag layer before and after the reaction was carried out using MK-6 Iatroscan manufactured by Mitsubishi Chemical Medience Corporation. Particularly, the result of analyzing the saturated compound, aromatic compound, resin, and asphaltene content of the liquid material prepared in Example 3 using thin film chromatography is shown in FIG.

Qualitative and quantitative analysis of the gas reaction product was carried out by gas chromatography (GC) equipped with a thermal conductivity detector (TCD) and a flame ionization detector (FID), a Clarus 600 GC-Model Arnel 1115PPC Refinery Gas Analyzer (RGA), PerkineElmer).

Analysis of the leg layers and the liquid phase of the product was analyzed using gas chromatography (Agilent Technologies 7890A) equipped with time-of-flight mass spectroscopy (TOF / MS). Particularly, the liquid material prepared in Example 3 was analyzed by a time-of-flight mass spectrometer-gas chromatography, and the results are shown in FIG.

Example  One

The rag layer used in this example contains 40% by weight of Colombian super-fine crude oil (Rubiales, 31.6 area% SARA assay; TAN 1.3 g KOH / g oil), 30% by weight Venezuelan alpine oil , TAN 5.05 g KOH / g oil), 30 wt% Venezuelan alpine oil (Bachaquero-13, 26.1 area% asphaltene content, TAN 4.21 g KOH / g oil) . Heptol mixed with 80% by volume of n-heptane and 20% by volume of toluene was mixed with 40% by weight of the crude oil for preparing the entire leg layer and mixed with each other. Then, ASTM D- Saline water of 1411 was added in an amount of 40% by weight based on the weight for preparing the entire leg layer, 4% by weight of lead acid for preparing the entire leg layer to increase the acidity of the leg layer, 4% by weight calcium persulfate was added and stirred in an incubator for 12 hours. Thereafter, the resultant was treated with an ultrasonic sonicator for 90 minutes, and then the solution prepared using the centrifugal separator was separated into three layers of an oil layer, a rag layer and a water layer. The produced rag layer was separated from the oil layer and water layer and recovered. An optical microscope (Nikon microscope, model # ECLIPSE Ti) image of the above-mentioned rag layer is shown in Fig. As shown in FIG. 1, it can be seen that a water-in-oil type (W / O) emulsion is formed. The produced rag layer was analyzed, and the results are shown in Tables 2 and 4.

The prepared rag layer and methanol were introduced into a batch type reactor having a volume of 140 ml at a concentration of 17% by weight. Then, the reactor was pressurized with nitrogen of 10 bar and the temperature was raised at a rate of about 20 ° C / min. The rag layer was reacted with supercritical methanol at a reaction pressure of 350 bar for 30 minutes. At this time, the generated gaseous products were collected in the Tedlar bag and the solid and liquid products were separated using a filter. Separation of crude oil and solvent (methanol / water) in liquid phase was carried out by adding dichloromethane, transferring the crude oil onto dichloromethane, and then forming a liquid-liquid interface to recover the crude oil. The properties of the recovered crude oil were evaluated and the results are shown in Tables 1 to 3.

Example  2

The reaction was carried out in the same manner as in Example 1 except that the reaction time was 60 minutes. The reacted lag layers were analyzed in the same manner as in Example 1, and the results are shown in Tables 1 to 3 .

Example  3

The reaction was carried out in the same manner as in Example 1 except that the reaction time was 90 minutes. The reacted lag layer was analyzed in the same manner as in Example 1, and the results are shown in Tables 1 to 3 .

Example  4

The lag layer was reacted in the same manner as in Example 3 except that the concentration of the lag layer was 20% by weight. The reacted lag layers were analyzed in the same manner as in Example 3, and the results are shown in Tables 1 to 3 Respectively.

Example  5

The lag layer was reacted in the same manner as in Example 3 except that the concentration of the rag layer was 25% by weight. The reacted rag layer was analyzed in the same manner as in Example 3, and the results are shown in Tables 1 to 3 Respectively.

Example  6

The reaction was carried out in the same manner as in Example 3 except that the reaction temperature was 375 ° C. The reacted lag layers were analyzed in the same manner as in Example 3, and the results are shown in Tables 1 to 3 .

