JP5875604B2 - Process for improving aromaticity of high-boiling aromatic hydrocarbons - Google Patents

Description

Detailed Description of the Invention

[Field of Disclosure]
The present disclosure relates to a process for producing raffinate with improved aromaticity.

[Definition of terms used in this patent specification]
As used in this patent specification, the term "fluid catalytic cracking (FCC)" refers to the refining of petroleum, which converts a high-boiling, high-molecular-weight fraction of crude oil into high-value products such as gasoline and olefinic gases It means the process used in the place.

  As used in this patent specification, the term “aromatic” indicates that the molecular activation of a conjugated unsaturated ring structure, lone pair or delocalized electron is more stable than the expected conjugation stability. Means chemical properties.

  As used herein, the term “raffinate” means a clarified FCC residual oil.

  The abbreviation “BMCT” stands for Bureau of Mines Correlation Index.

[Background technology]
CBFS is a mixture of high molecular weight carbon (C ₂₀ or C _50), a raw material which is a key of the carbon black production. Carbon black has a variety of uses in rubber production, such as being used to increase the strength of tires, tubes, conveyor belts, cables, and other rubber-applied machinery products. CBFS is also used as a fuel and heat source in some industrial facilities. Carbon black is obtained by partial combustion and pyrolysis of high boiling aromatic hydrocarbon oils and fats controlled under certain conditions. Important feedstocks in the production of carbon black include FCC residual oil (CSO) obtained from fluid catalytic cracking of light oil, residual oil in naphtha ethylene plants, and coal tar oil.

  The presence of paraffins in high-boiling aromatic hydrocarbons (boiling point of 300 ° C or higher) impairs their suitability for use in carbon black, carbon anode, needle coke production and asphaltene stabilization in heavy oil pyrolysis. Narrow. That is, regarding the above-mentioned use, the higher the boiling point aromatic hydrocarbon, the higher the value as the raw material, the lower the paraffin. Another important characteristic is BMCI. In order to obtain high productivity in the production of carbon black, CBFS must exhibit a high BMCI. Therefore, a high BMCI is also required for a high-boiling aromatic hydrocarbon for obtaining the CBFS. BMCI is an index indicating the aromaticity of aromatic hydrocarbons, and a high carbon black production amount can be obtained from a raw material having a high BMCI with the lowest heat source, leading to a reduction in production cost. In addition, it is important that the raw material for carbon black is low sulfur because sulfur impairs product quality and reduces production and erodes equipment.

  The BMCI value of CBFS must be 132 or higher; on the other hand, the BMCI of CSO residual oil obtained from FCC plant is in the range of 110 to 130, which is less than 126 as standard and varies depending on FCC plant. The higher the conversion amount, the higher the BMCI. However, in order for CSO to become a material for CBFS, which is a raw material for producing carbon black, it seems that the BMCI of CSO needs to be raised to 132 or more. In addition, there is a need to reduce the paraffin content of CSO to broaden the application of materials.

To date, various processes have been studied to increase CSO BMCI, including:
CSO vacuum distillation:
CSO vacuum distillation separates cracked light oil (LCO) components from CSO. Some improvements, such as the introduction of a CSO flasher in a vacuum distillation unit, achieved an improvement in the flash point of CSO, but no improvement in BMCI.

Extraction of CSO in solution with furfural or N-methylpyrrolidone (NMP):
The extraction method using NMP or furfural with the solution is not a suitable method because it has an aromatic component with high CSO and cannot be sufficiently separated from raffinate, making extraction difficult. .

Solution escape method:
This process removes asphalt components from FCC residual oil (CSO) by solution extraction and precipitation.

  Representative patents disclosing the solution escape method are shown below.

  US2002005374 is a disclosure relating to the improvement of non-hydrogenated raw materials. A first product comprising an oil and fat that has been removed from the raw material by a solution degreasing method and a second product comprising an asphalt are obtained, and the asphalt is hydrogenated and separated into an improved oil and fat and asphaltenes.

