JPH0670224B2 - Method for producing petroleum hydrocarbon solvent - Google Patents

Description

TECHNICAL FIELD The present invention relates to an improvement in a method for producing a petroleum hydrocarbon solvent. More specifically, the present invention has excellent characteristics such as excellent thermal stability and solubility, a low aromatic content, and a small adverse effect on the working environment and workers. Having, for example, a solvent for printing ink,
The present invention relates to a method for efficiently producing a petroleum hydrocarbon solvent which is preferably used as a solvent for dry cleaning, a solvent for paint, a solvent for washing metal parts and the like.

[Prior Art] Conventionally, petroleum hydrocarbon solvents have been mainly used as solvents for printing inks, paints, rubbers, etc., or as solvents for cleaning, extraction, dry cleaning and the like.

This petroleum-based hydrocarbon solvent can be obtained by simply distilling petroleum and recovering a fraction having a desired boiling point range. In the solvent thus obtained, aromatic hydrocarbons and It contains a lot of olefins. It is known that such a solvent containing a large amount of aromatic components and olefin components significantly contaminates the work environment and has an adverse effect on the health of workers. Regulations on family content are becoming stricter.

Therefore, various attempts have been made so far to produce low aromatic petroleum hydrocarbon solvents. For example, a method of hydrogenating petroleum-based hydrocarbons at high pressure and high temperature, or after hydrogenating petroleum-based hydrocarbons at low pressure, removing n-paraffin content,
Method for producing solvent having improved solubility (Japanese Patent Laid-Open No. 63-1588)
No. 9) is known.

However, in the former method, although the obtained hydrocarbon has a low aromatic content, it has a drawback that it has a high content of paraffins and poor solubility as a solvent product, while the latter method has a drawback. The obtained solvent still has a high aromatic content, and it cannot be said that the influence on the work environment and workers is sufficiently improved, and the heat stability and odor are not always satisfied. Not profitable.

By the way, during the production of ink, since it is exposed to high temperatures such as cooking, a solvent containing a large amount of aromatic components, which is inferior in thermal stability, may discolor during cooking, leading to a reduction in the product value of the ink. In addition, the solubility of the ink solvent is an important factor in terms of storage stability and selection of usable resin and resin concentration. Solvents with better solubility are more likely to cause resin separation during storage. Trouble is unlikely to occur, the resin concentration at the desired viscosity can be increased, and high quality ink can be provided. Therefore, a high-quality ink requires a solvent having excellent thermal stability and solubility. However, until now, as described above, it has been difficult to obtain a solvent that simultaneously satisfies the requirements for thermal stability and solubility, and technical development has been delayed.

[Problems to be Solved by the Invention] Under the circumstances, the present invention has excellent thermal stability and solubility, and also has a low aromatic content, which is suitable for working environments and workers. The object of the present invention is to provide a method for efficiently producing a petroleum-based hydrocarbon solvent having excellent characteristics such as less adverse effects and low odor.

[Means for Solving the Problem] As a result of intensive studies conducted by the present inventors to develop a method for producing a petroleum-based hydrocarbon solvent having the above-mentioned excellent characteristics, petroleum in a specific boiling range is obtained. It was found that the objective can be achieved by subjecting a distillate to hydrogenation by contacting it with a hydrogenation catalyst under predetermined conditions, and then subjecting the obtained liquid product to a specific treatment, and based on this finding, The invention was completed.

That is, the present invention has a boiling point of 130 in the presence of a hydrogenation catalyst.
Petroleum distillate in the range of ~ 400 ℃, temperature 150 ~ 500 ℃, pressure 1
It is characterized in that it is hydrogenated under the conditions of 70 to 230 kg / cm ² -G, and then the obtained liquid product is subjected to a treatment for removing n-paraffins and a precision distillation treatment, which has a boiling point of 130 to 400 ° C. and a naphthene content of Provided is a method for producing a petroleum hydrocarbon solvent having a weight ratio of naphthene content of 0.35 or more and an aromatic content of 2 weight% or less with respect to the total amount of benzene and paraffin content.

