WO2024034930A1 - Method for storing petroleum-based high-softening-point pitch - Google Patents

Abstract

A method for storing petroleum-based high-softening-point pitch, of the present invention, comprises the steps of: (a) injecting petroleum-based high-softening-point pitch into a storage tank; and (b) storing the petroleum-based high-softening-point pitch, wherein the softening point of the petroleum-based high-softening-point pitch is 150-300°C, and step (b) comprises (b-1) a process of periodically charging an inert gas into the petroleum-based high-softening-point pitch and/or (b-2) a process of stirring the petroleum-based high-softening-point pitch.

Description

How to store petroleum-based high softening point pitch

The present invention relates to a method of storing petroleum-based high softening point pitch.

High softening point pitch is used as a raw material or precursor material for various carbon materials and graphite materials such as carbon fiber, activated carbon, and secondary battery anode materials. To produce high softening point pitch, coal-based or petroleum-based materials are used as raw materials and undergo an oxidation process and heat treatment. Manufacturing methods through processes are generally known.

The technology for producing high softening point pitch using conventional petroleum-based raw materials or coal-based raw materials has the advantage of producing high-quality petroleum-based high softening point pitch with significantly less quinoline insoluble substances, and does not require a catalyst or high pressure conditions, eliminating the catalyst. There is an advantage in that high-quality petroleum-based high softening point pitch can be produced economically as a separate process and expensive high-pressure vessel are not required. However, when storing high softening point pitch after manufacturing, changes in physical properties may occur during long-term storage. There are no measures proposed to suppress it.

The object of the present invention is a method of storing petroleum-based high softening point pitch that can suppress or significantly reduce changes in physical properties while storing petroleum-based high softening point pitch for a long period of time and does not require the addition of separate chemicals and does not cause environmental pollution problems. is to provide.

The object of the present invention is not limited to the object mentioned above, and other objects and advantages of the present invention that are not mentioned can be understood through the following description and will be more clearly understood by the examples of the present invention. Additionally, it will be readily apparent that the objects and advantages of the present invention can be realized by the means and combinations thereof indicated in the patent claims.

In order to achieve the above object, the storage method of the petroleum-based high softening point pitch of the present invention includes the steps of (a) introducing the petroleum-based high softening point pitch into a storage tank; And (b) storing the petroleum-based high softening point pitch; the softening point of the petroleum-based high softening point pitch may be 150°C to 300°C, and step (b) includes, (b-1) the petroleum-based high softening point pitch. It may include one or more of the steps of continuously or periodically charging an inert gas to the petroleum-based high softening point pitch and (b-2) the process of stirring the petroleum-based high softening point pitch.

The temperature of the storage tank in step (a) and the storage temperature in step (b) may be 30 to 150°C higher than the softening point of the petroleum-based high softening point pitch.

The temperature of the storage tank in step (a) and the storage temperature in step (b) may be 180°C to 450°C.

In step (b), the process (b-1) and the process (b-2) may be performed simultaneously.

Step (b) may be performed for 1 minute to 240 hours.

The inert gas in the process (b-1) may include one or more of nitrogen and argon.

The charging flow rate of the inert gas in the process (b-1) may be 0.01 L/min to 10 L/min relative to 1 kg of the petroleum-based high softening point pitch, and the charging of the inert gas in the process (b-1) may be performed on a total storage basis. It may be performed in cycles of 1/50 to 1/5 of the time, and the charging time for each cycle may be 30 seconds to 30 minutes.

The stirring speed of the process (b-2) may be 1 rpm to 400 rpm.

The softening point of the petroleum-based high softening point pitch after storage is 150°C to 300°C, and the difference in softening point before and after storage of the petroleum-based high softening point pitch may be 10°C or less.

The difference in toluene insoluble content before and after storage of the petroleum-based high softening point pitch may be 5% by weight or less.

The storage method of petroleum-based high softening point pitch according to the present invention can suppress or significantly reduce changes in physical properties while storing petroleum-based high softening point pitch for a long period of time, and does not require the addition of separate chemicals, so it does not cause environmental pollution problems. There is an advantage to not having it.

In addition to the above-described effects, specific effects of the present invention are described below while explaining specific details for carrying out the invention.

The above-described objects, features, and advantages will be described in detail below, so that those skilled in the art will be able to easily implement the technical idea of the present invention. In describing the present invention, if it is determined that a detailed description of known technologies related to the present invention may unnecessarily obscure the gist of the present invention, the detailed description will be omitted. The terms described below are terms written in consideration of the function and operation in the present invention, and the meaning of each term should be interpreted based on the content throughout the present specification.

