JPH11269764A - Oil agent for textile processing and method for producing the same - Google Patents

Abstract

(57) [Problem] To provide a fiber processing oil agent which has a polycyclic aromatic content of less than 3% by weight, prevents troubles due to wax precipitation, and does not cause discoloration of fibers after application. SOLUTION: It is a mineral oil-based oil agent having a boiling point at normal pressure in a range of 240 to 470 ° C, a 50% by volume distillation temperature in a range of 310 to 350 ° C, and a kinematic viscosity at 40 ° C of 6 to 40 ° C. It is in the range of 11 mm ² / s, the pour point is −5 ° C. or less, the sulfur content is 0.1% by weight or less, and the polycyclic aromatic component is less than 3% by weight. Oil for textile processing.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oil agent for fiber processing which is effectively used for fiber processing, especially spinning, drawing, spinning and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, industrial fluid paraffins and naphthenic oils have been used as mineral oil oils for fiber processing. However, these oils may cause uneven application to fibers due to poor emulsification stability during use, and may cause discoloration of fibers after processing due to lack of thermal stability and weather resistance of the oil itself. . In order to solve these problems, there is a naphthenic (naphthene content: 285 or more) oil agent having an aromatic content of 1% or less and an iodine value of 3 or less (JP-A-64-45869). However, even in this case, sufficient weather resistance cannot be obtained, or a wax component in oil precipitates at a low temperature treatment, which takes in additives such as an antistatic agent used together with the oil agent, and reduces the effect of the additive. There was a problem.

A number of synthetic oils have been developed (for example, see JP-A-51-32897 and JP-A-55-22).
024) These are quite different from the general lubricating oil production process from mineral oil and are very expensive and the types of fibers processed are limited.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above, and it has been proposed that wax at a low temperature be deposited in an oil agent,
Accordingly, an object of the present invention is to provide an oil agent for fiber processing, which can prevent a decrease in oil agent performance due to precipitation and separation of additives such as an antistatic agent together with wax. It is another object of the present invention to provide an oil agent for textile processing capable of reducing the polycyclic aromatic component of a harmful substance to a level that is substantially harmless.

Another object of the present invention is to provide a method for producing an oil agent for fiber processing, which can easily obtain an oil agent having such performance and function at a relatively low cost.

[0006]

Means for Solving the Problems As a result of diligent research, the present inventors have found that an oil agent having specific physical properties and properties can be an excellent oil agent for fiber processing satisfying the above-mentioned objects, and that such an oil agent having a high performance can be obtained. As a method for producing oils for textile processing, using a highly refined fraction of a specific petroleum fraction as a raw material,
The present inventors have found that a novel manufacturing method in which a dewaxing treatment or the like is added thereto is preferable and is a practically advantageous method, and completed the present invention.

That is, the present invention has the following gist. (1) Boiling range of 240 to 470 ° C, 50% by volume
The distillation temperature is in the range of 310 to 350 ° C, the kinematic viscosity at 40 ° C is in the range of 6 to 11 mm ² / s, the pour point is -5 ° C or less, and the sulfur content is 0.1% by weight or less. Mineral oil-based fiber processing oil agent characterized by having a polycyclic aromatic content of less than 3% by weight. (2) The cloud point is -5 ° C or less and the density is 0.8
The oil agent for fiber processing according to (1), wherein the oil content is 40 to 0.869 g / cm ³ and the total aromatic content is 15% by weight or less. (3) The oil agent for fiber processing according to (1) or (2), wherein the polycyclic aromatic component is 0.5% by weight or less and the total aromatic component is 3% by weight or less.

(4) A fraction having a boiling range of from 120 to 500 ° C. obtained by distilling crude oil is subjected to hydrorefining to reduce the sulfur content to 0.05% by weight or less, and a fraction having a boiling point of 260 ° C. or more Wherein the fraction is subjected to hydrodewaxing treatment, and the fraction is subjected to hydrodewaxing treatment. (5) The method for producing an oil agent for fiber processing according to (4), wherein a hydrofinishing treatment is further added after the hydrodewaxing treatment.

[0009]

Embodiments of the present invention will be described below. First, the fiber processing oil agent of the present invention will be described. The oil agent of the present invention shown in the above (1) can be realized as those having various compositions and properties according to the purpose and the production method, but it is necessary to satisfy at least all of the conditions of the above (1). It is important.

