KR20030087047A - Heavy Oil Refining Method - Google Patents

Abstract

The crude oil having a hydrogen content of 12 wt% or less is subjected to solvent extraction to increase the hydrogen content by 0.2 wt% or more with respect to the crude oil, and then hydrogenated and purified so that the hydrogen content increases by 0.5 wt% or more with respect to the crude oil to obtain a refined oil. Thereby, refined oil can be manufactured by the simple and reliable method using the cheap heavy oil as a raw material.

Description

Heavy Oil Refining Method {Heavy Oil Refining Method}

Petroleum products using crude oil as starting materials are produced by performing various physical or chemical refining treatments starting from atmospheric pressure and reduced pressure distillation separation because impurities originating in their origin are present in crude oil.

In general, petroleum fractions, ie effluent oil separated from the top of the tower by distillation, are high quality petroleum products that are highly impurity-free, because they contain less impurities and can be removed by simple refining processes. It is used as high grade fuel oil, such as fuel, and a raw material for petrochemicals.

On the other hand, with respect to heavy oils such as distillation residue oil, impurities are concentrated and present in a large amount, and are present in a form that is particularly difficult to remove. Hydrogen refining, which is a basic refining means, has limitations in removing the impurities. In particular, in the case of highly purified, excessive reaction conditions of high temperature and high pressure are required in the presence of hydrogen and a catalyst, a large amount of hydrogen and a catalyst are consumed, and a large investment including equipment costs is required and economical. What is not true is reality. Therefore, a method for easily and economically obtaining high quality refined oil having high added value from heavy oil, that is, highly free of impurities is expected.

High quality refined oil has one of its uses as a raw material for petrochemicals. Lower olefins such as ethylene and propylene, which are basic substances in the petrochemical field, are produced by pyrolysis using light oils such as ethane and naphtha as the main raw materials, but some of the heavy fractions such as light gas oil and reduced pressure gas oil are also used as raw materials. It is used by. In the United States and the Middle East where natural gas is abundant and cheap, ethylene plants made from ethane, the former, are the mainstream. In Japan, Asia, and Europe, where naphtha is cheaper, most of them are made from the latter naphtha.

In naphtha-based ethylene plants, the formation of by-products such as tar and asphalt is more likely than that of ethane, which leads to coking and contamination in the main reactor pyrolysis tube and the subsequent quench heat exchanger. It is necessary to respond. Pressure-sensitive gas oil having a higher molecular weight than naphtha and having a large amount of metal and sulfur is considered as a raw material of the ethylene plant and is considered to be a commercial operation limit.

On the other hand, from the viewpoint of raw material supply amount and raw material cost, if it is possible to use raw material heavier than the light oil fraction as the raw material for lower olefin production, the raw material cost is lowered and the problem of stable supply of raw material oil accompanying the petroleum resource neutralization This can be solved, and it is a very big contribution to the industry.

This invention is made | formed in view of the said situation, and provides the method of economically recovering refined oil with high added value from the heavy oil which contains the impurity of a crude oil origin to high concentration. In particular, by providing a simple and reliable method of refining heavy oils such as atmospheric residual oil which are conventionally unsuitable as raw materials for lower olefins, a method for purifying heavy oils which can economically recover refined oils suitable for raw materials for olefin production.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for purifying heavy oil that can efficiently remove impurities of crude oil origin by solvent extraction treatment and hydrogenation refining treatment. In particular, the present invention relates to the production of lower olefins from heavy oils that have not been used as raw materials for the production of lower olefins. The present invention relates to a method for obtaining refined oil suitable as a raw material.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to achieve the said objective, the present inventors made heavy oil with a hydrogen content of 12 wt% or less as a raw material, processed it to increase the hydrogen content by fixed amount or more by solvent extraction, and then obtained deasphaltene oil By treating the hydrogen content to increase the hydrogen content by a certain amount or more, it has been found that impurities in heavy oil can be efficiently removed and high quality refined oil with highly impurities removed can be obtained.

The purification method of the heavy oil of this invention is a process containing the solvent extraction process of solvent-extracting raw material oil and obtaining an extraction oil, and the hydrogenation refinement process which obtains refined oil by hydrogenating the obtained extraction oil in presence of hydrogen and a catalyst. To obtain refined oil. The raw material oil is a heavy oil having a hydrogen content of 12 wt% or less.

In the solvent extraction step, the raw material oil is solvent extracted to increase the hydrogen content by 0.2 wt% or more relative to the raw material oil, and deasphaltene oil (DAO) is obtained as the extracted oil. In the hydrorefining step, the deasphaltene oil is hydrogenated and purified to increase the hydrogen content by 0.5 wt% or more relative to the deasphaltene oil to obtain a refined oil.

In this way, impurities that are hard to be removed in the subsequent hydrorefining are treated in advance under conditions in which the hydrogen content is increased by a predetermined amount or more by solvent extraction, and then treated under conditions in which the hydrogen content is increased by a predetermined amount or more by the hydrogenation purification step. It is possible to reliably obtain a high-quality refined oil which is highly impurity removed, which is unpredictable in each purification process alone.

The inventors have focused on the fact that impurities can not be removed reliably simply by simply performing the solvent extraction step and the hydrorefining process, and the hydrogen content of the heavy oil to be treated is used as an index. It was conceived that the refined oil from which highly impurity was removed reliably and efficiently by processing so that a predetermined amount of hydrogen content may increase each in a refinement | purification process was considered. Thereby, it is possible to obtain on the economic conditions that load balance is maintained, without making conditions of a solvent extraction process and a hydrogenation purification process into an excessive condition.