In this specification, when an element is referred to as being on another element, it means that it may be formed directly on the other element or that a third element may be interposed between them.

The terminology used herein is for describing embodiments and is not intended to limit the invention. As used herein, singular forms also include plural forms, unless specifically stated otherwise in the context. As used herein, descriptions such as 'includes' and 'contains' do not exclude the presence or addition of one or more other components.

In interpreting the components in this specification, they are interpreted to include the margin of error even if there is no separate explicit description.

In this specification, '%' can be interpreted as 'weight% (wt%)' unless otherwise specified.

Below, the present invention is described in more detail.

In storing the petroleum-based high softening point pitch of the present invention, the present inventors completed the present invention by focusing on the importance of uniform heat transfer of the stored petroleum-based high softening point pitch.

Specifically, the method for storing petroleum-based high softening point pitch of the present invention includes the steps of (a) introducing petroleum-based high softening point pitch into a storage tank; and (b) storing the petroleum-based high softening point pitch, wherein step (b) includes: (b-1) continuously or periodically charging an inert gas to the petroleum-based high softening point pitch; and (b-2) It may include one or more processes among the processes of stirring the petroleum-based high softening point pitch, and the softening point of the petroleum-based high softening point pitch may be 150°C to 300°C, and may be 200°C to 300°C. there is.

Generally, high softening point pitch is drained from a reactor after production and then shipped as solid-phase pitch, or transferred to a storage tank and processed into liquid-phase or solid phase before shipping. However, in the former case, because high-temperature pitch is discharged, manufacturers usually select the latter case due to fume generation and safety reasons.

At this time, for reasons such as the transfer of high softening point pitch, the storage temperature of the storage tank (temperature of the storage tank) must be stored at a temperature higher than the softening point of the high softening point pitch to ensure the flowability of the pitch. On the other hand, since the storage temperature of the storage tank is higher than the softening point of the pitch, depending on the location and shape of the heat source device for supplying heat at the storage temperature of the storage tank, the softening point of the high softening point pitch immediately after production increases, and the toluene in the high softening point pitch increases. It was found that the physical properties of the manufactured high softening point pitch changed as the content of insoluble matter increased.

From the above viewpoint, the temperature of the storage tank in step (a) and the storage temperature in step (b) of the present invention are 30 to 150°C higher than the softening point of the manufactured petroleum-based high softening point pitch as the storage object. It is preferable, and it is more preferable that the temperature is as high as 50°C to 100°C, and it was confirmed that when this is satisfied, it is possible to prevent deterioration of physical properties while ensuring the flowability of petroleum-based high softening point pitch.

The temperature of the storage tank in step (a) and the storage temperature in step (b) may be 180°C to 450°C, preferably 180°C to 400°C, and more preferably 200°C to 350°C. You can.

In step (b), the process (b-1) and the process (b-2) may be performed simultaneously in order to evenly transfer heat to minimize the suppression of physical property changes while storing the petroleum-based high softening point pitch.

The storage step (b) can be performed for 1 minute to 240 hours, and has the advantage of allowing both short-term and long-term storage by selecting the storage time as needed.

The inert gas in the process (b-1) may include one or more of nitrogen and argon, and for example, nitrogen and argon may be mixed.

Since the charging of the inert gas in the process (b-1) is done for the purpose of minimizing changes in pitch physical properties, from the viewpoint of efficiently achieving the purpose, the charging flow rate of the inert gas is, for example, the petroleum-based high softening point. It may be 0.01 L/min to 10 L/min compared to 1 kg of pitch, for example, it may be 0.5 L/min to 10 L/min compared to 1 kg of the petroleum-based high softening point pitch, and for example, it may be 1.0 compared to 1 kg of the petroleum-based high softening point pitch. It may be L/min to 5.0 L/min, for example, 2.0 L/min to 5.0 L/min relative to 1 kg of the petroleum-based high softening point pitch.

The cycle of charging the inert gas in the process (b-1) can be adjusted by a person skilled in the art according to the convenience and needs of the process within an interval of 1/50 to 1/5 of the total storage time, for example, for a total of 24 hours. When performing a storage process, inert gas can be charged at intervals of 1 hour, which is an interval of 1/24. In addition, the charging time for each cycle can also be appropriately adjusted, for example, it can be 30 seconds to 30 minutes, for example, it can be 1 minute to 10 minutes, for example, it can be 2 minutes to 10 minutes, for example 2 It may be from 1 minute to 5 minutes, but is not limited thereto.