Hereinafter, the present invention will be described in detail.

In the method of the present invention, the boiling point of the petroleum fraction of the raw material is
Petroleum hydrocarbons derived from mixed base or paraffin base crude oil in the range of 130 to 400 ° C are used. Preferred examples thereof include kerosene, light oil, and hydrocracked oil.

In the method of the present invention, these petroleum fractions are first contacted with a hydrogenation catalyst to carry out hydrogenation. The hydrogenation catalyst is not particularly limited, and those conventionally used as aromatic compound hydrogenation catalysts can be used. As such a hydrogenation catalyst, for example, on a carrier such as alumina, silica-alumina, crystalline aluminosilicate, zeolite, or activated carbon, a metal element belonging to Group VIA or Group VIII of the periodic table and its oxide or sulfide. The thing carrying at least 1 sort (s) selected from the thing etc. is used. The second
Examples of the VIA group metal element include chromium, molybdenum and tungsten, among which molybdenum and tungsten are preferable, while group VIII metal elements include, for example, iron, cobalt, nickel and ruthenium.
Rhodium, palladium, silver, osmium, iridium,
Platinum and the like can be mentioned, and among these, nickel and cobalt are preferable.

The hydrogenation catalyst used in the present invention is preferably one containing both a metal element of Group VIA and a metal element of Group VIII, and particularly, a combination of nickel and molybdenum and a combination of nickel and tungsten are preferable. Is. As a method for supporting the carrier, a known method such as a coprecipitation method or an impregnation method can be used. Furthermore, if necessary, a small amount of halogen such as chlorine or fluorine may be added to these catalysts for modification.

In the present invention, the catalyst may be used in powder form,
You may shape and use it for a desired shape. When molding into a desired shape, for example, kaolin, silica, alumina or the like can be used as the binder, and the amount thereof is preferably 80% by weight or less based on the total weight. Further, the catalyst may be used in a plurality of stages arranged in series or in parallel.

In the present invention, the hydrogenation catalyst has a boiling point of 130 to 400 ° C.
Hydrogenation is carried out by contacting the petroleum fraction of the above. Regarding the contacting conditions at this time, the reaction temperature is 150 to 500 ° C., preferably 20
It is selected in the range of 0-350 ℃, while the reaction pressure is 170-230kg.
It is selected in the range of / cm ² -G. If the reaction temperature is lower than 150 ° C, the hydrogenation does not proceed sufficiently, and if it exceeds 500 ° C, side reactions such as cracking occur and the olefin content tends to increase. On the other hand, when the reaction pressure is less than 170 kg / cm ² -G, the hydrogenation does not proceed sufficiently, and when it exceeds 230 kg / cm ² -G, side reactions such as decomposition and isomerization tend to occur preferentially. Absent.

The liquid hourly space velocity LHSV in this hydrogenation reaction is usually
It is selected in the range of 0.1 to 10 hr ^-1 , preferably 0.1 to 5 hr ^-1 . Furthermore, this hydrogenation reaction may be carried out batchwise or continuously.

In the method of the present invention, the liquid product obtained by hydrogenating the petroleum fraction as the raw material is thus subjected to the n-paraffins removing treatment and the precision distillation treatment, but the order is not particularly limited. After performing the removal treatment of n-paraffins, the precision distillation treatment may be performed, or after performing the precision distillation treatment, the removal treatment of n-paraffins may be performed.

As a method for removing the n-paraffins, a conventionally known method such as a hydrogenation method, a molecular sieve method, a solvent dewaxing method or the like can be used. The hydrogenation method is a method of removing n-paraffins by contacting with hydrogen by using a shape-selective crystalline zeolite or the like as a catalyst, and the shape-selective crystalline zeolite particularly has an oxygen 10-membered ring or more. Those having pores, for example ZSM-5, ZSM-11, ZSM
-23, ZSM-35, ISI-1, ISI-4, ISI-5, ISI-
6, etc. are preferably used. Regarding the reaction conditions for this hydrogenation, the reaction temperature is usually 200 to 400 ° C., preferably 30
The liquid hourly space velocity LHSV is usually 0.1.
Is selected in the range of -10 hr ^-1 , preferably 0.5-2 hr ^-1 .
When the reaction temperature is lower than 200 ° C. or the liquid hourly space velocity LHSV is higher than 10 hr ⁻¹ , the removal of n-paraffin does not proceed sufficiently, and when the temperature exceeds 400 ° C. or the liquid hourly space velocity is 0.1 hr.
If it is less than ^-1, decomposition may occur, which is not preferable.