It is preferable that the hydrogen content of the obtained refined oil is 11.5 wt% or more, More preferably, it is 12.0 wt% or more. In this case, by applying to the raw material for producing olefins, which is a raw material for petrochemicals, the occurrence of caking and contamination is suppressed even during the pyrolysis reaction, thereby enabling commercial operation. Therefore, in the present invention, it is possible to reliably and efficiently obtain refined oil with high added value, and it is also economically excellent.

Hereinafter, a preferred embodiment of the method for purifying heavy oil according to the present invention will be described. However, the present invention is not limited to the following examples, and for example, the elements of these examples may be appropriately combined.

In the present invention, heavy oil having a hydrogen content of 12 wt% or less, preferably 10 to 12 wt% is used as a raw material, and each is treated under conditions of achieving a predetermined degree of purification in the solvent extraction step and the hydrorefining step.

The heavy oil of 12 wt% or less used in the present invention generally includes residue oil such as atmospheric residual oil, ultra heavy crude oil, and the like, and its use is limited because of its high impurity concentration. The hydrogen content of these heavy oils is generally 9 to 12.5 wt%, and more preferably 9 to 11.5 wt%. Conventionally, impurities cannot be sufficiently removed even if refined, and they are not suitable for petrochemical raw materials such as olefins. .

The present invention uses a heavy oil having a hydrogen content of 12 wt% or less as a raw material oil, performs a solvent extraction treatment as a first step, and recovers deasphaltene oil, which is an extraction oil having an increased hydrogen content of 0.2 wt% or more. In this solvent extraction process, the asphaltene part with little hydrogen content is selectively removed.

This asphaltene portion has a micellar structure composed of a compound containing a small amount of hydrogen such as a condensed polycyclic aromatic and a cyclo paraffin ring, and the inside contains a residual carbon and a porphyrin compound which is a metal such as V and Ni, and the impurities are concentrated. It is known. It is known that the asphaltene portion significantly suppresses the hydrogenation purification reaction and promotes the deterioration of the catalyst. In the present invention, the asphaltene portion is subjected to solvent extraction under a condition in which the hydrogen content increases by 0.2 wt% or more. Remove the volume selectively.

The solvent extraction process can apply the conventionally well-known solvent removal process, The heavy oil is made to countercurrently contact with C3-C5 solvent in an extraction tower, and the deasphaltene oil, hydrogen content is low, and metal and residual carbon are concentrated. Separate with asphaltenes. By appropriately selecting the type of solvent to be used, the amount of the solvent for the heavy oil, and the extraction temperature conditions, the extraction processing conditions can be obtained by controlling the extraction treatment conditions to increase the hydrogen content by 0.2 wt% or more.

As the C3 to C5 solvent, at least one selected from propane, butane and heptane can be preferably used.

The deasphaltene oil can be obtained by recovering the solvent from the top of the tower along with the solvent as an extract and separating and removing the solvent in the extract in a supercritical state. Asphaltene is recovered from the bottom of the column together with some solvents to the extraction residue, and the solvent in the extraction residue is recovered by evaporation.

In the present invention, the hydrogen content of the deasphaltene oil obtained in such a solvent extraction treatment step is increased by 0.2 wt% or more than the hydrogen content of the raw material heavy oil. In particular, it is preferable to increase by 0.2 to 1.5 wt%, and more preferably by 0.2 to 1.2 wt%.

It is preferable to change the increase amount of the hydrogen content of a solvent extraction process with the hydrogen content value of raw material heavy oil. That is, when the hydrogen content of the raw material oil is 11 wt% or more, it is preferable to control the extraction treatment conditions so that the hydrogen content increases from 0.2 to 1.0 wt%, especially 0.2 to 0.5 wt%, relative to the raw material oil in the solvent extraction step. If the hydrogen content is less than 11.0 wt%, an increase in the range of 0.5 to 1.5 wt%, especially 0.8 to 1.3 wt% is preferred.

In the solvent extraction step, the increase in the hydrogen content is an essential condition because the removal of asphaltene, which is an impurity, becomes insufficient when it is 0.2 wt% or less, and the removal of impurities is not sufficient even if it is treated in a subsequent hydrogenation purification step. The upper limit of the increase is better in terms of refining degree, but it is not economical because the recovery of deasphalten oil is lowered when it is increased by 1.5 wt% or more.

In the present invention, deasphalten oil subjected to solvent extraction in such a manner that the hydrogen content increases by 0.2 wt% or more in the solvent extraction treatment is then subjected to hydrorefining treatment as a second step.

In the hydrorefining process of this invention, it processes on the conditions which increase hydrogen content 0.5weight% or more. This hydrorefining treatment is a typical purification treatment for treating hydrocarbons at high temperature and high pressure in the presence of a catalyst and hydrogen, and may include all reactions such as hydrocracking, hydrodehydration, hydrodemetallization, and hydrodenitrification. That is, hydrocracking to obtain low molecular weight refined oil from raw heavy oil, hydrogen compounds in hydrocarbons are reacted with hydrogen, separated as emulsified hydrogen, hydrohydrogenation to obtain crude oil of lower sulfur concentration than raw oil, and metals in hydrocarbon under high temperature and high pressure hydrogen. Hydrogenation of the compound, depositing on the catalyst as an elemental metal, dehydrogenation to obtain a refined oil of low metal concentration, nitrogen compound in hydrocarbon under high temperature and high pressure hydrogen, reacted with hydrogen, separated as ammonia, It is good to include all reactions, such as hydrodenitrification, which obtain the refined oil of nitrogen concentration.

The heavy oil contains a sulfur portion, a metal, and the like as impurities, but since impurities that are difficult to remove are removed only by the solvent extraction treatment step of the previous step, impurities can be efficiently removed to low concentrations without excessive conditions.

