JPH1180755A - Production method of non-carcinogenic aromatic hydrocarbon oil by solvent extraction and hydrorefining method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce the subject hydrocarbon oil containing little polycyclic aromatic compound and usable for the production of rubber, ink product, etc., by producing a deasphalted oil from the vacuum distillation residue of petroleum, extraction-treating it with a solvent to obtain a specific extracted oil and hydrogenating the oil under a specific condition. SOLUTION: An extracted oil containing >=30% of carbon constituting aromatic compound determined by the composition analysis in conformity to ASTM D 2140 and <=8% of polycyclic aromatic compounds determined by IP 346 test method is produced from a deasphalted oil obtained from the vacuum distillation residue of petroleum. The objective non-carcinogenic hydrocarbon oil containing >=26% of carbon constituting aromatic compounds determined in conformity to ASTM D 2140 and <3% of polycyclic aromatic compound determined by IP 346 test method can be produced by hydrogenating the extracted oil at 280-360 deg.C under hydrogen pressure of 40-90 kg/cm<2> at a raw material space velocity of 0.5-3.0 LHS.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a process for producing a substantially non-carcinogenic aromatic hydrocarbon oil containing substantially no polycyclic aromatic compounds. In particular, the present invention relates to a method for producing a petroleum-based aromatic hydrocarbon oil used in the production of rubber, ink products, and the like, and relates to a substantially non-carcinogenic aromatic hydrocarbon oil containing almost no polycyclic aromatic compound. Related to the production method.

[0002]

2. Description of the Related Art Generally, a petroleum-based aromatic hydrocarbon oil has a boiling point range of from 260 to 260 obtained by vacuum distillation in the refining of crude oil.
In the solvent extraction purification method of a lubricating oil production fraction at 650 ° C.,
It is well known to those skilled in the art that it is produced as a fraction rich in aromatic hydrocarbon compounds. Therefore, although petroleum-based aromatic hydrocarbon oils differ in their properties and chemical composition depending on the type of crude oil and the conditions of the extraction and refining method, they basically contain a considerable amount of aromatic hydrocarbon compounds as constituent components. Features.

It is well known to those skilled in the art that this petroleum-based aromatic hydrocarbon oil is usefully used as a processing oil for rubber such as natural rubber or SBR used for tires and the like, and as an extension oil for raw SBR. ing. That is, these petroleum-based aromatic hydrocarbon oils are used to improve the series of workability in rubber processing and the physical properties of the final rubber product after vulcanization by utilizing the compatibility with the rubber. It has been added to.

[0004] In order to exhibit compatibility with the rubber, these petroleum-based aromatic hydrocarbon oils are typically used in ASTM D 2140.
In the composition analysis method defined in the above, the carbon content (hereinafter, sometimes referred to as aromatic carbon content, sometimes referred to as Ca%) which forms an aromatic ring, which substantially means the aromatic compound content, is 27 to 55%. I have.

[0005]

However, these petroleum-based aromatic hydrocarbon oils contain, as an additional component, 15 to 28% of a polycyclic aromatic compound (hereinafter referred to as PCA) among the aromatic hydrocarbon compounds contained as components. (Polycyclic aromatics)
May be included). In recent years, by EU directive,
Petroleum products containing 3% or more of this polycyclic aromatic compound have been suggested to be carcinogenic, and efforts have been made worldwide to reduce the amount of polycyclic aromatic compounds in petroleum products.

[0006] Process oils and extender oils for rubber are no exception and many proposals have been made.
-50524 (GB2252978, US550413
5, EP575400), the viscosity is 32 to 50 cS.
t. The aromatic component is 30 to 55% by weight, the saturated hydrocarbon component is 40 to 65% by weight, and the polycyclic aromatic compound or PCA measured by the IP346 method is 30 to 55% by weight according to the clay-gel method specified in ASTM D 2007. Although a petroleum hydrocarbon oil of less than 3% is proposed, the aromatic carbon content (Ca%) specified in ASTM D2140 does not reach 26% in the range of aromatic components by the clay-gel method. , Because it cannot exhibit compatibility and affinity with rubber, it is unsuitable as a substitute for petroleum-based aromatic hydrocarbon oils that have been conventionally used, and especially for SBR and natural rubber. Was unusable at all.