On the other hand, the molecular sieve method is a method in which a synthetic zeolite having appropriate pores is used as the molecular sieve, and a liquid product obtained by hydrogenating a petroleum fraction is passed through this to adsorb and remove n-paraffin. In this molecular sieve method, the branched paraffin in the liquid product,
Aromatic hydrocarbons, naphthenes and the like have a molecular shape larger than the pore diameter of the synthetic zeolite used as the molecular sieve, and therefore cannot enter the pores of the synthetic zeolite and are not adsorbed. The n-paraffin is more easily adsorbed as the molecular shape is larger, and is adsorbed as the temperature is lower or the pressure is higher. Therefore, as a method for desorbing the n-paraffins adsorbed on the molecular sieve, A heat swing method in which the temperature is higher than the adsorption temperature to perform desorption and a pressure swing method in which the pressure is reduced to perform desorption can be used. Furthermore, a TSF method using a suitable solvent to replace the adsorbed n-paraffins to desorb the n-paraffins, BP
The method and the Molex method can also be used.

Further, the solvent dewaxing method is used to separate aromatic hydrocarbons such as toluene and benzene, which have high solubility in oil, and wax components (n
-A mixed solvent of ketones such as methyl ethyl ketone or acetone having a low solubility in paraffins) is added to the hydrogenated liquid product, which is cooled to a temperature at which wax components (n-paraffins) are precipitated, In this method, the wax component (n-paraffins) is deposited, and then the deposit is separated and removed by a commonly used means. As the solvent dewaxing method, it is possible to use the MEK dewaxing method which is most widely used at present or the dirutile method equipped with a special crystal generator in order to improve the filtration rate and the dewaxed oil yield. it can.

Among these methods for removing n-paraffins, the crystalline zeolite catalyst is used for hydrogenation to obtain n-paraffins from the viewpoints of yield of solvent fraction, efficiency of operation of the apparatus, selectivity of feed oil, and the like. Is most preferred.

On the other hand, the precision distillation method is not particularly limited, and a commonly used method in which a desired precision fraction is subjected to distillation separation by utilizing the difference in boiling points thereof is used.
As the precision distillation method, for example, the light fraction and the heavy fraction may be separated in the same column, or the light fraction may be separated in the first column and then the heavy fraction may be separated in the second column. Alternatively, this operation may be sequentially performed.

In the present invention, this precision distillation treatment is usually performed after the removal treatment of the n-paraffins. However, if desired, the precision distillation treatment may be performed and then the n-paraffins removal treatment may be performed. .

The petroleum hydrocarbon solvent thus obtained has a boiling point of
It is in the range of 130 to 400 ° C., and the weight ratio of the naphthene component to the total amount of the naphthene component and the paraffin component (hereinafter referred to as “naphthene ratio”) is 0.35 or more, preferably 0.40 to 0.60, and the aromatic component is 2 It is not more than 1% by weight, preferably not more than 1% by weight. When the naphthene ratio is less than 0.35, the solubility is not sufficient, and when the aromatic content exceeds 2% by weight, the working environment and workers are adversely affected, and the thermal stability tends to decrease.

The petroleum hydrocarbon solvent having such a composition has excellent characteristics such as excellent thermal stability and solubility and less adverse effects on the working environment and workers. It is preferably used as a solvent for solvent, a solvent for dry cleaning, a solvent for paint, a solvent for cleaning metal parts, and the like.

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

The obtained solvent was evaluated as follows.