As a catalyst used in the hydrorefining process of this invention, it is preferable to use combining the at least 2 sort (s) chosen from a hydrometal hydride catalyst, a hydrocracking catalyst, a hydrocracking metal hydride catalyst, and hydrocracking catalyst. As a catalyst used for hydrogenation purification, Co / Mo, Ni / Co / Mo, Ni / Mo system is preferable.

Although there are no particular restrictions on the hydrogenation purification reaction conditions, a range of hydrogenation purification reaction conditions generally carried out is preferable. That is, 60-150 kg / cm <2> is preferable and, as for hydrogen partial pressure, 80-130 kg / cm <2> is more preferable. The hydrogen / oil ratio is preferably 400 to 1200 Nm 3 / Pa, more preferably 600 to 1000 Nm 3 / Pa. 0.1-1.0 / hr is preferable and, as for LHSV, 0.2-0.8 / hr is more preferable. 340-440 degreeC is preferable and 350-420 degreeC of reaction temperature is especially preferable.

Such conditions are general conditions for hydrorefining, and in the present invention, if the hydrorefining process is carried out under the condition that the hydrogen content increases by 0.5 wt% or more after the solvent extraction step of the previous step, impurities as the final refined oil can be efficiently removed. have.

In the present invention, when the hydrogen content of the raw material oil is 11 to 12 wt%, the increase in the hydrogen content of the refined oil obtained in the hydrorefining step to the deasphaltene oil is preferably 0.5 to 1.0 wt%, particularly 0.5 to 0.9 wt%. Do. When the hydrogen content of the raw material oil is less than 11 wt%, the increase in the hydrogen content of the refined oil obtained in the hydrorefining step to the deasphaltene oil is preferably 0.6 to 1.5 wt%, particularly 0.8 to 1.3 wt%.

Moreover, in the hydrogenation purification process of this invention, when the hydrogen content of the deasphalten oil obtained by the solvent extraction process of the previous step is 11.5 wt% or more, it is preferable that it is an increase of 0.5-1.0 wt%, If it is less than 11.5 wt%, it is preferable that it is an increase amount of 0.6-1.5 wt%.

If the increase in the hydrogen content in the hydrorefining treatment step is less than 0.5 wt%, impurity removal of the deasphalten oil becomes insufficient, and when the increase amount is 1.5 wt% or more, the hydrorefining reaction such as the hydrogen partial pressure, the reaction temperature, and the catalyst loading amount It is not economical because the processing conditions of must be excessive.

That is, from the viewpoint of the hydrorefining reaction conditions, in the solvent extraction treatment step, hydrogen is refined in the subsequent hydrorefining treatment step by selectively removing the asphaltene portion, which is an impurity that is difficult to remove in the hydrorefining treatment step, in advance. Impurities can be efficiently removed to low concentrations without increasing the partial pressure and reaction temperature and increasing the catalyst amount drastically without lengthening the reaction time.

As a result, Conradson Carbon Residue and metal parts such as Ni and V, which are present in a form difficult to be concentrated and removed in asphaltenes, are selectively removed by solvent extraction, and then removed in a hydrorefining process. Impurities such as sulfur, metals such as Ni and V, which are present in an easy form, can be removed intensively.

The refined oil treated in the refining process according to the present invention is used as a raw material for producing lower olefins, even when subjected to high temperature pyrolysis. Yield and continuous operability are increased, making it suitable for commercial production. This is because high quality refined oil can be obtained by simple refining using heavy oil such as residue oil and ultra-heavy raw material, which are conventionally considered unsuitable as lower olefin raw materials.

In the present invention, the refined oil treated under the conditions satisfying the above is effective as the refined oil of the present invention, but especially when used as a raw material for producing lower olefins, the hydrogen content is required to be 11.5 wt% or more, and more preferably 12.0 wt% or more. desirable.

In the present invention, the hydrogen content of the refined oil obtained by solvent extraction of the heavy oil and two-stage purification of hydrogenation purification is required to increase by 0.7 wt% or more than the raw heavy oil, and preferably 0.8 to 2.7 wt%, particularly 1.0 to More preferably, it is 2.2 wt%. When using as a raw material for lower olefin manufacture, it is preferable that the hydrogen content of final refined oil is 11.5 wt% or more, and it is especially preferable that it is 12.0-13.5 wt%.

The solvent extraction treatment and the hydrorefining treatment are carried out so that the hydrogen content of the refined oil is increased by 11.5 wt% or more and 0.7 wt% or more than the raw heavy oil, and the characteristics are complemented in each treatment, and the solvent extraction and hydrogenation of each process are performed. It is possible to obtain highly refined refined oil in high yield, without excessive load on the device for petroleum, and it is hard to cause caking and contamination even when applied as raw material for petrochemical, and suitable for petrochemical raw material with high yield Refined oils can be prepared.

In the process of solvent extraction of the heavy oil of the present invention, the extraction operation is performed under the condition of increasing the hydrogen content of the raw material oil by 0.2 wt% or more, and the Ni + V metal contains dozens to thousands of wtppm in the residue oil and the ultra heavy raw material. It is. They are concentrated in asphaltenes, and since the asphaltenes can be selectively removed in the solvent extraction process, the metal concentration of Ni + V in the deasphaltene oil, which is a refined oil extracted from the deasphaltene oil in the solvent extraction process, can be removed. It is preferable to set it as 70 wtppm or less, especially 50 wtppm or less. Furthermore, it is preferable to perform a solvent extraction process so that residual carbon content may be 15 wt% or less, especially 12 wt% or less. That is, it is preferable to increase the hydrogen content by 0.2 wt% in the solvent extraction process, and to make the Ni + V metal concentration 70 wtppm or less and the residual carbon 15 wt% or less. It is possible to reliably remove impurities and to obtain a high quality refined oil without excessively deteriorating.