That is, it is important that the oil agent of the present invention has a boiling point at normal pressure in the range of 240 to 470 ° C., and preferably in the range of 250 to 460 ° C.
More preferably, it is in the range of 60 to 450 ° C. It is important that the 50% by volume distillation temperature is in the range of 310 to 350 ° C, preferably in the range of 320 to 345 ° C, and more preferably in the range of 325 to 340 ° C. If the 50% by volume distillation temperature is too high, the amount of high molecular weight normal paraffins used as the basis for the wax in the high boiling fraction increases. If the amount is large, it is relatively easy to lower the pour point in the hydrotreating step, but it is difficult to lower the cloud point. In addition, the measured value of the above distillation is AST
It is a value according to the MD-2887 method.

It is also important that the oil agent of the present invention has a kinematic viscosity at 40 ° C. in the range of 6 to 11 mm ² / s, and in particular, those having a kinematic viscosity in the range of 6.5 to 10.5 mm ² / s. Those having a range of preferably 7 to 9.5 mm ² / s are more preferable. Viscosity is important during fiber processing, and coating unevenness is likely to occur if the viscosity is too high or too low. Furthermore, the optimum viscosity must be selected according to the fiber type, processing machine, and processing conditions. Adjustment of the viscosity is also important to ensure the smoothness of the fiber, and it is important that the viscosity be in the above range.

It is also important that the oil agent of the present invention has a pour point of -5 ° C or lower, and particularly preferably -10 ° C or lower, and more preferably -15 ° C or lower. This makes it possible to ensure low-temperature fluidity of the oil agent, not only to sufficiently cope with use in a low-temperature environment, but also to prevent deposition of wax components at low temperatures and to eliminate uneven coating. In addition, the additive may be taken into the wax at the same time as the wax is precipitated, and the effect of the additive is reduced. However, this can be prevented.

Further, it is important that the sulfur content of the oil agent of the present invention is as low as 0.1% by weight or less. If it exceeds 0.1% by weight, the oxidation stability is remarkably reduced, which is not preferable.
Preferably less than 0.05% by weight, 0.02% by weight
The following are more preferred. In oils produced from mineral oil, the sulfur content can be said to be a measure of the degree of refining. Therefore, the oil agent of the present invention having a low sulfur content has a high degree of refining, has improved weather resistance and heat resistance, and can inevitably prevent discoloration of the processed fiber.

As described above, the polycyclic aromatic content of the present invention must be less than 3% by weight, preferably 0.5% by weight or less, more preferably 0.1% by weight, due to the carcinogenicity problem.
The following is good. Note that the value of the polycyclic aromatic component here is I
It was measured by the P346 / 92 method. The oil agent of the present invention can exhibit sufficient performance by satisfying the above conditions.

The oil agent of the present invention shown in the above (2) has the cloud point of -5 ° C. in addition to the properties described in the above (1).
Or lower, preferably -10 ° C or lower. The clouding point is an index of wax deposition directly from the pour point, and by setting the above range, it is possible to prevent uneven application of the oil during fiber processing, poor emulsification of the oil agent due to a decrease in the effect of the emulsifier, a decrease in the antistatic effect, and the like. it can. In addition, the cloudy point is JIS K226
This is measured by the method of No. 9. The density is 0.84
0 to 0.869 g / cm ³ , preferably 0.85 g / cm ³
In the range of 0 to 0.867 g / cm ³ , with a total aromatic content (% C _A ) of 15% by weight or less, preferably 3% by weight or less.
% By weight (NDM method) or less. If the aromatic content is too high, the weather resistance and heat resistance of the oil agent decrease.

The oil agent described in the above (3) contains 0.5% by weight or less of a polycyclic aromatic component which is pointed out as harmful in the above (1) or (2), and tends to cause fiber coloring. An oil agent having an aromatic content of 3% by weight or less and particularly improved performance.

The oil agent of the present invention can be used alone or by mixing or adding various additives depending on the purpose and application. That is, the oil agent of the present invention can be used as an oil agent by itself, but it is generally preferable to use the oil agent dispersed in water and adding various additives such as an emulsifier and an antistatic agent. Various additives such as known ones can be used as additives, and polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene alkylamide are used as emulsifiers. And the like, and anionic surfactants such as alkyl benzene sulfonate and alkyl naphthalene sulfonate. The amount of these additives is preferably about 0.001 to 10% by weight based on the amount of the oil, but it is at least better if effects such as emulsification of the oil and dispersion of other additives are obtained.

As the antistatic agent, when used before the fiber dyeing step, a temporary antistatic agent is often used, and a sulfate ester type, an anionic activator, a phosphate ester type anionic activator, and a quaternary ammonium type cationic activator are used. Those which depend on the hygroscopicity and ionicity of these surfactants, such as betaine-type amphoteric surfactants, can be used. A washing-resistant antistatic agent such as a water-soluble polymer containing an epoxy or quaternary ammonium base can also be used.

