KR101971360B1 - Method of manufacturing a naphthene-rich dearomatized hydrocarbon fluids - Google Patents

Abstract

The present invention relates to a method for manufacturing a naphthene-rich dearomatized hydrocarbon fluid (oil content less than 1000 ppm based on the weight of aromatics) having a lower sulfur content (less than 5 ppm by weight) through a hydrogenation step of a raw material, wherein the raw material is a mixture of kerosene or diesel with low sulfur content (less than 10 ppm by weight) with a boiling point in a range of 130 to 350°C, or aromatic rich oil (oil content having an aromatic content of 99% or more by weight) having a boiling point range (130 to 400°C) higher than or similar to a boiling point of a middle distillate including all or part of kerosene and diesel.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for producing a naphthene-rich dearomatic hydrocarbon fluid,

The present invention relates to a process for the preparation of a dearomatic (less than 1000 ppm by weight aromatic hydrocarbon) hydrocarbon fluid rich in naphthene with a lower sulfur compound content (less than 5 ppm by weight). Specifically, kerosene or diesel having a low boiling point in the range of 130 to 350 ° C (less than 10 ppm by weight), or a middle distillate containing all or part of kerosene and light oil, Rich aromatics (oil with an aromatic content of 99% or more by weight) having a similar or higher boiling point range (130 to 400 ° C) to the aromatic component To a naphthenic component to produce a naphthenic enriched dearomatic hydrocarbon fluid having a lower sulfur compound content (5 ppm by weight or less).

Hydrocarbon fluids are widely used as solvents for liquid detergents, paints and printing inks, metal extraction and metalworking, drilling fluids, and the like. More broadly, it can be used as a solvent in a chemical reaction. Such a hydrocarbon fluid can be produced through a hydrogenation step using kerosene or light oil, or an intermediate oil including kerosene and light oil as raw materials. This treatment process is called a hydro-dearomatization process, and generally consists of a distillation column for separating raw materials, a reactor in which a hydrogenation step is carried out, and a distillation column for classifying the produced reactants according to product specifications. Generally, the hydrogenation step consists of one or more reactors. Since the sulfur component of the raw material acts as a poison to the catalyst used in the hydrogenation step, a plurality of reactors used for converting the aromatic component and a reactor for removing the sulfur component are provided. The catalyst in the reactor used to remove the sulfur component will degrade as the sulfur component is adsorbed, requiring a short cycle of catalyst replacement to avoid overflowing the next reactor. In the case of a reactor for converting an aromatic component, the catalyst replacement cycle is relatively long as a hydrocarbon fluid having a very small sulfur content is supplied.

It is an object of the present invention to provide a method for adjusting the physical properties of a product in the process of producing a dearomatic (less than 1000 ppm by weight) hydrocarbon fluid with a lower sulfur content (less than 5 ppm by weight). Specifically, the aim is to control the solvency of a product by controlling the content of naphthene of the product by controlling the aromatic content of the raw material.

The present invention relates to a process for the production of a de-aromatized hydrocarbon fluid rich in naphthene content with a lower sulfur content (5 ppm by weight or less), wherein the boiling point is from 130 to 350 ° C A mixture of aromatics rich in aromatics (oils with an aromatics content of 99% or more by weight) in kerosene or diesel with low sulfur content (less than 10ppm by weight) in the range or middle distillate containing them . Preferably an aromatic rich oil having a boiling point in the range of 130 to 250 ° C and a boiling point (130 to 400 ° C) similar to or higher than 99% by weight on light oil in the range of 200 to 350 ° C is used . This is because the aromatic component is converted into the naphthenic component through the hydrogenation step and the boiling point thereof is lowered. Examples of aromatics-rich oils include Aromatic 150 (A-150), Aromatic 200 (A-200) and Aromatic 300 (A-300) products having an aromatic component content of 99.5% or more in aromatic solvent products. The aromatic content of the feedstock is controlled by controlling the mixing ratio of the two oils depending on the product to be produced, and the heat generated in the hydrogenation stage is regulated by the ratio of the product re-introduced into the hydrogenation stage and the recycle ratio (recycle / fresh ratio).