The stirring speed of the process (b-2) may be, for example, 1 rpm to 400 rpm, for example, 10 rpm to 100 rpm, for example, 20 rpm to 100 rpm, for example, 20 rpm to 50 rpm. It could be rpm.

The softening point after storage of the petroleum-based high softening point pitch may be, for example, 150°C to 300°C, for example, 200°C to 300°C, from the viewpoint of reducing the softening point and physical property change of the input petroleum-based high softening point pitch. It can be.

In addition, the smaller the difference in softening point before and after storage of the petroleum-based high softening point pitch, the smaller the change in physical properties can be minimized. The difference in softening point before and after storage of the petroleum-based high softening point pitch may be, for example, 10°C or less, for example, 5°C or less, for example, 3°C or less, and for example, 2°C or less. and, for example, may be 1°C or less.

In order to minimize changes in physical properties before and after storage of the petroleum-based high softening point pitch, the difference in toluene insoluble content before and after storage of the petroleum-based high softening point pitch may be, for example, 5% by weight or less, for example For example, it may be 3% by weight or less, for example, it may be 2% by weight or less, and for example, it may be 1% by weight or less.

Below, the present invention will be explained in more detail by way of examples. However, the following examples only illustrate the present invention, and the content of the present invention is not limited to the following examples.

Example 1

Petroleum-based high softening point pitch, which was manufactured using pyrolysis fuel oil (PFO), a petroleum residue, as a raw material and has a softening point of 245°C and a toluene insoluble content (TI) of 19% by weight, was introduced into the storage tank. Nitrogen, an inert gas, was charged to the storage tank at a flow rate of 2.0 L/min per 1 kg of petroleum-based high softening point pitch at 1-hour intervals for 5 minutes. At this time. The temperature of the storage tank was 300°C, and the storage process was performed for 24 hours.

After storage, the softening point of the petroleum-based high softening point pitch was 247°C, and the toluene insoluble content (TI) was 22% by weight.

Example 2

The same petroleum-based high softening point pitch as in Example 1 was added to the storage tank, and then stirred at a stirring speed of 50 rpm using a stirrer. The temperature of the storage tank was 300°C, and the storage process was performed for 24 hours.

After storage, the softening point of the petroleum-based high softening point pitch was 248°C, and the toluene insoluble content (TI) was 21% by weight.

Example 3

The same petroleum-based high softening point pitch as in Example 1 was introduced into the storage tank, and then nitrogen, an inert gas, was charged into the storage tank at a flow rate of 1.0 L/min relative to 1 kg of petroleum-based high softening point pitch at 1-hour intervals for 5 minutes. At this time. The temperature of the storage tank was 300°C, and the storage process was performed for 24 hours. At the same time, the mixture was stirred at a stirring speed of 20 rpm using a stirrer. The temperature of the storage tank was 300°C, and the storage process was performed for 24 hours.

After storage, the softening point of the petroleum-based high softening point pitch was 246°C, and the toluene insoluble content (TI) was 20% by weight.

Comparative Example 1

The same petroleum-based high softening point pitch as in Example 1 was introduced into the storage tank, and then nitrogen, an inert gas, was charged into the storage tank at a flow rate of 15.0 L/min relative to 1 kg of petroleum-based high softening point pitch at 1-hour intervals for 2 minutes. The temperature of the storage tank was 300°C, and the storage process was performed for 24 hours.

After storage, the softening point of the petroleum-based high softening point pitch was 260°C, and the toluene insoluble content (TI) was 27% by weight.

Comparative Example 2

The same petroleum-based high softening point pitch as in Example 1 was added to the storage tank, then no inert gas was charged or stirred, the temperature of the storage tank was 333°C, and the storage process was performed for 24 hours.

After storage, the softening point of the petroleum-based high softening point pitch was 232°C, and the toluene insoluble content (TI) was 33% by weight.

In Examples 1 to 3 and Comparative Examples 1 to 2, the temperature of the storage tank, the flow rate of nitrogen, which is an inert gas, the stirring speed of the stirrer, and the physical properties of the petroleum-based high softening point pitch analyzed before and after storage are shown in Table 1 below. It was.