[0007] Further, in EP04179801, an aromatic content of 50% by weight or more and an IP3
46, a method is proposed in which a process oil for rubber having a PCA content of less than 3% is produced from a petroleum-based lubricating oil fraction by a two-stage extraction method. When removing aromatic compounds, a useful non-polycyclic aromatic compound having similar polarity or solubility in a solvent is also dissolved and extracted together with a large amount of loss. It is hard to say that this method is advantageous in terms of process cost, such as lowering the temperature and requiring solvent recovery twice by two-stage extraction.

In Japanese Patent Application Laid-Open No. 7-501346,
Establish a unique relationship between mutagenicity indices and physical properties, and use the process conditions to extract non-carcinogenic bright stock extracts or deoiled oils from hydrocarbon atmospheric distillate resid feedstocks. Although a manufacturing method has been proposed, the present invention provides a EU of substantially less than 3% of PCA.
It is hard to say that the order has been reached.

In addition, DE 40 38 458 proposes a method by a critical extraction method, and WO 9528458 proposes a method by an air oxidizing action. However, any of these methods has a low aromatic content and lacks affinity with rubber. Petroleum aromatic hydrocarbon oil that satisfies its performance and the carcinogenicity recommendation according to EU Directive, that is, less than 3% PCA at the same time, such as those that are not suitable for replacement of rubber process oil and that are too costly in terms of technology and process. No production method which is advantageous in terms of both technology and cost has been proposed.

There is a strong demand for simple and economical production of non-carcinogenic petroleum aromatic hydrocarbon oils.

[0011]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a non-carcinogenic petroleum-based aromatic hydrocarbon having the same performance as existing petroleum-based aromatic hydrocarbon oils including PCA used as a process oil for rubber. It is to satisfy this need by providing a new method for producing hydrogen oil. In particular, an object of the present invention is to provide a simple and economically advantageous non-carcinogenic petroleum-based fragrance from deasphalted oil from the vacuum distillation residue of petroleum by designing strict operating conditions in relation to solvent extraction and hydrorefining. It is an object of the present invention to provide a novel method for producing an aromatic hydrocarbon oil.

[0012]

Means for Solving the Problems Polycyclic aromatic hydrocarbons having the same performance as petroleum aromatic hydrocarbon oils conventionally used as rubber process oils and having carcinogenicity according to the IP346 test method. A new petroleum-based aromatic hydrocarbon oil that is safe and does not pollute the environment by reducing the compound to less than 3%.
An extracted oil having a carbon content of 30% or more for forming an aromatic compound according to the composition analysis method specified in D 2140 and a polycyclic aromatic compound, that is, a PCA content of less than 8% according to the IP346 test method, is obtained. This is achieved by the present invention in which hydrogenation is carried out under conditions for selectively hydrogenating a polycyclic aromatic compound, particularly under conditions that do not cause excessive hydrogenation and hydrogenolysis of a non-polycyclic aromatic compound.

As the feedstock oil to be used in the present invention, a deasphalted oil from which asphalt substances have been removed from light residue such as propane from vacuum distillation residue is applied.

The deoiled oil from the vacuum distillation residue has a boiling point of 26, which is a raw material for the petroleum aromatic hydrocarbon oil currently used.
It is known that it contains basically only a small amount of a polycyclic aromatic compound exhibiting carcinogenicity as compared with a lubricating oil fraction directly distilled under reduced pressure at 0 to 650 ° C.

The carcinogenic polycyclic aromatic compounds according to the EU Directive are strictly speaking DMSO according to the IP346 test method.
(Dimethylsulfoxide) extract, generally 3 to
It is a seven-ring polycyclic aromatic compound. These compounds are almost in agreement with the boiling point range of the lubricating oil fraction after vacuum distillation, which is the current raw material for petroleum aromatic hydrocarbon oil.