Example  7

The reaction was carried out in the same manner as in Example 3 except that the reaction temperature was 350 ° C. The reaction was carried out in the same manner as in Example 3 to analyze the rag layer. The results are shown in Tables 1 to 3 .

Example  8

The reaction was carried out in the same manner as in Example 3 except that ethanol was used in place of methanol to react with the rag layer, and the reacted rag layer was analyzed in the same manner as in Example 3. The results are shown in Tables 1 to 3 .

Example  9

The reaction was carried out in the same manner as in Example 3 except that isopropyl alcohol was used instead of methanol to react the lag layer. The reacted lag layer was analyzed in the same manner as in Example 3, and the results are shown in Tables 1 to 3 Respectively.

Example  10

The reaction was carried out in the same manner as in Example 3 except that butanol was used in place of methanol to react the rag layer, and the reacted rag layer was analyzed in the same manner as in Example 3. The results are shown in Tables 1 to 3 .

<Characteristic Analysis of Product>

The yield of the finally obtained product in the above examples was calculated from the weight of each component according to the following equations (1) to (3). In the case of equations (1) to (3), the rag layer used in the above examples contains 60% by weight of water and 10% by weight of an inorganic substance, so that the inorganic layer is removed and the weight of the dried rag layer is used for calculating the liquid and vapor yield , And the yield of the solid residue was the dried rag layer weight.

[Equation 1]

&Quot; (2) &quot;

&Quot; (3) &quot;

The yields of vapor, liquid and solid materials according to the reaction of the rag layer using the supercritical alcohol calculated according to the above formula are shown in Table 1 below.

Supercritical fluid reaction
Temperature
(° C) reaction
pressure
(bar) reaction
density
(wt%) reaction
time
(minute) Liquid phase
yield
(wt%) solid
Residue
yield
(wt%) weather
yield
(wt%) Example 1 Supercritical
Methanol 400 350 17 30 68.7 10.8 0.5 Example 2 Supercritical
Methanol 400 350 17 60 72.7 11.0 0.7 Example 3 Supercritical
Methanol 400 350 17 90 76.7 12.4 0.1 Example 4 Supercritical
Methanol 400 350 20 90 76.0 11.5 0.3 Example 5 Supercritical
Methanol 400 350 25 90 80.0 15.9 1.0 Example 6 Supercritical
Methanol 375 350 17 90 79.0 14.5 0.1 Example 7 Supercritical
Methanol 350 350 17 90 69.9 9.9 0.1 Example 8 Supercritical
ethanol 400 350 17 90 77.5 12.5 0.7 Example 9 Supercritical
Iso
profile
Alcohol 400 350 17 90 79.2 11.5 0.3 Example 10 Supercritical
Butanol 400 350 17 90 75.9 12.9 0.5

As shown in Table 1, when the rag layer was reacted with supercritical methanol at 400 ° C. and 350 bar pressure for 30 to 90 minutes in Examples 1 to 3, the reacted liquid yield Of 68.7 to 76.7% by weight, a solid residue yield of less than 13% by weight, and a vapor phase yield of about 0.1 to 0.7% by weight, the liquid yield was extremely high and the vapor yield was extremely low. Thus, it can be seen that most of the rag layer has been converted to the liquid phase.

On the other hand, even when the reaction concentration was increased to 20 to 25 wt% in Examples 4 to 5, the liquid yield was 76 to 80 wt%, the solid residue yield was 11.5 to 15.9 wt%, the vapor yield was 0.3 to 1.0 wt %, It can be understood that even when a high concentration of the lag layer is reacted, the conversion into the liquid phase is mainly achieved.

On the other hand, even when the reaction temperature was lowered to 375 ° C and 350 ° C in Examples 6 to 7, the liquid yield was about 70 to 79 wt%, the solid residue yield was 9.9 to 14.5 wt%, the vapor yield was 0.1 wt% %, And the liquid phase is mainly generated at a low temperature.

Also, when supercritical ethanol, supercritical isopropanol and supercritical butanol were used as supercritical alcohols in Examples 8 to 10, the liquid yield was about 76 to 79 wt%, the solid residue yield was 11.5 to 12.9 wt% , And a vapor phase yield of 0.3 to 0.7% by weight. This is because supercritical alcohols can effectively provide hydrogen to inhibit condensation or repolymerization reactions that produce solid residues and can be used for esterification, It is considered that the alkylation, alkoxylation and the like effectively proceed to stabilize the unstable intermediate which occurs upon decomposition of the organic material present in the rag layer, thereby increasing the liquid phase yield.