(1) Thermal stability A resin (pentalin 10
4) Take 150g, 150g of solvent, 200g of flaxseed oil, 150 ℃ in oil bath
A varnish is prepared by cooking for 6 hours while heating and stirring. The coloring degree of the varnish formed at this time is determined by ASTM D-
Measure according to 1500.

(2) Solubility in resin (a) Cloud point Resin (pentalin 104) in a glass test tube with an internal volume of 30 ml
After weighing so that the total amount of the solvent and the solvent is 10 g, a glass thermometer and a stirring rod are attached to the test tube using a cork stopper, and this is heated and stirred in an oil bath at 175 ° C. The resin and solvent are made into a uniform solution, then taken out from the oil bath and gradually cooled while stirring at a rate of 5 ° C / min. The temperature at which the resin separates from the solution and becomes cloudy is determined as the cloud point.

The resin concentration (C) of the solution at this time is calculated by the following equation.

WR: sampling weight of resin sample (g) WS: weight of test tube set including test solution- (W + W
R) (g) W: Total weight of test tube, thermometer, stir bar, cork stopper (g) The above operation was repeated 5 to 6 points in the resin concentration range of 2.5 to 40 wt% to measure the cloud point at each resin concentration. The result is linearly approximated according to the following equation by the least squares method.

P = −a × c + b P: Cloud point (° C.) C: Resin concentration (wt%) a, b: Constant (b) In a glass beaker with a viscosity of 100 ml, the total amount of resin (pentalin 104) and solvent is 10 g. After weighing so that it becomes, a lid is covered with an aluminum wheel and heated on a hot plate at 175 ° C, and the beaker is stirred occasionally to form a uniform solution.
Then, allow to cool to room temperature and use a Raleigh viscometer to
Measure the viscosity under conditions of ℃ and load 1000g. This operation is repeated at 5 to 6 points in the resin concentration range of 30 to 70 wt%, and the measurement result of the viscosity at each resin temperature is linearly approximated according to the following equation by the least square method.

log η = a × C + b η: viscosity Note that a solution that is cloudy at room temperature (resin is separated) is not measured.

In this way, the obtained relationship between cloud point and viscosity is shown in a graph, and the solubility in resin is evaluated.

Example 1 A light oil fraction having a boiling range of 210 to 340 ° C. obtained by distilling a mixed base oil (quat crude oil) at atmospheric pressure (paraffin content 64% by weight, naphthene content 22% by weight, aromatic content 12% by weight). )
Temperature 300 ℃, pressure 200 kg / cm ² -G, liquid space velocity 1 hr ^-1
Under the conditions of 20% on a silica-alumina carrier.
Hydrogenation was carried out using a sulphided nickel-tungsten catalyst having wt.% Nickel, 20 wt.% Tungsten and 2 wt.% Fluorine, and the resulting liquid product was subjected to a ZSM-5 type synthetic zeolite catalyst at a temperature of 330 ℃, pressure 50kg / cm
Hydrogenation was carried out under the conditions of ^2- G and liquid hourly space velocity of 1 hr ^-1 , to remove n-paraffin. Then, this was distilled using a precision distillation apparatus, and a fraction having a boiling point of 270 to 300 ° C was used as a solvent fraction.

The properties of this solvent are shown in Table 1, and the thermal stability and the solubility in resin are shown in the graphs of FIGS. 1 and 2, respectively. Fig. 1 shows cooking time and color of resin solution ASTM D-
FIG. 2 is a graph showing the relationship with 1500, and FIG. 2 is a graph showing the relationship between the viscosity of the resin solution and the extrapolation cloud point.

Example 2 Using the ZSM-5 type synthetic zeolite catalyst in Example 1, temperature is 300 ° C., pressure is 50 kg / cm ² -G, and liquid hourly space velocity is 1 hr ^−1.
A solvent was obtained in exactly the same manner as in Example 1 except that the n-paraffin was removed by hydrogenation under the conditions of.