The deoiled oil from the vacuum distillation residue has a boiling point much higher than those of these lubricating oil fractions and is composed of a high molecular weight hydrocarbon compound. The inclusion of only a small amount is an essential requirement suitably used in the present invention.

The deoiled oil of the vacuum distillation residue has a different hydrocarbon structure of paraffin, naphthene and aromatic as the hydrocarbon compound composition, like other petroleum hydrocarbon oils such as lubricating oil fractions after vacuum distillation. It is a mixture of compounds. Aromatic hydrocarbon oils currently used as process oils for rubbers have a chemical composition containing more aromatic compounds among them, and are therefore useful because they have compatibility and affinity with rubber.

The aromatic hydrocarbon oil intended for the present invention is also
It is to provide a useful rubber process oil having an aromatic carbon content of 26% or more and containing a large amount of an aromatic component.

Therefore, it is necessary to purify the deoiled oil from the vacuum distillation residue into an aromatic hydrocarbon oil containing a larger amount of an aromatic compound by using a generally used countercurrent contact type extraction column. This is achieved by a solvent extraction method.

The solvent in the extraction operation of the present invention is furfural, phenol, which selectively dissolves aromatic compounds.
Polar solvents such as n-methylpyrrolidone are preferred. These solvents may be used alone or as a mixed solvent of two or more.

The operating conditions in the extraction operation can be appropriately varied depending on the properties of the deoiled oil from the vacuum distillation residue as the feed oil, particularly the aromatic compound content and the polycyclic aromatic compound content. Temperature 90-125 ° C, tower bottom temperature 50-
It is preferable to select at 85 ° C. and a solvent ratio of 1.0 to 5.0.

Naturally, the residue of vacuum distillation changes its properties depending on the type of crude oil and the severity of vacuum distillation, and the deoiled oil also changes its physical properties and chemical composition.

The factor that determines the conditions for the extraction operation of the present invention is the chemical composition of the deasphalted oil as a raw material. First, if the content of the aromatic compound in the deasphalted oil is small, the extraction operation conditions can be made milder, that is, the above-mentioned conditions. Within the range of extraction conditions, select the conditions to lower the extraction temperature at the top and the bottom and lower the solvent ratio to keep the extraction oil yield low, and to increase the aromatic carbon content (Ca%) of the obtained extraction oil. Can do things. Conversely, if the content of the aromatic compound in the deoiled oil is large, the extraction operation conditions are severe, that is, the extraction temperature is increased and the solvent ratio is increased to increase the extraction oil yield. The carbon content (Ca%) can be adjusted.

If the PCA content of the deoiled oil is large,
The extraction conditions are severely adjusted, that is, the extraction temperature is increased and the solvent ratio is increased to increase the extraction oil yield so that the PCA content of the extracted oil is controlled to be low. Thus, the tower top temperature is preferably in the range of 90 to 125C, more preferably in the range of 100 to 120C.

The temperature at the top of the column is an important factor that determines the solubility in the extraction operation and the polarity of the dissolved fraction, that is, the solubility in the solvent. The solubility of the aromatic compound also increases, making it difficult to achieve an aromatic carbon content of 30% or more in the extracted oil supplied to the next hydrorefining. Aromatic compounds are mainly dissolved, and it is difficult to reduce the PCA content of the extracted oil supplied to the next hydrorefining to 8% or less. It becomes difficult to produce a non-carcinogenic useful aromatic hydrocarbon oil having a content of 26% or more and a PCA content of 3% or less. Therefore, the top temperature is 90-125
C., preferably in the range of 100 to 120.degree.

The bottom temperature is calculated by utilizing the difference from the top temperature.
The internal reflux of the solute, ie, that dissolved in the solvent at the top of the column, elutes at a lower temperature at the bottom of the column, which is an important factor in the selectivity of the solute in the extraction operation by reflux in the column.

In this sense, it is advantageous to adopt a lower temperature for the bottom of the tower and to take a large temperature gradient with the top of the tower. This causes a phenomenon that the extraction operation cannot be performed.