In addition, an extreme pressure agent, an antiwear agent, an oil agent and the like may be added. Any extreme pressure agent may be used, such as a sulfur-based, phosphorus-based, or halogen-based extreme pressure agent. Examples of the antiwear agent include molybdenum compounds such as MoDTP and MoDTC, graphite and boron compounds, and examples of the oily agent include higher fatty acids such as oleic acid and stearic acid, higher alcohols, amines, esters, and fats and oils.

The oil agent of the present invention is not particularly limited as a general production method, but can be suitably and efficiently produced by the method of the present invention described in the above (4) or (5). Hereinafter, the method described in the above (4), which is a preferred method for producing the oil agent of the present invention, and subsequently the method described in the above (5) will be described in detail.

As the raw material, it is preferable to use paraffin-based crude oil and mixed base crude oil or a mixture thereof.
The target oil agent is basically produced from the crude oil by an essential oil process comprising an atmospheric distillation step, a hydrorefining step, a vacuum distillation step and a hydrodewaxing step, as shown below.

(Step 1) Atmospheric distillation step The crude oil is subjected to atmospheric distillation to have a boiling point of 120 to 500 ° C.
Within the range, a fraction having a 50% by volume distillation temperature of 330 ° C. or lower is obtained, and the fraction is subjected to a hydrorefining step.

(Step 2) Hydrorefining Step As a catalyst used in the hydrorefining step, silica alumina, alumina, titania, boria, zeolite or the like is used as a carrier, and a metal of Group VIB of the periodic table and / or VIII is used as the carrier. A material carrying a group III metal is used. Here, the group VIB metals of the periodic table include Cr, Mo and W,
Among them, Mo and W are preferable. Examples of the Group VIII metal of the periodic table include Co, Ni, Rh, Ru, Pd, and Pt, but Co is usually preferred. These metals can be used alone or in combination of two or more, but usually,
Combinations of Co-Mo, Ni-W and the like are preferred. When zeolite is used, for example, X-type, Y-type
Various types such as a mold, faujasite, ZSM-5, and mordenite can be used. Among them, a Y type is particularly preferably used. Further, a plurality of types of carriers may be appropriately mixed or combined for use. For example, in the case of zeolite, one formed by using alumina, silica alumina, or the like as a matrix is preferably used. Further, as the catalyst, those containing a carrier component and a metal component other than those described above can be used as appropriate.

The purification conditions are preferably carried out as follows. That is, the hydrogen partial pressure is usually 5.6 to 10M.
Pa, preferably 6 to 8 MPa, more preferably 6
It is preferable to select a value within the range of 7 MPa. The ratio of the supplied hydrogen gas is usually 100 to 1 kl of the supplied oil.
1000 nm ^3, preferably, more preferably 200 to 800 nm ^3, may be adjusted to a range of 250~650Nm ^3. The reaction temperature is usually from 200 to 450 ° C, preferably from 250 to 400 ° C, more preferably from 260 to 450 ° C.
It is preferable to select a temperature in the range of 380 ° C. The liquid hourly space velocity (LHSV) is usually 0.1 to 10 based on the supply oil.
hr ^-1, preferably, 0.3～8Hr ^-1, more preferably, it may be suitably adjusted to a range of 0.5~5hr ^-1. By the above hydrorefining process, the sulfur content is reduced to 0.05% by weight or less.

(Step 3) Vacuum Distillation Step The fraction obtained in the step 2 is distilled under reduced pressure to obtain a boiling point of 2
A fraction in the range above 60 ° C. is obtained. Note that the boiling point is a normal-pressure-converted boiling point.

(Step 4) Hydrodewaxing In this method, the fraction is subjected to catalytic reaction with hydrogen in the presence of a suitable catalyst to perform dewaxing. This hydrodewaxing can be carried out basically according to a conventional method, but usually, it is preferable to carry out the hydrogenation reaction for dewaxing under the following conditions. The raw material to be subjected to the hydrodewaxing treatment is not limited to only the 100% fraction at 260 ° C. or higher from Step 3. Light oil obtained by hydrocracking under reduced pressure medium gas oil, reduced pressure heavy gas oil, degreasing oil, or any of these two or more mixed oils under the conditions of a hydrogen partial pressure of 150 MPa or more and a reaction temperature of 350 ° C. or more Any blended oil with 60 neutral can also be used as a feed.