  US20090166253 discloses a system and method for obtaining deasphalted oil (DAO), which can be obtained hydrocarbon products by cracking, by hydrocarbon treatment and selective separation. This method includes: adding heavy oil, light oil, asphaltene to one or more solutions to obtain a first mixture. From this, asphaltenes are separated to obtain a second mixture comprising deasphalted heavy oil and deasphalted light oil. The de-alfaluted heavy oil is selectively separated from the second mixture into a third mixture consisting of the solution and deasphalted gas oil. Further, the solution is selectively separated therefrom to obtain deasphalted light oil.

  US2010243518 discloses an integrated method of slurry bed hydrocracking (SHC) and solution degassing (SDA) to obtain slurry bed hydrocracking (SHC) distillate. SHC diesel oil is processed by the SDA method to obtain desorbed oil (DAO) and SDA pitch. Meanwhile, part of DAO is recycled to the SHC reaction zone.

  US20090166266 discloses a method for dehydrating and removing crude oil containing hydrocarbons, asphaltenes and water with one or more solutions.

  The materials used in the currently known deflocculation methods are usually vacuum residue oil and atmospheric residue oil with an asphaltene content of 5 wt% or more. It is known that the currently known escape process cannot be used when the asphaltene content of the input material is less than 5 wt%.

  Another disadvantage of the known escape process is that the residue of these processes (asphalt) is solid at room temperature, making it difficult to transport.

  In addition, at least 40% of DAO yield is required for the currently known escape method to be economically effective, below which the process is not economically available.

  In addition, the currently known exfoliation methods do not mention any improvement in properties such as aromaticity and BMCI.

  Thus, there is a need to develop a new process that will allow the production of raffinates with improved aromaticity and BMCI by removing the paraffin component from raffinate / CSO (FCC residue oil).

[Task]
Some of the challenges of the present disclosure, realized by at least one embodiment within the present disclosure, are as follows:
One problem of the present disclosure is to provide a paraffin extraction process that can also be applied to low asphaltene materials such as CSO.

  Another object of the present disclosure is to provide a process for improving the aromaticity of high boiling aromatic hydrocarbons.

  Another problem of the present disclosure is to provide a process for improving the aromaticity of CSO.

  Another problem of the present disclosure is to provide a process for reducing the paraffin content of CSO.

  Furthermore, another object of the present disclosure is to provide a process for obtaining a CSO having a BMCI value of 132 or higher.

  In addition, another problem of the present disclosure is to provide a process that can obtain useful by-products such as oils with high paraffin content while improving the aromaticity of CSO.

  Other objects and advantages of the present disclosure will become apparent from the following description when read in conjunction with the accompanying drawings. The following description and figures do not have the purpose of limiting the scope of application of the present disclosure.

[wrap up]
According to the present disclosure, the process of producing raffinate with improved aromaticity consists of the following steps:
-The raw material raffinate with BMCI of 110 to 130 is mixed with the solution in a suitable device to obtain an oil-solution mixture;
Heating the oil-solution mixture to a temperature in the range of 50 to 200 ° C. to obtain a heated mixture;
-Stirring the heated mixture vigorously in the range of 0.5 to 2 hours to obtain an oil-solution dispersion;
-Separating the dispersion into a paraffin-containing layer and a raffinate layer;
-The raffinate layer is separated from the paraffin-containing layer to obtain a raffinate having an aromatic component of 90 wt% or more and a BMCI value of 132 or more.

  According to one embodiment of the present disclosure, the process includes heating the separated paraffin-containing layer to a range of 40 to 80 ° C. to separate and recycle the solution.

As a standard, the solution is at least one selected from the group consisting of C ₂ or C ₇ hydrocarbons and C ₃ or C ₇ ketones.

According to one embodiment of the present disclosure, the solution is at least one selected from the group consisting of C ₂ or C ₇ alkanes, C ₂ or C ₇ alkenes, and C ₃ or C ₇ ketones.