Next, the liquid component contained in the lag layer before and after the reaction was analyzed, and the components of the gas reaction product were analyzed in Table 2 and shown in Table 3.

First, the total acid number (TAN) of the lag layer before and after the reaction was measured using Metrohm 848 Titrino plus according to ASTM D664 method, with the amount of KOH required to neutralize the acid contained in the lag layer 1g. Saturated compounds, aromatic compounds, resin, and asphaltene contents of the lag layer before and after the reaction were analyzed using MK-6 Iatroscan manufactured by Mitsubishi Chemical Medience Corporation. Particularly, the result of analyzing the saturated compound, aromatic compound, resin, and asphaltene content of the liquid material prepared in Example 3 using thin film chromatography is shown in FIG.

Qualitative and quantitative analysis of the gas reaction product was carried out by gas chromatography (GC) equipped with a thermal conductivity detector (TCD) and a flame ionization detector (FID), a Clarus 600 GC-Model Arnel 1115PPC Refinery Gas Analyzer (RGA), PerkineElmer).

Saturated compound
(area%) Aromatic compound
(area%) Resin
(area%) Aspanten
(area%) TAN
(Mg KOH / g) Crude oil 1
(Rubiales) 23.3 35.4 9.7 31.6 1.30 Crude Oil 2
(Laguna) 10.4 43.2 18.9 27.5 5.05 Crude Oil 3
(Bachaquero-13) 10.5 46.5 16.9 26.1 4.21 Rag layer 11.5 14.2 25.1 49.2 58.7 Example 1 27.3 43.8 16.4 12.5 11.7 Example 2 19.9 32.9 45.2 2.0 6.0 Example 3 25.8 32.4 41.8 0.0 5.0 Example 4 25.7 37.7 36.6 0.0 9.7 Example 5 24.2 34.0 41.8 0.0 13.1 Example 6 21.8 48.8 16.8 12.7 11.7 Example 7 21.0 34.9 19.1 25.1 18.6 Example 8 26.0 36.7 40.2 2.1 7.8 Example 9 25.2 35.2 43.2 1.5 8.2 Example 10 23.1 32.8 41.7 2.7 5.6

CO ₂
(mol%) CO
(mol%) H ₂
(mol%) CH ₄
(mol%) C ₂ H ₄ + C ₂ H ₆
(mol%) C ₃ H ₆ + C ₃ H ₈
(mol%) C4 +
(mol%) Waste yield (wt%) Example 1 32.47 7.85 0.40 51.74 5.77 1.30 0.47 0.5 Example 2 29.13 6.58 0.50 54.23 5.95 2.73 0.88 0.7 Example 3 11.09 5.13 9.80 60.59 4.11 5.86 3.42 0.1 Example 4 44.85 26.46 4.63 21.48 1.38 0.93 0.28 0.3 Example 5 51.52 34.36 4.63 7.78 0.95 0.61 0.15 1.0 Example 6 26.67 11.27 2.12 52.85 2.91 2.87 1.3 0.1 Example 7 38.29 9.85 2.04 41.11 7.39 0.93 0.39 0.1 Example 8 34.21 20.45 10.25 50.29 5.24 4.38 3.98 0.3 Example 9 25.69 29.84 14.20 41.20 7.23 4.21 3.14 0.2 Example 10 37.57 15.47 9.98 45.69 3.25 3.47 2.64 0.2

As shown in Table 2, in the case of the lag layer, the content of saturated compounds and aromatic compounds, which are useful components, is lower than that of resin and asphaltene. It can be seen that the rag layer contains an excessive amount of heavy component. The content of saturated compounds and aromatics, which are useful components in the rag layer, was very low, 25.7 area%. In Example 1, when the supercritical methanol was reacted at 400 ° C for 30 minutes, the content of the useful component (saturated compound + aromatic compound) was increased to 71.1 area%, and the content of resin and asphaltene decreased As a result, it can be seen that the conversion of the effective rag layer to the useful component proceeded. After the reaction, the TAN was 11.7 ㎎ KOH / g, which was significantly reduced when compared to the TAN of the rag layer (58.7 mg KOH / g). It was found that the graphene contained in the rag layer was successfully removed.