In the extraction operation of the present invention, the extraction operation was most stably achieved when the temperature gradient from the top of the column was 30 to 40 ° C. Therefore, the bottom temperature is preferably applied in the range of 50 to 85 ° C. so as to be correlated with the top temperature, that is, to make the temperature gradient 30 to 40 ° C.

The ratio of the flow rate of the solvent to the flow rate of the raw material is referred to as the solvent ratio, and is an important factor that determines the amount of extraction and dissolution together with the extraction temperature.

The solvent ratio is 1.0 to 5.0, preferably 1.
The range is 5 to 4.0. When the solvent ratio is less than 1.0, the polycyclic aromatic compound of the deoiled oil and the aromatic compound having a similar polarity to the solvent are mainly dissolved, and the PCA content of the extracted oil can be reduced to 8% or less. If it exceeds 5.0, the dissolved amount of not only aromatic compounds but also non-aromatic compounds will increase, making it difficult to achieve an aromatic carbon content of 30% or more in the extracted oil. Extra energy is required for recovery, which is disadvantageous in process cost. Therefore, the solvent ratio is preferably 1.0 to 5.0, and 1.5 to 4.0.
Is more desirable.

As described above, by appropriately selecting the extraction conditions depending on the properties of the deoiled oil, it is possible to obtain an aromatic compound having a carbon content of 30% or more by the composition analysis method specified in ASTM D 2140 and an IP346 test method. An extracted oil having a polycyclic aromatic compound content of 8% or less PCA is obtained. This property of the extracted oil is that the following hydrotreating is carried out under mild reaction conditions of relatively low pressure to medium pressure and relatively low temperature to medium temperature, and the extracted oil has an aromatic carbon content of 26% or more and PCA content. 3%
Finishing to less than aromatic hydrocarbon oils is an essential requirement of the present invention.

[0032] Petroleum hydrorefining is a widely practiced process in the petroleum refining industry. The purpose of hydrorefining is broad and its embodiment is mainly a relatively high temperature and high pressure hydrocracking method applied to the production of light fuel oil, a hydrodesulfurization method mainly to remove the sulfur content of the fuel oil, mainly a lubrication Hydrothermal treatment at relatively high temperature and pressure applied to the removal of aromatic compounds by nuclear hydrogenation of oil fractions, mainly applied to color finishing and stability improvement by hydrogenation of olefins and other unstable substances in lubricating oil fractions And hydrodewaxing methods for selectively hydrocracking wax components in liquid hydrocarbons.

The hydrorefining of the extracted oil of the present invention can be made technically easy and advantageous in process cost by applying mild reaction conditions of relatively low pressure to medium pressure and relatively low temperature to medium temperature. , Designed strictly in relation to the deoiled oil extraction process.

That is, the aromatic oil content and the PCA content of the extracted oil provided as the raw material are limitedly realized by the extraction operation,
The polycyclic aromatic compound is hydrogenated and hydrocracked, and the non-polycyclic aromatic compound of the feedstock is embodied by hydrotreating under mild reaction conditions that do not excessively hydrogenate and hydrocrack.

In order to apply these relatively mild hydrogenation conditions, the catalyst used in the present invention comprises one or more metal oxides of iron, cobalt, nickel and molybdenum supported on an inorganic oxide carrier. A catalyst is preferably used. The supported amount of these metal oxides is preferably 23% by weight or more based on the total weight of the catalyst.

The hydrogenation reaction of petroleum is a competitive reaction between the decomposition reaction of the inorganic oxide carrier at the acid point and the hydrogenation by the supported metal. By adjusting the amount of the metal supported on the catalyst, the reaction can be sufficiently performed under mild reaction conditions. The hydrogenation reaction can proceed.
If the amount of the metal oxide carried is less than 23% by weight, the decomposition reaction due to the acidic point of the carrier will prevail and the catalyst will be deactivated such as carbonaceous deposition on the catalyst, which is not preferable.

As the inorganic oxide carrier, alumina, silica, zeolite, aluminosilicate, clay and the like are used, but not limited thereto. Mixtures of silica and alumina are particularly preferred as carriers.