The invention comprises at least one hydrogenation step operated at a temperature between 50 and 250 ° C and a pressure between 30 and 60 bar, wherein the hydrogenation step consists of a plurality of reactors. Preferably, the hydrogenation step according to the invention comprises two or more reactors connected in series.

The hydrogenation step according to the invention permits a hydrogenation rate of between 50 and 1500 Nm ³ / m ³ of the feedstock (volume ratio of hydrogen and feedstock fed into the reactor, volume fraction of hydrogen fed into the feedstock reactor per unit volume). The hydrogenation rate is operated in a suitable range within the above range depending on the aromatic content in the raw material.

In the present invention, the hydrogenation step proceeds at a liquid hourly space velocity of 0.5 to 3 h < ^{-1 &} gt ;. Preferably, if the boiling point of the raw material is 130 ~ 250 ℃ range it has a liquid space velocity of 1 to 2h ^-1, if the boiling point of the raw material is 200 ~ 350 ℃ range has a liquid space velocity of between 0.5 and 1.5h ^-1.

The amount by weight of the catalyst in the two reactors connected in series in the hydrogenation step according to the invention is 0.05-0.40 / 0.60-0.95, respectively. And preferably 0.2 to 0.3 / 0.7 to 0.8. The filled catalyst is a catalyst in which a transition metal or a noble metal, preferably nickel, gold or palladium, and more preferably nickel, is supported as a hydrogenation catalyst. The supported nickel is a catalyst having a content of 10% or more, preferably 15% or more, more preferably 20% or more, based on the catalyst weight.

The present invention adjusts the naphthene content of a deodorized product by controlling the aromatic content of the raw material by adding an aromatic rich oil having kerosene or diesel or an intermediate oil containing the aromatic content of 99% or more by weight. It can control the solvency of the whole product by controlling the naphthene content of the product. It is advantageous for physical property management according to product specifications, and is excellent in terms of economy and efficiency.

FIG. 1 is a schematic view of a hydro-dearomatization process in which an aromatic-rich oil is added to kerosene or light oil or a middle oil fraction containing it as a raw material according to a specific embodiment of the present invention.

The present invention relates to a process for preparing a dearomatic hydrocarbon fluid rich in naphthene.

It is to be understood that the following description sets forth preferred embodiments and the invention is not necessarily limited thereto.

The raw materials are generally mixed with aromatic oil having a boiling point in the range of 130 to 350 占 폚, in which the content of the sulfur compound is 10 ppm or less, and an aromatic rich oil having an aromatic content of 99% or more. Preferably Aromatic-150 (A-150) or Aromatic-300 (A-300) having an aromatic content of 99.5% or more is mixed with kerosene at a boiling point of 130 to 250 ° C, Aromatic-200 (A-200), Aromatic-300 (A-300) or Heavy-aromatic (HA, with boiling point in the range of 200 ~ 400 ℃) with an aromatic content of 99.5% do. Depending on the target product, the aromatic content of the mixed raw material is changed, and a suitable recycle / fresh ratio is set to suppress the temperature rise of the reactor. For example, when A-300, an aromatic oil, is added to kerosene to make a mixed raw material having an aromatic content of 24% by weight, the recycle ratio is preferably 2 to 4. When a mixed raw material having an aromatic content of 22% by weight is added to heavy oil by adding heavy aromatic aromatic oil, the recycle ratio is preferably 1 to 3.