As shown in Table 3, when the components of the gaseous product of Example 1 were analyzed, CO ₂ (32.47 mol%) was detected in excess, indicating that the oxygen contained in the rag layer was removed by the decarbonylation reaction H ₂ (0.40 mol%) was detected, and supercritical methanol generates hydrogen, without providing hydrogen from the outside, so that recombination or condensation reaction which may occur in the reaction can be obtained And the yield of the reacted liquid phase was high. A small amount of C ₂ H ₄ + C ₂ H ₆ (5.77 mol%), C ₃ H ₆ + C ₃ H ₈ (1.30 mol%) and C4 + vapor material (0.47 mol% The reaction was inhibited.

As shown in FIG. 3, when the leg layer was analyzed using a gas chromatography-time-of-flight mass spectrometer, some linear and branched hydrocarbons were detected along with the lead acid component. However, the liquid phase prepared in Example 2 was C11 C40 linear hydrocarbons were the main compounds and diesel and lube oil components were mainly produced.

When the rag layer was reacted with supercritical methanol by increasing the reaction time from 400 ° C to 60 ° C for 90 minutes in Examples 2 to 3, the asphaltene content was compared with the rag layer of 49.2 area% before reaction , The content of useful components increased to 52.8 area% and 58.2 area%, respectively, and the amount of resin component increased to 45.2 area% and 41.8 area%, respectively. In the long reaction time, highly effective asphaltene cracking and useful ingredient conversion Indicating that the reaction proceeded. After the reaction, the TAN was decreased to 5 ~ 6 ㎎ KOH / g when compared with the pre - reaction lag layer, and it was found that the long - term reaction more effectively removed the H - acid contained in the rag layer. As shown in Table 3, the gas components were analyzed to find that C ₂ H ₄ + C ₂ H ₆ (4.11 to 5.95 mol%), C ₃ H ₆ + C ₃ H ₈ (2.73 to 5.86 mol% A small amount of gaseous matter (0.88 ~ 3.42 mol%) was detected, and it was found that the gas phase conversion reaction of the rag layer was inhibited even when the reaction proceeded for a long time.

On the other hand, in Examples 4 to 5, when the reaction concentrations were increased to 20 to 25 wt% at 400 ° C, the asphaltenes contained in the rag layer were mostly saturated compounds, aromatic compounds , And a resin component. After the reaction, the TAN was 9.7 ~ 13.1 ㎎ KOH / g, which was significantly decreased when compared with the lag layer before reaction. It was found that when the lag layer was reacted at a high concentration, the acid contained in the rag layer was effectively removed. As shown in Table 3, the components of the gaseous products of Examples 4 to 5 were analyzed to find that CO ₂ (44.85 to 51.52 mol%) and CO (26.46 to 34.36 mol%) were excessively detected, It was found that the oxygen contained in the rag layer was removed by the carbonylation and decarboxylation reaction, and C ₂ H ₄ + C ₂ H ₆ (0.95 to 1.38 mol%), C ₃ H ₆ + C ₃ H ₈ 0.61 to 0.93 mol%) and C4 + gaseous material (0.15 to 0.28 mol%) were detected in a small amount, and it was found that the gas phase conversion reaction of the rag layer was inhibited even when the reaction proceeded for a long time.

In Examples 6 to 7, when the reaction temperature was reduced to 375 ° C and 350 ° C, respectively, under the reaction time of 90 minutes, the asphaltene content was 12.7 area% and 25.1 area%, respectively, , The content of the useful component (saturated compound + aromatic compound) was as high as 70.6 area% at 375 ℃ and 55.9 area% at 350 ℃ reaction condition, It was found that the conversion reaction proceeded to an effective useful component. After the reaction, the TAN was 11.7 ~ 18.6 ㎎ KOH / g, which was significantly decreased when compared with the pre - reaction lag layer.