The catalyst is vulcanized and activated by a sulfur-rich petroleum feedstock, such as a vacuum straight cut of petroleum, or a liquid sulfur compound, such as carbon disulfide.

The reaction temperature is suitably in the range of 280-360 ° C, preferably in the range of 300-340 ° C.
Excessive reaction temperatures cause not only the hydrogenation and hydrocracking of the raw polycyclic aromatic compounds, but also the hydrogenation and hydrocracking of the useful non-polycyclic aromatic compounds, and the resulting aromatic hydrocarbons It is not preferable because the aromatic carbon content of the oil cannot be maintained at 26% or more. Furthermore, temperatures above 360 ° C. should not be used, as excessive temperatures will lead to decomposition of the feedstock and deactivation by carbonaceous deposition on the catalyst.

The reaction temperature is preferably 280 ° C. or higher.
If the temperature is lower than 280 ° C., the hydrogenation and hydrocracking of the polycyclic aromatic compound in the raw material extraction oil do not proceed sufficiently, and as a result, an aromatic hydrocarbon oil with a PCA of 3% or less cannot be obtained.

If the polycyclic aromatic compound, ie, the PCA content of the feed oil exceeds 8%, the PCA content of the obtained aromatic hydrocarbon oil cannot be reduced to less than 3% in this temperature range. It is an essential requirement of the present invention to adjust the PCA content of the feedstock oil to 8% or less in the previous extraction step.

The lower the PCA content of the raw extract oil, the milder the conditions of hydrorefining and the less hydrogenation and hydrocracking of the non-polycyclic aromatic compound. PCA of extracted oil in extraction operation
The content and the aromatic carbon content are not unique but fluctuate in a correlated manner, that is, in order to obtain an extracted oil having a lower PCA content, the aromatic carbon content becomes lower, and the aromatic carbon content becomes lower. % Or more, and it is difficult to obtain an aromatic hydrocarbon oil having an aromatic carbon content of 26% or more from such a raw material oil under these reaction temperature conditions. Therefore, in the extraction operation prior to hydrorefining, the PCA content is 8% or less and the aromatic carbon content is 30%.
It is an indispensable requirement of the present invention to adjust the extracted oil to at least%.

The hydrogen pressure for the reaction is preferably in the range of 40 to 90 kg / cm 2. Within this range, the selective hydrogenation and hydrocracking of the polycyclic aromatic compounds of the adjusted raw extract oil of the present invention is achieved, and the excessive hydrogenation and hydrocracking of the non-polycyclic aromatic compounds is achieved. Can be suppressed.

At a pressure of less than 40 kg / cm 2, the hydrogenation and hydrocracking of the polycyclic aromatic compound of the feed oil do not proceed sufficiently, resulting in an aromatic hydrocarbon oil having a PCA content of less than 3%. Things become difficult. Furthermore, since the hydrogenation reaction is not sufficiently achieved, there is a problem in that the feedstock is decomposed and the carbonaceous material is deposited on the catalyst, resulting in deactivation of the catalyst. At a pressure of 90 kg / cm2, the non-polycyclic aromatic compound of the feedstock is hydrogenated and hydrocracked. As a result, it is difficult to obtain a useful aromatic hydrocarbon oil having an aromatic carbon content of 26% or more. Become.

The flow rate of the raw material supplied to the reaction tower is preferably in the range of 0.5 to 3.0 LHSV at a space velocity based on the amount of the charged catalyst. Within this range, in conjunction with the above reaction conditions, selective hydrogenation and hydrocracking of the polycyclic aromatic compounds of the adjusted raw extract oil of the present invention is achieved, and excessive conversion of non-polycyclic aromatic compounds is achieved. Hydrogenation and hydrocracking can be suppressed.

