阅读说明：本技术 提高馏分油馏程的方法 (Method for improving distillation range of distillate oil ) 是由 林伟国 涂志强 彭茜 荣峻峰 谢婧新 宗明生 吴耿煌 余伟发 于 2019-10-25 设计创作，主要内容包括：本发明涉及催化裂化轻循环油处理领域,公开了一种提高馏分油馏程的方法。该方法包括：在引发剂的存在下,使馏分油在温度为170-500℃、压力为1-3MPa的条件下反应0.5-12h；所述馏分油中芳烃含量在80重量％以上,烷烃含量为1-20重量％,馏程为150-500℃。本发明的方法获得了以下有益的技术效果：(1)本发明能够有效提高馏分油的馏程,适应现有焦化炉焦化要求,制备中间相沥青及针状焦等产品,实现催化裂化循环油全流程综合利用；(2)可以在较温和的条件下进行反应得到具有较高馏程的馏分油,操作过程安全；(3)本发明方法工艺过程简单,不需要加入其它催化剂,不会额外带来其它杂质影响最终产品品质。(The invention relates to the field of catalytic cracking light cycle oil treatment, and discloses a method for improving the distillation range of distillate oil. The method comprises the following steps: in the presence of an initiator, the distillate oil is reacted for 0.5 to 12 hours at the temperature of 170-500 ℃ and the pressure of 1 to 3 MPa; the aromatic hydrocarbon content in the distillate oil is more than 80 weight percent, the alkane content is 1-20 weight percent, and the distillation range is 150-500 ℃. The method of the invention achieves the following beneficial technical effects: (1) the invention can effectively improve the distillation range of distillate oil, is suitable for the coking requirement of the existing coking furnace, prepares products such as mesophase pitch, needle coke and the like, and realizes the full-flow comprehensive utilization of catalytic cracking cycle oil; (2) the reaction can be carried out under mild conditions to obtain distillate oil with higher distillation range, and the operation process is safe; (3) the method has simple process, does not need to add other catalysts, and does not bring other impurities to influence the quality of the final product.)

1. A process for increasing the distillation range of a distillate, comprising: in the presence of an initiator, the distillate oil is reacted for 0.5 to 12 hours at the temperature of 170-500 ℃ and the pressure of 1 to 3 MPa; wherein, the aromatic hydrocarbon content in the distillate oil is more than 80 weight percent, the alkane content is 1-20 weight percent, and the distillation range is 150-500 ℃.

2. The process as claimed in claim 1, wherein the distillate has an aromatics content of 85-95 wt%, an alkanes content of 5-15 wt% and a distillation range of 160-380 ℃.

3. The method as claimed in claim 1, wherein the reaction temperature is 270-400 ℃.

4. The process according to claim 1 or 2, wherein the reaction time is 1-6 h.

5. A process according to claim 1 or 2, wherein the initiator is oxygen and the oxygen content of the reaction atmosphere is 1-21 vol%, preferably 10-21 vol%.

6. The process according to claim 1 or 2, wherein the initiator is used in an amount of 0.8 to 30g, relative to 100g of distillate, the initiator is a peroxide, and the reaction is carried out in an inert atmosphere.

7. The method of claim 6, wherein the peroxide is benzoyl peroxide and/or hydrogen peroxide.

8. The process of claim 1, wherein the aromatics in the distillate are selected from the group consisting of monocyclic aromatics, bicyclic aromatics, and tricyclic aromatics, wherein the distillate has a monocyclic aromatics content of 5-25 wt.%, a bicyclic aromatics content of 55-75 wt.%, and a tricyclic aromatics content of 8-16 wt.%;

preferably, the monocyclic arene is selected from alkylbenzenes and/or indanes;

preferably, the bicyclic aromatic hydrocarbon is selected from naphthalene and/or acenaphthylene;

preferably, the tricyclic aromatic hydrocarbon is selected from anthraquinones.