The sulfur concentration of the deasphaltene oil is preferably 5 wt% or less, particularly 4 wt% or less. Thereby, the sulfur part of the final refined oil obtained by the next hydrorefining process can be reliably treated so that it may be 0.5 wt% or less, preferably 0.3 wt% or less.

By adjusting the Ni + V concentration of the deasphalten oil to 70 wtppm or less, the residual carbon concentration to 15 wt% or less, and the sulfur concentration to 5 wt% or less, the Ni + V concentration of the final refined oil obtained in the subsequent hydrorefining process was 2 It can be reliably treated to be wtppm or less, preferably 1 wtppm or less, residual carbon concentration of 1 wt% or less, and sulfur concentration of 0.5 wt% or less, preferably 0.3 wt% or less.

By adjusting the sulfur portion of the final refined oil to 0.5 wt% or less, even when used as a raw material for lower olefins, corrosion of the pyrolysis device can be suppressed within the allowable range of the material, and substantial commercial production of lower olefin raw materials is possible. Done.

In this invention, it is preferable to perform a solvent extraction process and a hydrorefining process so that Ni + V metal content of final refined oil may be 2 wtppm or less, especially 1.0 wtppm or less.

Deasphalten oil having a Ni + V metal content of 70 wtppm or less in the solvent extraction treatment can be significantly reduced in caking by making the Ni + V metal content of 1 wtppm or less particularly in hydrorefining. It is possible to obtain refined oil in high yield and to use the refined oil as a raw material for pyrolysis for producing lower olefins.

In the industrial process for the production of lower olefins containing ethylene and propylene by pyrolysis, the maintenance of tack removal and contamination by by-product heavy oils and the yield of olefins dominate the economics, in particular lower olefins. Yield of 25 wt% or more is the target. In particular, when looking at the lower olefins in detail, an ethylene yield of 15% or more and a propylene yield of 10% or more are targeted.

Contamination by caking and by-product heavy oil, which affects the maintainability of the pyrolysis device, corresponds to regular caking removal and cleaning. In particular, with respect to by-product heavy oil, the high-temperature decomposition products decomposed in the cracking pipe are quenched by downstream heat exchange to prevent excessive decomposition, and in the case of heavy oil production, the heat exchanger and piping are blocked, and long-term continuous operation is impossible. Let's do it.

As in the present invention, when starting from heavy oil, the amount of by-product heavy oil produced in the pyrolysis reaction can be aimed at commercial operation.

The refined oil obtained in the present invention is a crude oil having a hydrogen content of 12 wt% or less which is not conventionally used as a raw material for producing lower olefins such as ethylene, and is provided as a raw material for producing lower olefins. The caking characteristic is good, and industrial production is possible.

In the present invention, when the content of impurities in the effluent oil obtained by simple distillation such as crude oil is small, or when the content of impurities can be reduced by simple refining, the crude oil is used as a starting material and separated into effluent oil and residue oil. In addition, the atmospheric distillation residue oil and the vacuum distillation residue oil, which are residue oil, may be subjected to solvent extraction and hydrorefining to obtain refined oil as described above, and the refined oil may be mixed with at least a portion of the oil refined by hydrogenation.

In this case, when the solvent extraction step and the hydrogenation refining step satisfy the increase standard of hydrogen content of the present invention, the total impurity concentration can be reduced, and in particular, the supply amount of refined oil can be increased by mixing the effluent oil having a low impurity content. have.

When it is supplied as a raw material oil for producing lower olefins, caking and contamination are particularly hard to occur in the pyrolysis reaction, and commercial production is possible.

Experimental Example

The present invention will be described in detail with reference to the following experimental examples, but the present invention is not limited to the following experimental examples.

Experimental Example 1

Heavy oil (hydrogen content: 11.25 wt%, Ni + V metals: 65 wtppm), Conradson residual carbon (hereinafter referred to as CCR): 11.1 wt%, S: 3.95 wt%) Introduced into a solvent extraction treatment device, and extracted using a normal pentane solvent (solvent / oil ratio: 8/1) to obtain an extraction ratio of 81 wt% to obtain deasphaltene oil (hereinafter referred to as DAO). Asphalten oil was refine | purified under the following hydrogenation refinement | purification conditions, and the refined oil 1 of this invention was obtained.

Hydrogenation Purification Conditions: Ni / Mo + Ni / Co / Mo Catalyst (Volume Ratio 1/9), Hydrogen Partial Pressure: 90atm, H ₂ / oil Ratio: 600 Nm 3 / Pa, Temperature: 380 ° C, LHSV: 0.5 L / hr

Table 1 shows the yield, hydrogen content, increase in hydrogen content, V + Ni content, CCR, and sulfur concentration of the obtained deasphaltene oil and refined oil 1 in the raw material oil. Hydrogen content was measured by CHN elemental analysis.

Experimental Example 2

The crude oil used in Experimental Example 1 was introduced into a solvent extraction treatment apparatus, extracted and separated to obtain 84 wt% extraction rate using a normal pentane solvent (solvent / oil ratio: 8/1), and then deasphaltene oil was obtained. Purified hydrogen under the same conditions as in Experimental Example 1 to obtain a refined oil 2 of the present invention.

The yield, hydrogen content, increase amount of hydrogen content, V + Ni content, CCR, and sulfur concentration with respect to the raw material oil of the obtained DAO and refined oil 2 are shown in Table 1.