If the space velocity is less than 0.5 LHSV, the hydrogenation and hydrocracking reactions proceed excessively, and not only the removal of polycyclic aromatic compounds but also the addition and hydrogenolysis of non-polycyclic aromatic compounds, As a result, aromatic carbon content 2
It becomes difficult to obtain a useful aromatic hydrocarbon oil of 6% or more. When the space velocity exceeds 3.0 LHSV, the contact efficiency of the feedstock oil with the catalyst surface is extremely reduced, so that the hydrogenation and hydrocracking of the polycyclic aromatic compound in the feedstock oil do not proceed, and as a result, It is difficult to obtain a useful aromatic hydrocarbon oil having an aromatic compound content, that is, a PCA content of less than 3%.

The ratio of the hydrogen flow rate to the feed oil flow rate is not a limiting requirement in the present invention, but may be 200 to 600 sM.
A range of 3 / Kl is preferred. When the flow rate of hydrogen is lower than 200 sM3 / Kl, carbonaceous deposition on the catalyst cannot be suppressed and the catalyst deactivation is promoted, so that the life of the catalyst is shortened. It is disadvantageous in process cost.

The refined oil of the present invention after the hydrorefining treatment is
Finally, a very small amount of the light cracked oil produced by the low-grade hydrocracking accompanying the hydrorefining is removed by a light oil stripping tower to obtain a hydrorefined product, that is, an aromatic hydrocarbon oil.

The thus obtained petroleum aromatic hydrocarbon oil having an aromatic carbon content of 26% or more and a PCA content of less than 3% according to the present invention can be used in a conventionally used rubber process oil or ink formulation. It is a non-carcinogenic petroleum aromatic hydrocarbon oil that has the same performance as the agent and is safe and does not pollute the environment.

Particularly, when the aromatic carbon content is 26% or more,
%, The compatibility and affinity with the rubber are insufficient, and the physical properties of the rubber product using the same, particularly, a decrease in tensile strength and a decrease in elongation are caused. This is an essential requirement for the aromatic hydrocarbon oil of the present invention.

Examples of the present invention will be described below. The invention will be more clearly illustrated and fully understood by the following examples of data obtained from operating conditions that exhibit more salient features of the invention, and data provided as comparative examples. However, the present invention is not limited to these examples.

[0052]

【Example】

[Table 1] Table 1 shows the properties of the feedstock oil used in the present invention. The deoiled oil used as a feedstock oil varies depending on the type of crude oil, the severity of the distillation refining method, and the conditions of the deoiling operation, and its properties are not limited to these two types, but are generally representative of them. The properties of the feedstock are as follows: JIS K 2249 (Crude oil and petroleum products-Density test method and density / mass / volume conversion table)
5. Vibration density test method, viscosity is JIS K 2283 (crude oil and petroleum products-kinematic viscosity test method and viscosity index calculation method),
Refractive index is 14.4 of JIS C 2101 (Electrical insulating oil test method)
In the case of Abbe refractometer, the aniline point was measured according to JIS K2256 (test method for petroleum product aniline point and mixed aniline point).

[0053]

[Table 2] Table 2 shows the result of the extraction processing of the present invention. In Example 1, furfural was used as a solvent, using degreasing oil A as a raw material oil,
An extraction treatment was performed at a tower top temperature of 102 ° C., a tower bottom temperature of 67 ° C., and a solvent ratio of 1.8, and the aromatic carbon content (Ca%) was 36.0%.
And an extracted oil having a PCA content of 4.2%. Example 2
Was prepared by using leaching oil A as a raw material oil, phenol as a solvent, a top temperature of 115 ° C., a bottom temperature of 76 ° C., and a solvent ratio of 2.7.
And the aromatic carbon content (Ca%) is 34.0.
% And an extracted oil with a PCA content of 6.7%. In Example 3, the extraction oil B was used as a raw material oil, furfural was used as a solvent, an extraction temperature was 108 ° C., a tower bottom temperature was 72 ° C., a solvent ratio was 3.2, and an aromatic carbon content (Ca) was obtained. %) And an extracted oil having a PCA content of 5.8%.