9. The process of claim 1 wherein the alkanes in said distillate are selected from the group consisting of paraffins, monocycloparaffins, dicycloalkanes and tricycloalkanes, and wherein said distillate has a paraffin content of from 5 to 9 weight percent, monocycloparaffins content of from 1 to 2.5 weight percent, dicycloalkanes content of from 0.5 to 1.5 weight percent and tricycloalkanes content of from 0.1 to 0.8 weight percent.

10. The process of claim 1, 8 or 9 wherein the distillate has a sulfur content of 0.1 to 1 wt% and a nitrogen content of 0.01 to 0.1 wt%.

Technical Field

The invention relates to the field of catalytic cracking light cycle oil treatment, in particular to a method for improving the distillation range of distillate oil.

Background

The catalytic cracking light cycle oil is one of the main byproducts of the catalytic cracking process, has high aromatic hydrocarbon content and low cetane number, and can be used as a blending component of diesel oil after being subjected to hydrogenation treatment. Along with the rapid upgrading of the fuel quality and the aggravation of the surplus diesel, the catalytic cracking light cycle oil is more and more difficult to be used as a diesel blending component, and the application of the catalytic cracking light cycle oil is necessary.

At present, catalytic cracking devices at home and abroad mainly return catalytic cracking light cycle oil to a catalytic cracking reaction device for cracking again to produce gasoline fractions, but carbon deposition is easily formed in the catalytic cracking device due to high aromatic hydrocarbon content in the catalytic cracking light cycle oil, particularly aromatic hydrocarbons with double rings and above double rings, and the device is not favorable for stable operation. Therefore, many researches on the comprehensive utilization of catalytic cracking light cycle oil are carried out abroad, and the comprehensive utilization is used for producing toluene (BTX) or clean diesel oil, and certain results are obtained. Such as catalytic cracking light cycle oil-XTM process by UOP, ARO technology by Nova chemicals, canada, related technology by JX japan petroleum and energy companies, and the like. In the processes, heavy aromatics in the catalytic cracking light cycle oil are converted into light aromatics such as BTX (benzene-toluene-xylene) through hydrocracking or a combination of hydrotreating and catalytic cracking, and meanwhile, a certain amount of paraffins and naphthenes contained in the catalytic cracking light cycle oil are also converted into light hydrocarbons in the processing process, so that the loss of high-cetane components in the catalytic cracking light cycle oil is caused, and the hydrogen consumption and the energy consumption are increased.

CN1037274C discloses a method for producing petroleum asphalt by oxidizing heavy oil catalytic cracking slurry oil, which adopts air as an oxidant to oxidize paraffin-based heavy oil catalytic cracking slurry oil without removing catalyst powder in a kettle-type or tower-type asphalt oxidizing device to prepare petroleum asphalt. The method adopts the following oxidation conditions: the liquid phase temperature is 260-300 ℃, the gas phase temperature is 140-150 ℃, the air volume is 2-5L/min, and the oxidation time is 8-20 h.

CN105238430A discloses a method for preparing mesophase pitch by catalytic cracking slurry oil hydroisomerization-thermal polycondensation, and provides a method for preparing mesophase pitch by catalytic cracking slurry oil hydroisomerization-thermal polycondensation. The method comprises the steps of carrying out vacuum distillation on FCC oil slurry of naphthenic base crude oil or intermediate base crude oil to obtain distillate oil with the temperature of more than 400 ℃ as a raw material, and reacting for 4-8 hours at the temperature of 250-320 ℃ and the pressure of 5MPa in the presence of a hydroisomerization catalyst to obtain a modified raw material. The modified raw materials continue to react for 2-10h at the reaction temperature of 330-460 ℃ and the reaction pressure of 12MPa to obtain the high-quality mesophase pitch.