Also, when the supercritical ethanol, supercritical isopropyl alcohol and supercritical butanol were used in place of the supercritical methanol in Examples 8 to 10, the content of the useful ingredient was 55.9 to 62.7 area %, The asphaltene content was drastically reduced to 1.5 to 2.7 area%, and the resin content was as high as 40.2 to 41.7 area%. As with supercritical methanol, most of the asphaltene contained in the rag layer was successfully Cracked and converted into a useful component and a resin. When the supernatant ethanol, supercritical isopropyl alcohol and supercritical butanol were used as the supercritical alcohol, it was found that the lag of the lag layer It was found that the acid contained in the layer was successfully removed. As a result of analyzing the components of the gaseous products of Examples 8 to 10, excessive amounts of CO ₂ (25.69 to 37.51 mol%) and CO (15.47 to 29.84 mol%) were detected, and decarbonylation and decarboxylation reactions (3.25-7.23 mol%), C ₃ H ₆ + C ₃ H ₈ (3.47-4.38 mol%), and C ₂ H ₄ + C ₂ H ₆ (2.64 ~ 3.98 mol%) of C4 + vapor material was detected, and it was found that the gas phase conversion reaction of the rag layer was inhibited even if the reaction proceeded for a long time.

To investigate the impurity removal effect of the lag layer before and after the reaction, the liquid phase was analyzed using an Agilent 7500 Inductive Coupled Plasma-Mass Spectroscopy. The results are shown in Table 4.

Ingredient content Rag layer Example 3 Sulfur (wt%) 0.45 0.2 Ca (mg / kg) 1300 35.5 Ni (mg / kg) 21.8 <0.01 V (mg / kg) 231 63

The rag layer showed a sulfur content of 0.45 wt%, a Ca content of 1300 mg / kg, a Ni content of 21.8 mg / kg and a V content of 231 mg / kg, And the content of V was decreased to 63 mg / kg by 73%, and the effective amount of impurity reduction reaction was decreased by 56%, and the Ca content was decreased by 35.5 mg / kg, and the Ni content was less than 0.01 mg / It can be seen that this has been done.

Although the configuration of the present invention has been proven by the above embodiments, the present invention is not necessarily limited to the above configuration, and various permutations, modifications and variations are possible without departing from the technical idea of the present invention. Therefore, the above description does not limit the scope of the present invention, which is defined by the limitations of the following claims.

Claims (13)

A mixing step of mixing the rag layer and the alcohol solvent; And
Reacting the rag layer in the supercritical alcohol state of the alcohol solvent to remove or convert or remove and remove impurities including lead acid, calcium lead acid, asphaltene, heavy metal, and sulfur contained in the rag layer A method of converting a rag layer using supercritical alcohols comprising a reaction step. The method according to claim 1,
Further comprising the step of separating and recovering the reaction product after the reaction step and separating and recovering the reaction product. The method according to claim 1,
Wherein the lag layer is in the form of a water-in-oil (W / O) emulsion formed from untransformed crude oil or traditional crude oil. The method of claim 3,
Wherein said unconventional crude oil comprises at least one of high acidity crude oil, super crude oil, tight oil, and bitumen. delete The method according to claim 1,
Wherein the heavy metal is vanadium (V) and / or nickel (Ni). The method according to claim 1,
Wherein the rag layer comprises a supercritical alcohol having a water content of 20 to 80 wt%. The method according to claim 1,
The alcohol solvent may be at least one selected from the group consisting of methanol, ethanol, propanol, isopropyl alcohol, butanol, isobutanol, 2-butanol, tert-butanol, n- pentanol, isopentyl alcohol, Methyl-1-pentanol, 3-methyl-1-pentanol, 2-methyl-1-pentanol, Methyl-2-pentanol, 4-methyl-2-pentanol, 2-methyl-3-pentanol, 3- Dimethyl-1-butanol, 2,3-dimethyl-1-butanol, 2-ethyl A method for converting a rag layer using supercritical alcohols comprising at least one of 1-butanol, 1-heptanol, 2-heptanol, 3-heptanol and 4-heptanol. The method according to claim 1,
Wherein the mixing step comprises mixing the rag layer in an amount of 10 to 90% by weight based on the total amount of the alcohol solvent and the rag layer, using the supercritical alcohol. delete delete The method according to claim 1,
Wherein the reaction is carried out in a supercritical alcohol state at a reaction temperature of 200 to 600 DEG C and a reaction pressure of 30 to 700 bar. A crude oil recovered from a rag layer by the method of any one of claims 1 to 4, 6 to 9 and 12.

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