[0054]

[Table 3] Table 3 shows the result of the extraction processing not according to the present invention. In Comparative Examples 1 to 3, the extraction conditions according to the present invention, that is, the top temperature of 90 to 1
25 ° C, tower bottom temperature 50-85 ° C, solvent ratio 1.0-5.0
If one of the conditions is not satisfied, the aromatic carbon content is 30%
Obtaining an intermediate oil having an aromatic carbon content of 30% or more and a PCA content of 8% or less, which is to be supplied to the next hydrorefining step, even if either of the above conditions is satisfied or the PCA content is 8% or less. Can not.

[0055]

[Table 4] Table 4 shows the results of the hydrorefining according to the present invention, and the product shows an aromatic hydrocarbon oil obtained by stripping a very small amount of light cracked oil produced in the hydrorefining. Example 4
Uses the extracted oil obtained in Example 1 and has a hydrogen pressure of 70 kg
/ cm2, reaction temperature 320 ° C, raw material flow rate 1.0LHSV,
As a result of performing the hydrogenation treatment at a hydrogen flow rate of 400 GHSV, the aromatic carbon content was 32.5% and the PCA content was 2.2%.
Was obtained. Example 5 uses the extracted oil obtained in Example 1 and has a hydrogen pressure of 45 kg / cm.
2. As a result of performing the hydrogenation treatment at a reaction temperature of 340 ° C., a raw material flow rate of 0.8 LHSV and a hydrogen flow rate of 500 GHSV, an aromatic hydrocarbon oil having an aromatic carbon content of 31.0% and a PCA content of 2.4% was obtained. I got it. In Example 6, using the extracted oil obtained in Example 2, a hydrogen pressure of 90 kg / cm 2, a reaction temperature of 340 ° C., a raw material flow rate of 1.5 LHSV, and a hydrogen flow rate of 6
As a result of performing the hydrogenation treatment with 00GHSV, an aromatic hydrocarbon oil having an aromatic carbon content of 30.5% and a PCA content of 1.8% was obtained. In Example 7, a hydrogen pressure of 80 kg / cm 2, a reaction temperature of 360 ° C., a raw material flow rate of 2.0 LHSV, and a hydrogen flow rate of 500 G were obtained using the extracted oil obtained in Example 3.
As a result of hydrogenation treatment with HSV, the aromatic carbon content was 3
An aromatic hydrocarbon oil having 1.5% and a PCA content of 2.9% was obtained.

[0056]

[Table 5] Table 5 shows the results of hydrorefining not according to the present invention, and the product shows an aromatic hydrocarbon oil obtained by stripping a very small amount of light oil produced in hydrorefining. Comparative Example 4
Nos. 6 to 6 show the results obtained by using the intermediate oil obtained by the extraction operation according to the present invention as a feedstock and applying the conditions for hydrorefining under conditions not according to the present invention. The results show that, even when the extracted oil according to the present invention is used as a raw material, the conditions for hydrorefining according to the present invention, ie, a reaction temperature of 280 to 360 ° C and a hydrogen pressure of 40 to 90 kg / cm.
2. A non-carcinogenic useful aromatic hydrocarbon oil having an aromatic carbon content of 26% or more and a PCA content of less than 3% when at least one of the raw material space velocities of 0.5 to 3.0 LHSV is deviated. Indicates that it cannot be done. Comparative Examples 7 to 9 show the results of using the intermediate oil obtained by the extraction operation not according to the present invention as a raw material and applying the conditions of hydrorefining under the conditions of the present invention.
The results show that, if the extracted oil not according to the present invention is used as a raw material, the conditions for hydrorefining according to the present invention, ie, the reaction temperatures of 280 to 360
° C, hydrogen pressure 40 ~ 90Kg / cm2, raw material space velocity 0.5 ~
Even if 3.0 LHSV is applied, the aromatic carbon content is 26%
This indicates that a useful non-carcinogenic aromatic hydrocarbon oil having a PCA content of less than 3% cannot be obtained.

[0057]

[Table 6]

[Table 7] Table 6 shows the results of studying the aromatic hydrocarbon oil obtained by the present invention as a process oil for rubber. Table 7 shows the results of studies on aromatic hydrocarbon oils not according to the present invention and conventionally used process oils for aromatic rubbers.