  As a standard, the ratio of solution to oil is in the range of 4: 1 to 10: 1.

As a standard, heating is performed under a pressure of 10 to 50 kg / cm ² .

As a standard, stirring of the heated mixture is carried out with a static mixer or a mechanical stirrer at a temperature in the range of 50 to 200 ° C. under a pressure in the range of 10 to 50 kg / cm ² .

  As a standard, the heated mixture is agitated at a speed of 500 to 3000 rpm to allow for proper mixing.

As a standard, the pressure drop with a static mixer should be in the range of 1 to 10 kg / cm ² (g) to allow for proper mixing.

  According to another aspect of the present disclosure, the process provided by the present disclosure resulted in a raffinate having an aromatic component of at least 90 wt% and a BMCI of at least 132.

[Detailed description]
The examples contained herein and the advantages of the present invention are described below for the purpose of limitation. Descriptions of known elements and techniques are omitted as long as they do not interfere with the description of the present invention. The example shown here is for the purpose of facilitating the understanding of the embodiment and for the purpose of facilitating the realization thereof, and not for limiting the scope of the embodiment. .

  The following specific examples can be easily modified and applied based on current knowledge, so that they can be widely applied immediately without starting from basic concepts, and deepen understanding by analogy. It is a general indication of the nature of the invention so that it can. It should be understood that the expressions and terms used herein are for illustrative purposes and are not intended to be limiting. In addition, although the examples are preferred, skilled persons will recognize that they can be modified and applied while inheriting the intent and scope of the examples. .

  The present disclosure presents a novel process for the production of raffinate (CSO) that has increased aromaticity by extracting paraffin from materials such as CSO. Furthermore, the present disclosure also aims to reduce the paraffin content of CSO. The CSO thus obtained exhibits a high BMCI value, ie 132 or higher, so that it can be applied as a material for carbon black, carbon anode, needle coke production and for stabilization of asphaltenes in heavy oil pyrolysis It will be a thing. The process of the present disclosure also provides an extract (paraffin-containing oil) containing 50 to 90% of the total paraffin that the CSO feedstock contains. This by-product can be used as a material for FCC and hydrocracking processes, as a base for lubricating oils, or as a heat transfer liquid.

  A detailed description of the process for producing raffinate with improved aromaticity (CSO) according to the present disclosure is provided below.

As a first step, a raffinate material (CSO material) with a BMCI value of 110 to 130 is mixed with the solution in a suitable instrument to obtain an oil-solution mixture. The solution used is at least one selected from the group consisting of C ₂ or C ₇ hydrocarbons and C ₃ or C ₇ ketones. According to one preferred embodiment of the present disclosure, the solution is at least one selected from the group consisting of C ₂ or C ₇ alkanes and C ₂ or C ₇ alkenes. As a standard, the hydrocarbon structure is linear, branched (iso-based) or cyclic.

  CSO is highly aromatic; therefore, paraffin extraction is facilitated by taking advantage of its solubility in low molecular weight hydrocarbons and ketones and mixtures thereof. The choice of solvent or solvents used in the aromaticity reduction and paraffin content reduction process provided by the present disclosure depends on the process conditions and the intended use of the product raffinate and the by-product paraffin oil. For example, propylene or ethylene can be added to increase the selectivity of the paraffin-containing oil.

As a standard, the ratio of solution to oil is in the range of 4: 1 to 10: 1. The addition of the solvent and the formation of the mixture are typically carried out continuously in the conduit under a pressure of 10-50 kg / cm ² to obtain an oil-solution mixture.