Experimental Example 3

The raw material oil used in Experimental Example 1 was introduced into a solvent extraction treatment apparatus, extracted using a normal pentane solvent (solvent / oil ratio: 8/1) to obtain an extraction ratio of 81 wt%, and then DAO was obtained. Purification process was carried out under hydrogenation conditions to obtain the refined oil 3 of the present invention.

Hydrogenation Purification Conditions: Ni / Mo + Ni / Co / Mo Catalyst (Volume Ratio 1/9), Hydrogen Partial Pressure: 85atm, H ₂ / Oil Ratio: 600 Nm 3 / Pa, Temperature: 360 ° C, LHSV: 0.5 L / hr

The yield, hydrogen content, increase amount of hydrogen content, V + Ni content, CCR, and sulfur concentration with respect to the raw material oil of the obtained DAO and refined oil 3 are shown in Table 1.

Experimental Example 4

After introducing the raw material oil used in Experimental Example 1 into the solvent extraction processing apparatus, using an isobutane / normal pentane mixed solvent (solvent / oil ratio: 8/1) to extract the separation rate to 76 wt% to obtain a DAO, The purified oil 4 of the present invention was obtained by purifying DAO under the following hydrogenation purification conditions.

Hydrogenation Purification Conditions: Ni / Mo + Ni / Co / Mo Catalyst (Volume Ratio 1/9), Hydrogen Partial Pressure: 110atm, H ₂ / oil Ratio: 800 Nm 3 / Pa, Temperature: 380 ° C, LHSV: 0.3 L / hr

The yield, hydrogen content, increase amount of hydrogen content, V + Ni content, CCR, and sulfur concentration with respect to the raw material oil of the obtained DAO and refined oil 4 are shown in Table 1.

Table 1

Crude oil Experimental Example 1 Experimental Example 2 Experimental Example 3 Experimental Example 4 DAO Refined Oils1 DAO Refined Oils2 DAO Refined Oils3 DAO Refined oils4 Yield (wt%) 100 81 77 84 79 81 78 76 72 Hydrogen content (wt%) 11.25 11.55 12.33 11.50 12.28 11.55 12.14 11.75 12.65 Increase in hydrogen content (wt%) - 0.30 0.78 0.25 0.78 0.30 0.59 0.50 0.90 Total hydrogen increase amount (wt%) - - 1.08 - 1.03 - 0.89 - 1.40 V + Ni (wtppm) 65.0 7.3 <0.1 10.7 <0.1 7.3 <0.1 3.7 <0.1 Conradson Residual Carbon (wt%) 11.10 2.60 0.41 3.20 0.62 2.60 0.76 1.80 0.21 S (wt%) 3.95 3.35 0.06 3.45 0.16 3.35 0.26 3.19 0.02

Comparative Example 1

Except having made solvent extraction ratio 88% using the same raw material oil as Experimental Example 1, Experimental Example 1 extracted and separated under the same extraction conditions to obtain DAO, followed by hydrogenation and purification of DAO under the following hydrogenation purification conditions. Got.

Hydrogenation Purification Conditions: Ni / Mo + Co / Mo Catalyst (Volume Ratio 1/9), Hydrogen Partial Pressure: 90atm, H ₂ / oil Ratio: 600 Nm 3 / Pa, Temperature: 360 ° C, LHSV: 0.5L / hr

The yield, hydrogen content, increase amount of hydrogen content, V + Ni content, CCR, and sulfur concentration with respect to the raw material oil of the obtained DAO and refined oil A are shown in Table 2.

Comparative Example 2

Using the same raw material oil as Experimental Example 1, using a normal pentane solvent (solvent / oil ratio: 8/1), extraction and separation were carried out to obtain an extraction rate of 86 wt%, and then DAO was purified under the following hydrogenation purification conditions. Treatment gave Comparative Refined Oil B.

Hydrogenation Purification Conditions: Ni / Mo + Co / Mo Catalyst (Volume Ratio 1/9), Hydrogen Partial Pressure: 90atm, H ₂ / oil Ratio: 600 Nm 3 / Pa, Temperature: 360 ° C, LHSV: 0.5L / hr

The yield, hydrogen content, increase amount of hydrogen content, V + Ni content, CCR, and sulfur concentration with respect to the raw material oil of the obtained DAO and refined oil B are shown in Table 2.

Comparative Example 3

Using the same raw material oil as Experimental Example 1, using a normal pentane solvent (solvent / oil ratio: 8/1), extraction and separation were carried out so as to obtain an extraction ratio of 81 wt%, and then DAO was purified under the following hydrogenation purification conditions. Treatment gave Comparative Refined Oil C.

Hydrogenation Purification Conditions: Ni / Mo + Co / Mo Catalyst (Volume Ratio 1/9), Hydrogen Partial Pressure: 90atm, H ₂ / oil Ratio: 600 Nm 3 / Pa, Temperature: 345 ° C, LHSV: 0.6L / hr

The yield, hydrogen content, increase amount of hydrogen content, V + Ni content, CCR, and sulfur concentration with respect to the raw material oil of the obtained DAO and refined oil C are shown in Table 2.

Comparative Example 4

Using the same raw material oil as Experimental Example 1, using a propane solvent (solvent / oil ratio: 8/1), extraction and separation were carried out so that the extraction rate was 45 wt%, and then DAO was purified to purify the DAO under the following hydrogenation purification conditions. Comparative crude oil D was obtained.

Table 2 shows the yield, hydrogen content, increase in hydrogen content, V + Ni content, CCR, and sulfur concentration of the obtained crude oil D in terms of raw materials.