CN107032317A A device and method for producing carbon microsphere by polymerization of residual oil/coal tar whole fraction, the process method is that after raw oil is dewatered, deslagged and electrically desalted, the whole fraction is polymerized to produce carbon microsphere and impregnant pitch. The reaction pressure of the polymerization reactor is 15-30MPa in N₂The temperature is raised to 550 ℃ under the protection of (1-2), the stirring time in the temperature raising stage is 1-2 hours, then the temperature is raised to 1200 ℃ under the protection of (600-), and the stirring is continued for 1-2 hours.

The above processes usually require high temperature and pressure, or the process flow is complicated, and a catalyst, an oxidant, etc. are required to be added for reaction to obtain mesophase pitch with high boiling point.

Disclosure of Invention

The invention aims to overcome the problem of harsh conditions in the prior art, and provides a method for improving the distillation range of distillate oil, which can be carried out at lower temperature and pressure, requires shorter time and has simple flow.

In order to achieve the above object, the present invention provides a process for increasing the distillate distillation range (or producing a mesophase pitch or needle coke feedstock), which comprises: in the presence of an initiator, the distillate oil is reacted for 0.5 to 12 hours at the temperature of 170-500 ℃ and the pressure of 1 to 3 MPa; wherein, the aromatic hydrocarbon content in the distillate oil is more than 80 weight percent, the alkane content is 1-20 weight percent, and the distillation range is 150-500 ℃.

Through the technical scheme, the method provided by the invention has the following beneficial technical effects:

(1) the invention can effectively improve the distillation range of distillate oil, the content of distillate oil above 350 ℃ is improved from below 10 weight percent to above 30 weight percent, the content of distillate oil above 500 ℃ is improved to above 10 weight percent, the invention is suitable for the coking requirement of the existing coking furnace, and the products such as mesophase pitch, needle coke and the like are prepared, thereby realizing the full-process comprehensive utilization of catalytic cracking cycle oil;

(2) the reaction can be carried out under mild conditions to obtain distillate oil with higher distillation range, and the operation process is safe;

(3) the method has simple process, does not need to add other catalysts, and does not bring other impurities to influence the quality of the final product.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

The invention provides a method for improving distillation range of distillate oil, which is characterized by comprising the following steps: reacting the distillate in the presence of an initiator at a temperature of 170-; wherein, the aromatic hydrocarbon content in the distillate oil is more than 80 weight percent, the alkane content is 1-20 weight percent, and the distillation range is 150-500 ℃.

According to the invention, the process is particularly suitable for the treatment of distillates having an aromatic content and an alkane content in the above-mentioned ranges, preferably a content of aromatics in the distillate of from 85 to 95% by weight. Preferably, the alkane content of the distillate is 5-15 wt%. Preferably, the distillation range of the distillate is 160-.

According to the present invention, the object of the present invention can be achieved as long as the reaction is carried out within the above temperature range, but the inventors of the present invention found that the distillation range of the distillate can be effectively increased even if the reaction temperature is lowered in the presence of an initiator (particularly, in a preferable initiator), and therefore, it is preferable that the temperature of the reaction is 270-400 ℃. The reaction time is also, according to a preferred embodiment of the present invention, between 1 and 6 h.

In the present invention, the initiator may be a conventional substance capable of initiating a condensation reaction, and according to a specific embodiment of the present invention, the initiator is pure oxygen, and the inventors of the present invention found that a good effect of increasing the distillation range can be obtained when pure oxygen is used, but the use of pure oxygen is not recommended for the experiment due to the safety of the experiment. Thus, according to a preferred embodiment of the present invention, the initiator is oxygen, and the oxygen content of the reaction atmosphere is 1 to 21% by volume, more preferably 10 to 21% by volume. The reaction atmosphere refers to the gas composition in the environment where the reaction is performed, and may be composed of inactive gas (i.e. gas which does not react with the distillate, such as inert gas and/or nitrogen) and oxygen. More preferably, the initiator is provided by compressed air. As mentioned before, the distillation range of the distillate can be further increased under milder conditions according to this preferred embodiment. In this preferred embodiment, the initiator may be used in such an amount that the reaction pressure is controlled within the above range.