As the catalyst, various catalysts can be used, and usually, ZSM-5 or ZSM-5 type zeolite, silicon aluminum phosphorus composite oxide (SAPO)
A carrier having Ni, Pt, Pd or the like supported thereon is preferably used.

The hydrogen partial pressure is usually 1 to 10 MPa, preferably
Or 2 to 8 MPa, more preferably 2.5 to 5 M
It is preferable to select the range of Pa. Supply of hydrogen gas
The ratio is usually 100 to 100 per 1 kl of supplied oil.
0Nm ^Three, Preferably 250 to 800 Nm^ThreeMore preferred
Or 300-600Nm^ThreeIt is better to adjust to the range of
No. The reaction temperature is usually 200 to 420 ° C, preferably
Is from 250 to 400 ° C, more preferably from 300 to 36 ° C.
It is preferable to select a temperature in the range of 0 ° C. In addition, liquid space velocity
The degree (LHSV) is usually 0.1 to 10 hours based on the supply oil.
r^-1, Preferably 0.3 to 8 hours^-1, More preferably
Is 0.5 to 5 hours^-1May be adjusted as appropriate. Most
After that, it is subjected to distillation treatment to obtain a boiling point range, 50% outflow temperature,
Adjust the degree and possibly the density.

By the above steps 1-4, the production method of the present invention described in the above (4) is completed, and the above (1) or (2)
The described oil agent of the present invention can be produced efficiently, at low cost and with high productivity.

Next, the production method of the present invention described in the above (5) will be described. (Step 5) Hydrofinishing Treatment The oil treated by the method described in the above Steps 1 to 4 may be subjected to a hydrofinishing treatment before or after the last distillation treatment in the above Step 4. The hydrofinishing treatment may be carried out by a usual method. First, as a catalyst to be used, a silica alumina, alumina, titania, boria, zeolite or the like is used as a carrier, and a metal of Group VIB and / or VIII of the periodic table is supported on the carrier. Use what you have done. Here, as the VIB group metal,
Cr, Mo and W can be mentioned, among which Mo,
W is preferred. Group VIII metals include Co, Ni,
Rh, Ru, Pd, Pt and the like can be mentioned,
Co and Ni are preferred. These metals can be used alone or in combination of two or more, but usually a combination of Co-Mo, Ni-W or the like is preferable.

When zeolite is used, various types such as X-type, Y-type, faujasite, ZSM-5, mordenite and the like are used, and Y-type is particularly preferable. Further, a plurality of types of carriers may be appropriately mixed or combined for use. For example, in the case of zeolite, one formed by using alumina, silica alumina, or the like as a matrix is preferably used.

The reaction conditions for hydrofinishing with the above catalyst are suitably carried out under the following conditions. That is,
The hydrogen partial pressure is generally 10 to 30 MPa, preferably 15 to 25 MPa.
MPa, supply hydrogen gas is usually 50 for 1 kl of supply oil.
0 to 4000 Nm ^3, preferably 800 to 3000 N
m ³ , the reaction temperature is usually 240-360 ° C., preferably 25
0 to 320 ° C., the liquid hourly space velocity (LHSV) usually supply oil standards 0.1～5Hr ^-1 preferably 0.4～1.2Hr ^-1
The range may be adjusted.

The catalyst and reaction conditions depend on the performance of the target oil agent,
What is necessary is just to adjust suitably from the said range according to a function. Further, if necessary, a distillation treatment may be performed to adjust the boiling point range, 50% outflow temperature, kinematic viscosity, and, in some cases, the density to adjust the above (1).
The method (5) for producing an oil agent according to any one of (1) to (3) is completed. The fiber processing oil agent thus obtained can be effectively used in various fiber processing steps.