The properties of this solvent are shown in Table 1, and the thermal stability and the solubility in resin are shown in FIGS. 1 and 2, respectively.

Example 3 After hydrogenating the same mixed base oil as in Example 1 under the same conditions,
This product oil is subjected to precision distillation to obtain a fraction having a boiling point of 270 to 300 ° C., which is then used a ZSM-5 type synthetic zeolite catalyst at a temperature of 330 ° C., a pressure of 50 kg / cm ² -G, and a liquid hourly space velocity of 1 hr. ^-1
Hydrogenation was carried out under the conditions of and n-paraffin was removed to obtain a solvent.

The properties of this solvent are shown in Table 1, and the thermal stability and the solubility in resin are shown in graphs in FIGS. 1 and 2, respectively.

Comparative Example 1 In Example 1, hydrogenation conditions were a temperature of 300 ° C. and a pressure of 60 k.
Example 1 except g / cm ² -G and liquid hourly space velocity 1 hr ^-1
A solvent was obtained in the same manner as in.

The properties of this solvent are shown in Table 1, and the thermal stability and the solubility in resin are shown in graphs in FIGS. 1 and 2, respectively.

Comparative Example 2 A solvent was obtained in the same manner as in Example 1 except that the n-paraffin removal treatment was not performed.

The properties of this solvent are shown in Table 1, and the solubility in resin is shown in Table 2.
Shown in the figure.

From FIG. 1, it can be seen that the solvents of Examples 1, 2 and 3 do not discolor much even after the cooking time elapses, but the naphthene ratio is high and the solubility is excellent, but the comparative examples having a high aromatic content It can be seen that the solvent of No. 1 has a greater degree of discoloration as the cooking time elapses.

In addition, from FIG. 2, the solvents of Examples 1, 2 and 3 have considerably low extrapolation cloud points when the viscosities after resin dissolution are the same, as compared with the solvents of Comparative Examples 1 and 2, resulting in poor solubility. It turns out to be excellent. In particular, the solvent of Comparative Example having a low aromatic content but a low naphthene ratio has poor solubility in the resin and exhibits a cloud point even at room temperature.

[Effects of the Invention] As described above, the boiling point of 130 to 4 obtained by the method of the present invention
A petroleum hydrocarbon solvent with a temperature of 00 ° C, a naphthene ratio of 0.35 or more and an aromatic content of 2% by weight or less has excellent thermal stability and solubility, and has little adverse effect on the working environment or workers. It also has a characteristic of low odor, and is suitably used as, for example, a solvent for ink, a solvent for dry cleaning, a solvent for cleaning metal parts, a solvent for paints and the like.

[Brief description of drawings]

1 and 2 are graphs showing the relationship between the cooking time after resin dissolution and the degree of coloring, and the viscosity after resin dissolution and extrapolation in the solvents obtained in Examples and Comparative Examples of the present invention, respectively. It is a graph which shows the relationship with a cloud point.

Continuation of front page (56) Reference JP-A-63-15889 (JP, A) JP-A-51-117709 (JP, A) JP-A-53-95885 (JP, A) JP-A-54-101807 (JP , A) JP-A-55-65295 (JP, A) JP-A-57-151692 (JP, A)

Claims (3)

[Claims] 1. A petroleum fraction having a boiling point in the range of 130 to 400 ° C. in the presence of a hydrogenation catalyst is heated at a temperature of 150 to 500 ° C. and a pressure of 170 to 230 kg.
hydrogenation under the condition of / cm ² -G, and then subjecting the obtained liquid product to a treatment of removing n-paraffins and a precision distillation treatment, boiling point 130 to 400 ° C, naphthene content and paraffin content. Weight ratio of naphthene to total amount of and 0.35
The above and a method for producing a petroleum hydrocarbon solvent having an aromatic content of 2% by weight or less. 2. The method according to claim 1, wherein the liquid product is subjected to a treatment for removing n-paraffins and then subjected to a precision distillation treatment. 3. A liquid product, which has been subjected to precision distillation treatment,
The method according to claim 1, wherein the n-paraffins are removed.