  As a second step, the oil-solution mixture is heated to a temperature in the range of 50 to 200 ° C. to obtain a heated mixture. The temperature of the process depends on the type of solution and the required percentage of paraffin-containing oil removal. In the next stage, the heated mixture is vigorously stirred while maintaining the temperature and pressure in an autoclave in the range of 0.5 to 2 hours. Instead, thorough stirring may be performed by a machine such as a static mixer. The stirring speed is typically in the range of 500 to 3000 rpm. The resulting oil-solution dispersion is cooled to obtain a two-layer mixture consisting of an extraction layer (paraffin-containing layer) and a raffinate layer.

  In the next step, the paraffin-containing layer and the raffinate layer containing the highly aromatic CSO are separated.

  The paraffin-containing oil may then be heated in the range of 40 to 80 ° C. to separate the solution and recycle. The paraffin-containing oil obtained in this way has 50 to 90 wt% of the paraffin contained in the original material, and as a by-product of the process, as a raw material for FCC, either through hydrogenation or without hydroxylation It can be used in hydroconducting applications as a raw material for hydrocracking to obtain high quality diesel oil and other petroleum products, as a base for lubricating oil, or as a heat transfer oil. The production volume of paraffin-containing oil should be adjusted between 15 and 30 wt% of the paraffin content of the raw CSO by setting the processing temperature in the range of 50 to 85 ° C and changing the ratio of solution to oil. Can do.

  The CSO raffinate layer (fraction) obtained from the process of the present disclosure is characterized by a minimum of 90 wt% aromatic hydrocarbons, ie 5 to 10 wt compared to the raw CSO. Contains a lot of aromatic hydrocarbons.

  Furthermore, the BMCI of the raffinate is at least 132, which is higher than the raw material value.

  In the raffinate obtained when propane was used as a solvent, aromatic hydrocarbons increased by 6 wt%, the API degree increased by 2 degrees, and the boiling point increased by 8 ° C compared to the raw material CSO. BMCI rises from 127 to 134, as estimated from frequency and boiling point. The raffinate thus obtained is a valuable raw material in the following applications: production of carbon blacks widely used in tire and ink production; production of carbon anodes used in aluminum production; Production of needle coke for use in electrodes; stabilization of asphaltenes in pyrolysis of heavy oils, applying high aromaticity in cokers and bisbreakers to stabilize asphaltenes, preventing coking and extending coke life Use as a diluent for.

  In addition, the process provided by the present disclosure, namely the separation process of oils rich in paraffin and highly aromatic raffinate by solution extraction of CSO, is the product of both of these products (this product raffinate and by-product paraffin oil) ) And increase the range of industrial applications.

  The present disclosure will now be described by way of example and figures. These examples and figures are solely for the purpose of illustrating the present disclosure and are not intended to limit the scope of the application or the disclosure.

Example:
55 grams of feedstock raffinate (CSO) was mixed with propane in a propane 6: oil 1 ratio in an autoclave. The oil-solution mixture was heated to 85 ° C. under a pressure of 33 kg / cm ² and then stirred at 1000 rpm with the pressure and temperature maintained for 1 hour. Heating and stirring were stopped and the resulting dispersion was allowed to separate for 1 hour by gravity into a paraffin-containing layer (extraction layer) and a heavier aromatic layer (raffinate). The paraffin-containing layer (extracted layer) was separated from the upper layer by decantation, and further heated to 50 ° C. to separate propane. The paraffin-containing layer (extracted layer) was tested for degradation activity using an advanced cracking evaluation apparatus (ACE). The aromatic layer (raffinate) was separated as a result of decantation. Viscosity, density, high temperature distillation simulation and SARA (saturation, asphaltene, resin, aromatic) analysis were performed on the extracted layer and raffinate. SARA analysis was performed with a TLC-FID analyzer. Table 1 shows the characteristics of the feedstock CSO, raffinate, and extraction layer.

  Table 1: Characteristics of raw material oil (CSO), raffinate and extraction layer

表1に示されたデーターは、パラフィン含有油（抽出層）が18 wt %、芳香族層（ラフィネート）が82%のサンプルによる。このデーターは標準的な性質を示す値であり、プロセス自体をこの値をもって限定するものと理解してはならない。

The data shown in Table 1 is from a sample with 18 wt% paraffin-containing oil (extracted layer) and 82% aromatic layer (raffinate). This data is a value indicating a standard property and should not be understood as limiting the process itself with this value.