Comparative Example 5

Using the same crude oil as in Experimental Example 1, the refined treatment was carried out under the following hydrogenation and purification conditions to obtain comparative refined oil E.

Hydrogenation Purification Conditions: Ni / Mo + Co / Mo Catalyst (Volume Ratio 1/9), Hydrogen Partial Pressure: 150atm, H ₂ / oil Ratio: 1000 Nm 3 / Pa, Temperature: 380 ° C, LHSV: 0.25 L / hr

Table 2 shows the yield, hydrogen content, increase in hydrogen content, V + Ni content, CCR, and sulfur concentration of the obtained refined oil E in the raw material oil.

[Table 2]

Crude oil Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 DAO Refined Oil A DAO Refined Oil B DAO Refined Oil C D (extract only) E (hydrogen only) Yield (wt%) 100 88 84 86 82 81 77 45 95 Hydrogen content (wt%) 11.25 11.37 11.79 11.40 12.08 11.55 11.90 11.95 12.10 Hydrogen content increase amount (wt%) - 0.15 0.42 0.15 0.68 0.30 0.35 0.70 0.85 Total hydrogen increase amount (wt%) - - 0.57 - 0.83 - 0.65 - - V + Ni (wtppm) 65.0 16.8 <0.1 13.5 <0.1 7.3 <0.1 2.0 7.0 Conradson Residual Carbon (wt%) 11.10 4.30 1.47 3.70 0.81 2.60 1.21 0.50 5.70 S (wt%) 3.95 3.57 1.03 3.51 0.32 3.35 0.83 3.07 0.50

<Low olefin manufacture example>

It thermally decomposed on the following conditions using the final refined oil obtained by Experimental Examples 1-4 and Comparative Examples 1-5, respectively.

Reaction condition:

Reaction tube: The HPM material ethylene decomposition tube of 28 mm (phi) inner diameter and 1440 mm (heating part 1200 mm) is used.

Raw material feed: Raw oil = 1.69 L / Hr, water is adjusted to 1.0 in weight ratio with respect to raw oil.

Reaction temperature: 900 ℃

Pressure: normal pressure

Retention time: 0.5 seconds

The yield of the obtained lower olefins (ethylene and propylene) was calculated | required from the gas composition in the product gas analyzed using the amount of product gas and gas chromatography. The amount of by-product heavy oil was determined from the amount of bottom oil after separating the naphtha fraction by distillation from the product oil after cooling the pyrolysis gas.

Judgment of continuous operability was determined by using by-product heavy oil, which is the cause of contamination precipitated by the quenching section branched from the reaction tube, in the weight ratio of the raw material oil to 30 wt% or less = ○, 30 wt% or more = x.

The results are shown in Table 3.

Table 3

Experimental Example 1 Experimental Example 2 Experimental Example 3 Experimental Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Hydrogen content (wt%) 12.33 12.28 12.14 12.65 11.79 12.08 11.90 11.95 12.10 Ethylene Yield (wt%) 16.7 16.1 15.9 18.1 11.5 13.1 13.4 13.1 14.0 Propylene Yield (wt%) 13.1 12.5 12.2 14.8 8.5 9.7 10.2 10.1 10.4 By-product heavy oil (wt%) 28.1 28.7 29.5 24.5 36.5 33.2 34.8 34.6 32.9 Continuous operation ○ ○ ○ ○ × × × × ×

In Experimental Examples 1 to 4 of the present invention, the DAO obtained by the solvent extraction treatment was extracted so that the hydrogen content was increased by 0.2 wt% or more compared with the heavy raw material oil, and then, in the hydrogenated refined oil, the hydrogen content was increased by 0.5 wt% or more as compared with DAO. As a result, the final refined oil was treated to increase by at least 0.7 wt% relative to the heavy crude oil. In the refined oil of the present invention, all V + Ni obtained refined oil having impurities removed at 0.1 wtppm or less, Conradson residual carbon at 0.8 wt% or less, and sulfur concentration at 0.3 wt% or less. On the other hand, in Comparative Examples 1-5 which do not satisfy the increase of the hydrogen content of this invention, Conradson residual carbon of final refined oil is 0.8 wt% or more, and sulfur concentration is 0.3 wt% or more.

In particular, it can be seen that only the solvent extraction treatment does not lower the sulfur concentration even when the extraction rate of DAO is reduced, and that Conradson residual carbon is not removed even if the hydrogen consumption is drastically increased by the hydrogenation purification treatment alone.

From the result of pyrolysis treatment of the obtained refined oil to produce lower olefins, in the refined oil of the present invention, all ethylene yields exceeded 15% and propylene yields exceeded 10%. Judging by On the other hand, in the comparative example which does not satisfy this invention, it turns out that ethylene yield does not exceed 15%, and in particular, since the amount of by-product heavy oil production is large, continuous operation | movement is all problematic.

Experimental Example 5

Heavy oil (hydrogen content: 10.68 wt%, Ni + V metals: 246 wtppm, CCR: 25 wt%, S: 5.5 wt%), which is a residual oil having an API specific gravity of 4.2, is introduced into a solvent extraction treatment apparatus and Extracted and separated using a butane solvent (solvent / oil ratio: 8/1) to an extraction rate of 63 wt% to obtain DAO, and the asphaltene oil was purified by the following hydrogenation conditions to obtain the refined oil 5 of the present invention. .

Hydrogenation Purification Conditions: Ni / Co / Mo + Co / Mo Catalyst (Volume Ratio 2/8), Hydrogen Partial Pressure: 110atm, H ₂ / oil Ratio: 800 Nm 3 / Pa, Temperature: 380 ° C, LHSV: 0.3L / hr

The yield, hydrogen content, increase amount of hydrogen content, V + Ni content, CCR, and sulfur concentration with respect to the raw material oil of obtained DAO and refined oil 5 are shown in Table 4.