The rubber compound used in the study is JIS K 6383 (test method for synthetic rubber SBR) used in the study of compounding materials such as raw rubber, carbon black and process oil.
No. in the standard recipe No. A compounding system according to the compounding method for non-oiled rubber of No. 1 was used, and a kneading method using a rubber compounding roll was also performed by the method described in the same test method. The vulcanization conditions were determined from the results measured with a Japan Synthetic Rubber Curastometer, and vulcanized with a press vulcanizer. For the measurement of product properties, hardness is JIS K 6301 (vulcanized rubber physical test method), tensile strength and 300% tensile stress and elongation are JIS.
K 6251 (Tensile test method for vulcanized rubber), tear strength is JIS
K 6252 (Tear test method for vulcanized rubber) and oil bleedability were carried out by visual inspection after standing at room temperature for 48 hours.

Examples 8 and 9 are the results of investigations on the aromatic hydrocarbon oil according to the present invention, and it was confirmed that they exhibited product properties comparable to those of the commercially available process oil of Comparative Example 10. . Comparative Example 11 is a study result of a hydrocarbon oil not according to the present invention. Compared with the result of the commercially available process oil of Comparative Example 10, the tensile strength and elongation are extremely poor,
Oil bleed was observed in 20 parts of the process oil, and it was confirmed that the oil was not usable.

[0060]

Since the present invention is configured as described above, it has the following effects.
The present invention provides a non-carcinogenic petroleum-based aromatic hydrocarbon having the same performance as a petroleum-based aromatic hydrocarbon oil containing a carcinogenic polycyclic aromatic compound conventionally used as a rubber process oil. The present invention provides a simple and economically advantageous method for producing hydrogen oil from deasphalted oil of petroleum vacuum distillation residue by designing rigorously operating conditions for solvent extraction and hydrorefining.

[0061]

[Brief description of the drawings]

FIG. 1 is a process chart according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Extraction column solvent line 2 Extraction column feed oil line 3 Extraction column extraction residue 4 Extraction column extraction oil line 5 Hydrorefining product line 6 Light cracked oil 7 Aromatic hydrocarbon oil 8 Heat exchanger 9 Extraction column 10 Hydrorefining Tower 11 Light cracked oil stripping tower

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C10G 45/50 C10G 45/50

Claims (5)

[Claims] The present invention relates to an IP346 test method, which comprises extracting a deoiled oil obtained from a petroleum-based vacuum distillation residue by a solvent extraction treatment to form an aromatic compound by a compositional analysis method specified in ASTM D 2140 at a carbon content of 30% or more and an IP346. To obtain an extracted oil having a polycyclic aromatic compound content of 8% or less.
0 to 360 ° C., hydrogen pressure 40 to 90 kg / cm 2, raw material hourly space velocity 0.5 to 3.0 L The carbon content of the aromatic compound specified in ASTM D 2140 which is obtained by hydrogenation reaction is 2140. %, And a non-carcinogenic aromatic hydrocarbon oil having a polycyclic aromatic compound content of less than 3% according to the IP346 test method. 2. The solvent used in the solvent extraction treatment of deoiled oil is one kind of solvent selected from polar solvents of furfural, phenol and n-methylpyrrolidone, or a mixed solvent of two or more kinds. , Claims 1
The method described in the section. 3. A solvent extraction treatment of the deoiled oil is carried out by using a countercurrent contact type extraction column, with a top temperature of 90 to 125 ° C., a bottom temperature of 50 to 85 ° C., and a solvent ratio of 1.0 to 5.0. The method according to claim 1 or 2, wherein the method is performed. 4. The hydrogenation reaction of the extracted oil is carried out by one or more metal oxide catalysts of iron, cobalt, nickel and molybdenum supported on an inorganic oxide.
A method according to any of claims 1, 2 or 3. 5. The method according to claim 4, wherein the total weight of the metal oxide supported on the catalyst is not less than 23% of the total weight of the catalyst.