BMCI was calculated by the following equation:
BMCI = (48640 / T) + (473.7 * specific gravity)-456.8
Where T (° K) = 273 + (T ₁₀ + T ₃₀ + T _{50 +} T ₇₀ + T ₉₀ ) / 5
It was observed that the aromatic component of raffinate was improved by 6 wt% compared to the feedstock. Furthermore, compared to the feedstock, the raffinate API was improved by 2 units, and the BMCI by precipitation and distillation increased from 127 to 134. Higher density and lower boiling point contribute to improved BMCI. In addition, the propane removal process also showed its effect on the raffinate produced by removing 50% or more of the saturated content from the feedstock. This experiment was performed in a laboratory autoclave using a single stage stirrer. The extraction layer production and its saturated content are expected to be further improved by a multi-stage continuous process where better agitation and separation can be expected. The extraction layer obtained by the extraction process provided by the present disclosure has a low Conradson carbon content (CCR) and asphaltene content, and is a hydrogenated or non-hydrogenated FCC feedstock, hydrocracked feedstock, lubricating oil. It has properties suitable for use as a base material and heat transfer oil.

  The feedstock (CSO), raffinate and extracted layer were analyzed by gas chromatography (high temperature Simdist, D7169). The results are shown in Table 2.

  Table 2: High temperature Simdist temperature analysis of feedstock (CSO), raffinate and extraction layer

さらに、ACE装置により抽出層の接触分解活性が調べられた；データーは545℃の基礎条件下で、水素化された減圧軽油(HDT-VGO)と比較を行った。抽出分は、HDT-VGOと比べて低い分解が示された：複数の触媒対油の比率において、VGOの 70 - 80 wt %に対して40 - 45 wt %であった。これは、芳香族成分を多く含有している事実と符合する結果であり、低いUOP Kファクタを示すものである。高い芳香族成分の含有は、コークス産出の増加にもつながる。抽出層のCCRとアスファルテンの含有は、水素化分解原料としての要件により限定されるので、抽出層を水素化処理して芳香族成分およびUOP Kファクタの面における改善を行うことができる。 KBC VGO-HT反応速度モデルによれば、抽出層の芳香族成分の飽和度は65 % から 50 % wt 、UOPKファクタは10.4から10.7へと改善される。このような抽出層は、分解において約41 wt % (216 ℃)および約66 wt % (370 ℃)が変換される。水素化処理は、変換の率を向上させ、数値は約47 wt % (at 216 ℃)および約77 wt % (370 ℃)となった。このことは、抽出層がVGO-HTおよび FCCにより改質される相当な可能性を示している。表 3は、抽出層および水素化された抽出層をFCC処理した時の歩留まり(製品産出量)をKBC反応速度モデルにより算出したものである。

In addition, the catalytic cracking activity of the extraction layer was examined by ACE apparatus; the data were compared with hydrogenated vacuum gas oil (HDT-VGO) under the basic condition of 545 ° C. The extract showed low degradation compared to HDT-VGO: 40-45 wt% versus 70-80 wt% of VGO at multiple catalyst to oil ratios. This is a result consistent with the fact that it contains a large amount of aromatic components, and shows a low UOP K factor. Inclusion of high aromatic content also leads to an increase in coke production. Since the content of CCR and asphaltenes in the extraction layer is limited by the requirements as a hydrocracking raw material, the extraction layer can be hydrotreated to improve the aromatic component and the UOP K factor. According to the KBC VGO-HT kinetic model, the saturation of aromatic components in the extraction layer is improved from 65% to 50% wt and the UOPK factor is improved from 10.4 to 10.7. Such an extraction layer converts about 41 wt% (216 ° C.) and about 66 wt% (370 ° C.) upon decomposition. The hydrotreatment improved the conversion rate and the values were about 47 wt% (at 216 ° C.) and about 77 wt% (370 ° C.). This indicates a considerable possibility that the extraction layer is modified by VGO-HT and FCC. Table 3 shows the yield (product output) when the extraction layer and the hydrogenated extraction layer were FCC-treated using the KBC reaction rate model.