Experimental Example 6

Using the same raw material oil as Experimental Example 5, using an isobutane solvent (solvent / oil ratio: 8/1), extraction and separation were performed to obtain an extraction rate of 65 wt%, and then DAO was purified under the following hydrogenation purification conditions. Treatment gave a refined oil 6 of the present invention. Hydrogenation Purification Conditions: Ni / Mo + Co / Mo Catalyst (Volume Ratio 2/8), Hydrogen Partial Pressure: 140atm, H ₂ / oil Ratio: 1000 Nm 3 / Pa, Temperature: 375 ° C, LHSV: 0.2L / hr

The yield, hydrogen content, increase amount of hydrogen content, V + Ni content, CCR, and sulfur concentration with respect to the raw material oil of obtained DAO and refined oil 6 are shown in Table 4.

Table 4

Crude oil Experimental Example 5 Experimental Example 6 DAO Refined Oils5 DAO Refined Oils6 Yield (wt%) 100 63 59 65 59 Hydrogen content (wt%) 10.68 11.83 12.71 11.68 12.96 Hydrogen content increase amount (wt%) - 1.15 0.88 1.00 1.28 Total hydrogen increase amount (wt%) - - 2.03 - 2.28 V + Ni (wtppm) 246.0 41.0 <0.1 45.0 <0.1 Conradson Residual Carbon (wt%) 25.00 11.60 0.56 11.90 0.36 S (wt%) 5.50 4.30 0.20 4.32 0.13

Comparative Example 6

Using the same raw material oil as Experimental Example 5, using an isobutane solvent (solvent / oil ratio: 8/1), extraction and separation were performed to obtain an extraction rate of 65 wt%, and then DAO was purified under the following hydrogenation purification conditions. Treatment gave Comparative Refined Oil F.

Hydrogenation Purification Conditions: Ni / Mo + Co / Mo Catalyst (Volume Ratio 2/8), Hydrogen Partial Pressure: 80atm, H ₂ / oil Ratio: 800 Nm 3 / Pa, Temperature: 340 ° C, LHSV: 0.5L / hr

The yield, hydrogen content, increase amount of hydrogen content, V + Ni content, CCR, and sulfur concentration with respect to the raw material oil of the obtained DAO and refined oil F are shown in Table 5.

Comparative Example 7

Using the same raw material oil as in Experimental Example 5, using an isobutane solvent (solvent / oil ratio: 8/1), extraction and separation were carried out so that the extraction rate was 55 wt%, to obtain a comparative refined oil G.

Table 5 shows the yield, hydrogen content, increase in hydrogen content, V + Ni content, CCR, and sulfur concentration of the obtained refined oil G in terms of raw materials.

Comparative Example 8

Using the same crude oil as in Experimental Example 5, the refined treatment was carried out under the following hydrogenation and purification conditions to obtain comparative refined oil H.

Hydrogenation Purification Conditions: Ni / Mo + Co / Mo Catalyst (Volume Ratio 3/7), Hydrogen Partial Pressure: 140atm, H ₂ / oil Ratio: 1000 Nm 3 / Pa, Temperature: 375 ° C, LHSV: 0.21 L / hr

The yield, the hydrogen content, the increase in the hydrogen content, the V + Ni content, the CCR, and the sulfur concentration of the obtained refined oil H in the raw oil are shown in Table 5.

Table 5

Crude oil Comparative Example 6 Comparative Example 7 Comparative Example 8 DAO Refined Oil F G (extract only) H (hydrogen only) Yield (wt%) 100 65 61 55 91 Hydrogen content (wt%) 10.68 11.68 12.08 11.88 11.69 Hydrogen content increase amount (wt%) - 1.00 0.40 1.20 1.01 Total hydrogen increase amount (wt%) - - 1.40 1.20 1.01 V + Ni (wtppm) 246.0 45.0 <0.1 26.0 32.0 Conradson Residual Carbon (wt%) 25.00 12.20 3.91 9.20 9.25 S (wt%) 5.50 4.32 2.60 4.09 1.31

<Low olefin manufacture example>

Using the final refined oils obtained in Experimental Examples 5 to 6 and Comparative Examples 6 to 8, respectively, the yields of the lower olefins obtained, the yields of by-product heavy oils, and the continuous operability of the obtained lower olefins are shown in Table 6. It was.

Table 6

Experimental Example 5 Experimental Example 6 Comparative Example 6 Comparative Example 7 Comparative Example 8 Hydrogen content (wt%) 12.71 12.96 12.08 11.88 11.69 Ethylene Yield (wt%) 18.1 19.1 13.5 13.1 12.1 Propylene Yield (wt%) 14.7 15.2 9.4 9.1 8.6 By-product heavy oil (wt%) 25.0 23.8 33.2 35.9 36.1 Continuous operation ○ ○ × × ×

In Experimental Examples 5 to 6 of the present invention, in the solvent extraction process, the hydrogen content was extracted to increase by 0.2 wt% or more compared with the heavy raw material oil, and then the hydrogen content increased by 0.5 wt% or more as compared to DAO in the hydrorefining process. As a result, the final refined oil increased by more than 0.7 wt% with respect to the crude oil. In the obtained refined oil of the present invention, all V + Ni concentrations are 0.1 wtppm or less, CCR is 1 wt% or less, and sulfur concentration is 0.5 wt% or less, whereby high-quality refined oil having high impurities is obtained.