The invention comprises at least one hydrogenation step at a temperature between 50 and 250 ° C and a pressure between 30 and 60 bar, wherein the hydrogenation step consists of a plurality of reactors. Preferably, the process according to the invention comprises two or more reactors connected in series. The first reactor in the reactor is mainly used for removing a sulfur component and a part of aromatic components is hydrogenated, and a plurality of reactors connected in series at a downstream end are mainly provided for hydrogenation of an aromatic component. When two reactors are installed, they may be the same or different in size, and the size of the first reactor mainly adsorbing the sulfur component may be smaller than that of the second reactor, .

The process according to the invention permits a hydrogenation rate (volume fraction of hydrogen to the unit feed into the reactor) of between 50 and 1500 Nm < ³ > / m < ³ > The hydrogenation rate is operated within a suitable range within the above range depending on the raw material. Preferably, if the boiling point is to use the fuel of the 130-250 range, and operating at 300 ~ hydrogenation of 1000Nm ³ / m ^3, with 800 to hydrogenation rate of 1500Nm ³ / m ³ If the boiling point is to use the fuel of the 200 to 350 range Drive.

In the present invention, the hydrogenation step proceeds at a liquid hourly space velocity of 0.5 to 3 h < ^{-1 &} gt ;. Preferably, the raw material has a liquid-space velocity of 1 to 2 ^h-1 when the boiling point of the raw material is in the range of 130 to 250, and a liquid-space velocity of 0.5 to 1.5 ^{h -1} when the boiling point of the raw material is in the range of 200 to 350.

The amount by weight of the catalyst in the two reactors connected in series in the process according to the invention is 0.05-0.40 / 0.60-0.95, respectively. And preferably 0.2 to 0.3 / 0.7 to 0.8. The filled catalyst is a catalyst in which a transition metal or a noble metal, preferably nickel, gold or palladium, and more preferably nickel, is supported as a hydrogenation catalyst. The supported nickel is a catalyst having a content of 10% or more, preferably 15% or more, more preferably 20% or more, based on the catalyst weight.

Example 1

Production of naphthene-rich dearomatic hydrocarbon fluids from a mixture of kerosene oil and aromatic rich oil

Kerosene oil having a boiling point in the range of 160 to 250 ° C and A-300 (Aromatic-300) having an aromatic content of 99.5% or more having a boiling point in the range of 180 to 270 ° C were mixed and supplied to the hydrotreating reactor.

For hydrotreating catalyst was used as the commonly used nickel (nickel) catalyst, LHSV was 1 ~ 2hr ^-1, volume ratio of hydrogen to the feedstock 300 ~ 1000Nm ³ / m ^3, reaction pressure and temperature are respectively 35 ~ 50bar , And 80 to 180 ° C. Also, a part of the produced product was re-introduced into the hydrotreating reactor together with the feedstock, and the amount of fresh feedstock fed into the hydrotreating reactor and the fresh / recycle ratio of the recycled feedstock were 1 to 3 .

Table 1 below compares the analysis results of the physical properties of the reaction raw materials and the kerosene fractions of this example.

Table 2 below compares the results of physical property analysis for the naphthene-rich dearomatic hydrocarbon product and the existing dearomatic hydrocarbon product using only the kerosene fraction as the raw material. By controlling the aromatic content of the raw material, the naphthene content of the product can be efficiently controlled, which can be confirmed by the change of the aniline point.

Example 2

Preparation of naphthene-rich dearomatic hydrocarbon fluids from a mixture of diesel and aromatics rich oils

The diesel oil fraction having a boiling point in the range of 270 to 320 ° C and the aromatic fraction having an aromatic content of 99% or more in the range of 270 to 320 ° C were mixed and fed to the hydrotreating reactor.

The LHSV was 0.5 to 1.5 hr ^-1 , the volume ratio of hydrogen to the feedstock was 800 to 1500 Nm ³ / m ³ , the reaction pressure and temperature were 40 ~ 60 bar, and 120 to 220 ° C. Also, a part of the produced product was re-introduced into the hydrotreating reactor together with the feedstock, and the amount of fresh feedstock fed into the hydrotreating reactor and the fresh / recycle ratio of the recycled feedstock were 1 to 2 .