  Table 3: Product yield when FCC decomposition of the extracted layer obtained by the disclosed process

［技術的利点］
本開示が提供している高沸点芳香族炭化水素の改質プロセスは、以下のいくつかの技術的利点を有するがこれらに限られない：
・ CSO原料油の芳香族成分を5 から 10 wt.%増加させることができる；
・ パラフィン抽出後のCSO（ラフィネート）の BMCIは、少なくとも132である；
・ ラフィネートのパラフィン含有は、相当に減少させることができる；
・ ラフィネートの API度は高められる； さらに
・ ラフィネートおよび抽出層の応用範囲が広がり、それらの経済的利益が向上する。

[Technical advantages]
The high boiling aromatic hydrocarbon reforming process provided by the present disclosure has several technical advantages, including but not limited to:
• Increase the aromatic content of CSO feedstock by 5 to 10 wt.%;
• BMCI of CSO (raffinate) after paraffin extraction is at least 132;
The paraffin content of the raffinate can be significantly reduced;
• Raffinate API is increased; and • The application range of raffinate and extraction layer is expanded and their economic benefits are improved.

  Throughout this specification, words such as “consisting” or variants “consisting of” or “none” refer to the element, completeness, means, or collection of elements, completeness, or means described. It is understood that it is implied, but does not exclude any other element, whole body, means, or group of elements, whole body or means.

  The use of the expression “at least” or “at least one” in an embodiment of the invention to achieve one or more desired objects or results may include one or more elements, components, Suggest quantity.

  Any discussion or analysis of any document, act, material, device, article, or equivalent in this specification is included solely for the purpose of clarifying the context for the present invention and is pre- It does not approve the basic technology that already exists in Japan, nor does it approve that the present invention is included in the common general knowledge in the field.

  The various physical parameter, volume and quantity values shown here are only approximations, and in the present invention and in the claims, values higher than the physical parameter, volume and quantity values shown therein are Unless otherwise stated, it is expected to be acceptable.

Claims (6)

The process of producing raffinate with improved aromaticity; the process consists of the following steps:
a. Mix the raw material raffinate with BMCI of 110 to 130 and the solution in a suitable instrument with the ratio of the solution to oil raffinate (solution: oil) in the range of 4: 1 to 10: 1 To obtain an oil-solution mixture ,
Wherein the solution is at least one selected from the group consisting of C ₂ or C ₇ hydrocarbons and C ₃ or C ₇ ketones ;
b. The oil - the mixture solution was heated to a temperature in the range of 200 ° C. from 85 ° C., to obtain a heated mixture;
c. The heated mixture was vigorously stirred in the range of 0.5 to 2 hours, the oil - obtain a solution dispersion;
d. Separating the oil-solution dispersion into a paraffin-containing layer and a raffinate layer;
e. The raffinate layer separated from the paraffin-containing layer, has an aromatic component or 90 wt%, yet obtain a raffinate with a higher BMCI value 132. Billing is claimed in claim 1 process, wherein the process includes the separated the paraffins-containing layer is heated to a range of 80 ° C. 40, separates the solution. In the claimed process in claim 1, wherein the heating is carried out under a pressure of 10 or 50 kg / cm ^2. In step as claimed in claim 1, agitation of the heated mixture, at a temperature ranging from 50 to 200 ° C., is carried out under a pressure ranging from 10 to 50 kg / cm ^2. In step as claimed in claim 1, agitation of the heated mixture is divided lines at 3000rpm speed from 500. In the claimed process in claim 1, step c) dividing lines in a static mixer.