On the other hand, in the comparative 7 purified only by the solvent extraction treatment, it can be seen that the removal of impurities is not sufficient even if the extraction rate is reduced to 55%. Comparing Experimental Example 6 of the present invention and Comparative 8 purified only by hydrogenation purification, it can be seen that there are significant differences in the removal of impurities even though the hydrogenation purification is under the same conditions. After increasing, it can be seen that impurities are remarkably removed by hydrorefining to obtain high quality refined oil.

In particular, as a result of pyrolysing the obtained refined oil to produce lower olefins, the refined oil of the present invention has an ethylene yield of more than 15%, a propylene yield of more than 10%, and in particular, continuous operation is possible from the production of by-product heavy oil. It was judged by the range. On the other hand, in the comparative example which does not satisfy the conditions of the present invention, the ethylene yield does not exceed 15%. In particular, it can be seen that there is a problem in that all of the continuous operability is problematic because the amount of by-product heavy oil is large.

Experimental Example 10 Preparation of Refined Oil Based on Heavy Crude Oil

Arabian heavy crude having an API specific gravity of 27.4 was separated into distillate and residue by distillation, and a portion of the distillate was hydrogenated to obtain GO. On the other hand, using the heavy oil having a specific gravity API of 10.9 as the residue oil as the raw material oil 1, solvent extraction treatment and hydrogenation purification treatment was performed under the same conditions as in Experimental Example 1 of the present invention to obtain a refined oil 10.

A part of this refined oil 10 (20 parts by weight based on 100 parts by weight of crude oil) and the GO are mixed with raw material oil 2 and a part (10 parts by weight based on 100 parts by weight of crude oil), and are used as a raw material for pyrolysis for production of lower olefins. Olefin was prepared.

Table 7 shows the yield, hydrogen content, V + Ni metal content, CCR content, and S content of the atmospheric residual oil, deasphaltene oil, hydrogenated purified deasphaltene oil, and heavy ethylene raw material of Experimental Example 10.

Table 7

Raw Material Oil1 Raw oil 2 Raw oil (1 + 2) Atmospheric pressure DAO Refined oils10 GO Refined oil 10:20, GO: 10 Yield (wt%) 61 49 45 18 30 Hydrogen content (wt%) 11.20 11.42 11.95 13.70 12.53 Hydrogen content increase amount (wt%) - 0.22 0.53 - - Total hydrogen increase amount (wt%) - - 0.75 - - V + Ni (wtppm) 153.0 14.2 0.7 <0.1 <0.1 Conradson Residual Carbon (wt%) 12.50 3.60 1.90 0.00 1.20 S (wt%) 4.70 3.50 0.40 0.05 0.27 Ethylene Yield (wt%) - - - - 17.6 Propylene Yield (wt%) - - - - 14.1 By-product heavy oil (wt%) - - - - 25.8 Continuous operation - - - - ○

In Experimental Example 10, the residue oil was used as the raw material oil, and the refined oil obtained by performing the refining treatment of the present invention was mixed with effluent oil having a low impurity concentration to prepare a raw material for producing lower olefins. Both sexes confirmed satisfactory results.

By using the production method of the present invention, it is possible to obtain a refined oil in which heavy oil having a hydrogen content of 12 wt% or less is reliably and economically reduced to reduce impurities, and the use of heavy oil, which has been conventionally limited, can be greatly expanded. .

In the case where the refined oil obtained in the present invention is used as a raw material for producing lower olefins, ethylene and propylene can be produced in economical yield, and in particular, it can be in a range in which commercial operation is possible also in terms of continuous operation.

Claims (8)

As a manufacturing method of heavy oil, A solvent extraction step of extracting a heavy oil having a hydrogen content of 12 wt% or less as a raw material oil so that the hydrogen content increases by 0.2 wt% or more with respect to the heavy oil, and obtaining deasphaltene oil (DAO) as the extraction oil; A process for purifying heavy oil comprising hydrogenation refinement of the deasphalten oil to obtain a refined oil by hydrogenation to increase hydrogen content by 0.5 wt% or more relative to the deasphalten oil. The method of claim 1, The hydrogen content of the refined oil, in which the hydrogen content is increased by 0.7 wt% or more relative to the raw material oil, is 11.5 wt% or more. The method of claim 1, The increase in the hydrogen content of the deasphalten oil to the raw material oil is 0.2 to 1.5 wt%, the increase in the hydrogen content of the refined oil to the deasphalten oil is 0.5 to 1.5 wt%. The method of claim 1, The hydrogen content of the crude oil is 11 to 12 wt%, the increase in the hydrogen content of the deasphalten oil obtained in the solvent extraction step is 0.2 to 1.0 wt%, and the deasphalten oil of the refined oil obtained in the hydrorefining process. The increase in hydrogen content is 0.5 to 1.0 wt%, the process for purifying heavy oil. The method of claim 1, The hydrogen content of the raw material oil is less than 11 wt%, the increase in the hydrogen content of the deasphalten oil obtained in the solvent extraction step is 0.5 to 1.5 wt%, and the deasphalization of the refined oil obtained in the hydrogenation refining process. Method for purifying heavy oil, characterized in that the increase in hydrogen content relative to palten oil is 0.6 ~ 1.5 wt%. The method of claim 1, The total amount of Ni and V in the deasphaltene oil is 70 wtppm or less, and Conradson residual carbon is subjected to solvent extraction so as to be 15 wt% or less. The method of claim 1, V + Ni content of the refined oil is 2 wtppm or less, Conradson residual carbon content is 1 wt% or less, sulfur content is 0.5 wt% or less. The method of claim 1, At least a part of the refined oil is used as pyrolysis raw material oil for producing lower olefins, and the hydrogen content in the pyrolysis raw material oil is 12.0 wt% or more.