		Example 1	Example 2	Example 3	Comparative Example 1	Comparative Example 2
save condition	Storage tank temperature (℃)	300	300	300	300	330
	Inert gas charging flow rate (L/min·kg)	2.0	-	1.0	15.0	-
	Agitator stirring speed (rpm)	-	50	20	-	-
Before saving pitch	Softening point (℃)	245	245	245	245	245
	Toluene insoluble content (%)	19	19	19	19	19
After saving pitch	Softening point (℃)	247	248	246	255	232
	Toluene insoluble content (%)	22	21	20	27	33

Referring to Table 1, when comparing the softening point and toluene-insoluble content before and after storage of the petroleum-based high softening point pitch of Examples 1 to 3, it can be seen that the range of change is small.

On the other hand, in Comparative Example 1, unlike Example 1, the flow rate of the inert gas flowed compared to 1 kg of petroleum-based high softening point pitch was excessive, so the softening point and toluene insoluble content of the petroleum-based high softening point pitch increased significantly, resulting in a large change in physical properties. The results are shown.

In Comparative Example 2, unlike Examples 1 to 3, no inert gas was charged and the product was stored without stirring, so it can be confirmed that the softening point and the toluene insoluble matter content increased excessively. Unlike Example 2, in which heat was transferred uniformly, it can be assumed that localized heat transfer occurred, causing decomposition and bonding reactions of molecules within the petroleum-based high softening point, resulting in extreme changes in physical properties.

In addition, Example 3 is a case in which charging and stirring of nitrogen, an inert gas, were carried out simultaneously. Through charging and stirring of nitrogen, heat transfer was achieved evenly, and compared to Comparative Examples 1 and 2, as well as Examples 1 and 2. In comparison, it was confirmed that the change in physical properties was the least.

Although it has been described in more detail with reference to the embodiments of the present specification, the present specification is not necessarily limited to these embodiments, and various modifications may be made without departing from the technical spirit of the present specification. Accordingly, the embodiments disclosed in this specification are not intended to limit the technical idea of the present invention, but rather to explain it, and the scope of the technical idea of the present invention is not limited by these examples. Therefore, the embodiments described above should be understood in all respects as illustrative and not restrictive. The scope of protection of this specification and the present invention should be interpreted in accordance with the claims, and all technical ideas within the equivalent scope should be construed as being included in the scope of rights of this specification and the present invention.

Claims (10)

1. (a) Injecting petroleum-based high softening point pitch into a storage tank; and

   (b) storing the petroleum-based high softening point pitch,

   The softening point of the petroleum-based high softening point pitch is 150°C to 300°C,

   The step (b) includes one or more of the steps of (b-1) periodically charging an inert gas to the petroleum-based high softening point pitch and (b-2) stirring the petroleum-based high softening point pitch. ,

   Storage method of petroleum-based high softening point pitch.
2. According to paragraph 1,

   The temperature of the storage tank in step (a) and the storage temperature in step (b) are 30 to 150 ° C higher than the softening point of the petroleum-based high softening point pitch,

   Storage method of petroleum-based high softening point pitch.
3. According to paragraph 1,

   The temperature of the storage tank in step (a) and the storage temperature in step (b) are 180°C to 450°C,

   Storage method of petroleum-based high softening point pitch.
4. According to paragraph 1,

   In step (b), the process (b-1) and the process (b-2) are performed simultaneously,

   Storage method of petroleum-based high softening point pitch.
5. According to paragraph 1,

   Step (b) is performed for 1 minute to 240 hours,

   Storage method of petroleum-based high softening point pitch
6. According to paragraph 1,

   The inert gas in the process (b-1) includes one or more of nitrogen and argon,

   Storage method of petroleum-based high softening point pitch.
7. According to paragraph 1,

   The charging flow rate of the inert gas in the process (b-1) is 0.01 L/min to 10 L/min relative to 1 kg of the petroleum-based high softening point pitch,

   The charging of the inert gas in the process (b-1) is performed at intervals of 1/50 to 1/5 of the total storage time, and the charging time for each cycle is 30 seconds to 30 minutes,

   Storage method of petroleum-based high softening point pitch.
8. According to paragraph 1,

   The stirring speed of the process (b-2) is 1 rpm to 400 rpm,

   Storage method of petroleum-based high softening point pitch.
9. According to paragraph 1,

   The softening point of the petroleum-based high softening point pitch after storage is 150°C to 300°C,

   The difference in softening point before and after storage of the petroleum-based high softening point pitch is 10°C or less,

   Storage method of petroleum-based high softening point pitch.
10. According to paragraph 1,

    The difference in toluene insoluble content before and after storage of the petroleum-based high softening point pitch is 5% by weight or less,

    Storage method of petroleum-based high softening point pitch.