Table 3 below compares the analysis results of the physical properties of the reaction raw materials and light oil fractions in this Example.

Table 4 below compares the results of physical property analysis for a naphthene-rich dearomatic hydrocarbon product and a conventional dearomatic hydrocarbon product using only diesel oil as a raw material. By controlling the aromatic content of the raw material, the naphthene content of the product can be efficiently controlled, which can be confirmed by the change of the aniline point.

F01, F02: raw material
A01, A02: aromatic rich oil
S01: intermediate product
P01, P02, P03, P04, P05: Products
D01, D02, D03, D04: Distillation plant
R01, R02: hydrogenation reactor

Claims (9)

1. A process for producing a dearomatic hydrocarbon fluid rich in naphthene, having an aromatic compound content of not more than 1000 ppm by weight and a sulfur compound content of not more than 5 ppm,
The hydrocarbon fluid has a boiling point in the range of 130 to 350 DEG C measured according to ASTM D86 and is a mixture of kerosene and diesel having a sulfur content of 10 ppm or less or a middle distillate containing kerosene and light oil, (Aromatic oil content of 99% or more by weight) is used as a raw material, and the raw material is converted into an aromatic component as a naphthenic component through a hydrogenation step, Wherein the aromatic content of the raw material is adjusted to control the solubility of the entire product. The method according to claim 1,
The kerosene is an oil fraction having a boiling point in the range of 130 to 250 ° C. and a sulfur content of 10 ppm or less as measured according to ASTM D86 and having a boiling point in the range of 130 to 300 ° C. measured according to ASTM D86 A method for producing a dearomatic hydrocarbon fluid enriched in naphthene, comprising using as a raw material a compound mixed with an aromatic rich oil having a reference aromatic content of 99% or more. The method according to claim 1,
The diesel is an oil fraction having a boiling point in the range of 200 to 350 DEG C measured according to ASTM D86 and having a sulfur content of 10 ppm or less by weight and having a boiling point of 200 to 400 DEG C measured according to ASTM D86 A method for producing a dearomatic hydrocarbon fluid enriched in naphthene, comprising using as a raw material a compound mixed with an aromatic rich oil having a reference aromatic content of 99% or more. The method according to claim 1,
The middle distillate is an oil fraction having a boiling point of 130-350 ° C. and a sulfur content of 10 ppm or less as measured according to ASTM D86 and having a boiling point measured according to ASTM D86 in the range of 130-400 ° C. A method for producing a dearomatic hydrocarbon fluid rich in naphthenic content, comprising using as a raw material a compound which is mixed with an aromatic-rich oil having an aromatic content of 99% or more by weight. The method according to claim 1, 2, 3, or 4,
The mixing ratio of kerosene, light oil or intermediate oil and aromatic rich oil can be changed and the recycle / fresh ratio of the product re-introduced to the hydrogenation stage and the freshly introduced raw material can be varied depending on the aromatic content of the mixed compound Wherein the reactor heat removal is carried out by controlling the temperature of the reactor. The method according to claim 1,
Wherein the hydrogenation step is operated in at least two reactors in series and each reactor is operated at a temperature between 50 and 250 ° C and a pressure between 30 and 60 bar. The method according to claim 1,
Wherein the hydrogenation rate (volume ratio of hydrogen to unit volume feed into the reactor) in the hydrogenation step is between 50 and 1500 Nm ³ / m ³ . The method according to claim 1,
Wherein the hydrogenation step comprises injecting the feedstock into the reactor at a liquid hourly space velocity of from 0.5 to 3h <" ^{1 &} gt ;. The method according to claim 1,
Wherein the catalyst used in the hydrogenation step is a hydrogenation catalyst in which a catalyst in which a transition metal or a noble metal is supported is filled in a reactor to use the naphthene-enriched dearomatic hydrocarbon fluid.

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