[0034]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Example 1 Arabian Heavy Crude Oil Distillation Treatment Boiling Point 133-451 ° C., 50% by Volume Distillation Temperature 31 Obtained
A catalyst comprising cobalt and molybdenum supported on an alumina carrier using a straight ^- run light gas oil having a sulfur content of 1.4% by weight at 2 ° C., a hydrogen partial pressure of 6.0 MPa, an LHSV of 1.5 hr ⁻¹ , and a hydrogen / oil ratio of 250 Nm ³ / Hydrorefining was carried out under the conditions of kl and a reaction temperature of 341 ° C to obtain a light desulfurized gas oil having a sulfur content of 0.04% by weight. This was subjected to ordinary vacuum distillation to obtain a waxy heavy gas oil (raw material 1) having a temperature of 260 ° C. or higher. Using this as a raw material, ZSM-5 was prepared at a hydrogen partial pressure of 2.8 MPa, an LHSV of 1.0 hr ^-1 , a hydrogen / oil ratio of 450 Nm ³ / kl, and a reaction temperature of 300 ° C.
Hydrodewaxing was carried out using a catalyst supporting Ni on the surface, followed by finishing at a reaction temperature of 240 ° C. using a catalyst supporting cobalt and molybdenum on alumina. Light components and the like were removed from the obtained reaction product by distillation, and the viscosity, boiling point range, 50% outflow temperature, and density were adjusted to obtain a base oil 1. [Example 2] Base oil 2 was obtained by treating raw material 1 under the same conditions as in Example 1 except that the hydrodewaxing reaction temperature was 311 ° C. Example 3 A straight-run light gas oil having a boiling point of 137 to 456 ° C., a 50% by volume distillation temperature of 315 ° C., and a sulfur content of 1.6% by weight obtained by distilling a zakum-based crude oil was used as an alumina carrier for cobalt and molybdenum. And a hydrogen partial pressure of 6.
0MPa, LHSV1.5hr ^-1 , Hydrogen / oil ratio 250N
Hydrorefining under the conditions of m ³ / kl and reaction temperature of 343 ° C.
A light desulfurized gas oil having a sulfur content of 0.05% by weight was obtained. This was subjected to ordinary vacuum distillation to obtain a waxy heavy gas oil (raw material 2) at 260 ° C. or higher. Using this as a raw material, a hydrogen partial pressure of 2.8
MPa, LHSV 1.0 hr ^-1 , hydrogen / oil ratio 450 Nm
Hydrodewaxing was performed at ³ / kl at a reaction temperature of 332 ° C. with a catalyst supporting Ni on ZSM-5, and subsequently, finishing was performed at a reaction temperature of 240 ° C. with a catalyst supporting cobalt and molybdenum on alumina. The viscosity and the like of the obtained reaction product were adjusted by distillation in the same manner as in Example 1 to obtain Oil Agent 3. [Example 4] The oil agent obtained in Example 1 was subjected to a hydrofinishing treatment with a hydrofinishing catalyst in which nickel and tungsten were supported on an alumina carrier. The reaction conditions are a reaction temperature of 295 ° C., a hydrogen partial pressure of 20 MPa, and an LHSV
0.6 Hr ^-1 , a hydrogen / oil ratio of 2000 Nm ³ / kl,
The viscosity and the like of the obtained reaction product were adjusted by distillation in the same manner as in Example 1 to obtain an oil agent 4. .

In the above examples, the properties of the raw materials 1 and 2 are shown in Table 1 and the properties of the oils 1 to 4 are shown in Table 2.

[0036]

[Table 1]

[0037]

[Table 2]

[0038]

The oil agent of the present invention is a fiber processing oil agent having a polycyclic aromatic content of less than 3% by weight and having excellent low-temperature crystal precipitation resistance, weather resistance, heat resistance and smoothness. Further, according to the production method of the present invention, a pour point and a cloud point can be efficiently reduced, and a method for producing the above-mentioned oil agent of the present invention at low cost and with high productivity can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C10G 65/04 C10G 65/04 C10M 101/02 C10M 101/02 // C10N 20:00 20:02 30:00 40:00 70 : 00

Claims (5)

[Claims] 1. A boiling point range of 240 to 470 ° C. and 50
The volume% distillation temperature is in the range of
The kinematic viscosity at 0 ° C. is in the range of 6 to 11 mm ² / s, the pour point is -5 ° C. or less, the sulfur content is 0.1% by weight or less, and the polycyclic aromatic component is 3% by weight. Mineral oil-based fiber processing oil agent, 2. A cloud point of -5 ° C. or lower, a density of 0.840 to 0.869 g / cm ³ , and a total aromatic content of 1
The fiber processing oil agent according to claim 1, wherein the amount is 5% by weight or less. 3. The polycyclic aromatic component is 0.5% by weight or less,
3. The textile processing oil agent according to claim 1, wherein the total aromatic content is 3% by weight or less. 4. The boiling point range obtained by distilling crude oil is 1
The fraction at 20 to 500 ° C. is hydrorefined to a sulfur content of 0.05% by weight or less, then the fraction having a boiling point of 260 ° C. or higher is separated by distillation, and the fraction is hydrodewaxed. The method for producing an oil agent for fiber processing according to any one of claims 1 to 3, wherein: 5. The method for producing an oil agent for fiber processing according to claim 4, wherein the fraction is further subjected to hydrofinishing after the hydrodewaxing treatment.