According to another preferred embodiment of the invention, the initiator is used in an amount ranging from 0.8 to 30g (or from 0.9 to 10g) with respect to 100g of distillate, the initiator is a peroxide and the reaction is carried out in an inert atmosphere. More preferably, the peroxide is benzoyl peroxide and/or hydrogen peroxide.

According to the invention, the aromatics in the distillate are generally selected from monocyclic aromatics, bicyclic aromatics and tricyclic aromatics, the content of monocyclic aromatics in the distillate being from 5 to 25% by weight, the content of bicyclic aromatics being from 55 to 75% by weight and the content of tricyclic aromatics being from 8 to 16% by weight.

Preferably, the monocyclic arene is selected from alkylbenzenes and/or indanes. Preferably, the bicyclic aromatic hydrocarbon is selected from naphthalene and/or acenaphthylene. Preferably, the tricyclic aromatic hydrocarbon is selected from anthraquinones.

According to the invention, the alkanes in the distillate are generally selected from the group consisting of paraffins, monocycloparaffins, dicycloalkanes and tricycloalkanes, the quantity of paraffins in the distillate being between 5 and 9% by weight, the quantity of monocycloparaffins being between 1 and 2.5% by weight, the quantity of dicycloalkanes being between 0.5 and 1.5% by weight and the quantity of tricycloalkanes being between 0.1 and 0.8% by weight.

According to the invention, the sulphur content of the distillate is generally between 0.1 and 1 wt.% (or between 0.8 and 0.9 wt.%), and the nitrogen content is generally between 0.01 and 0.1 wt.% (or between 0.07 and 0.08 wt.%).

The process according to the invention is particularly suitable for increasing the distillation range of distillates whose composition and distillation range are within the preferred ranges mentioned above. Furthermore, the process of the present invention is particularly suitable for the preparation of mesophase pitch or needle coke feedstocks based on the above-mentioned distillate oils.

The present invention will be described in detail below by way of examples. In the following examples and comparative examples, the normal temperature was 25 ℃; the compositions of the distillates used are shown in tables 1 and 2 below:

TABLE 1

TABLE 2

The composition of hydrocarbons in distillate oil and products is measured by adopting a method of Chinese petrochemical industry standard SH/T0606-2005;

the distillation range of distillate oil is measured by adopting a simulated distillation method standard ASTM D2887-2008 method;

the ash content of distillate oil and products is measured by adopting the method of the Chinese petrochemical industry standard SH/T0029-1990;

the analysis of the content of nitrogen element in the distillate oil is measured by adopting the method of the Chinese petrochemical industry standard SH/T0657-2007;

the analysis of the sulfur element content in the distillate oil is measured by adopting a method of the Chinese petrochemical industry standard SH/T0689-2017;

the analysis of the content of nitrogen element in the product is determined by adopting a method of national standard GB 17040;

the analysis of the sulfur element content in the product is determined by adopting the method of the Chinese petrochemical industry standard SH/T0704-2001;

the distillation range distribution of the product was determined using a simulated distillation standard ASTM D6352-2004 method.

Example 1

30mL (30.6g) of distillate oil 1 is added into a high-pressure reaction kettle, compressed air (the content of oxygen is 21 volume percent) is introduced to control the reaction pressure in a reaction system, the temperature, the pressure and the time of the reaction are shown in a table 3, a liquid product 30.6g is obtained after the temperature is reduced to the normal temperature, the performance tests such as the distillation range distribution of the product are shown in the table 3, and the element composition of the product is shown in the table 4.

Example 2

30mL (30.6g) of distillate oil 1 is added into a high-pressure reaction kettle, the reaction pressure in a reaction system is controlled by introducing a mixture of oxygen and nitrogen (the content of oxygen is 15 vol%), the reaction temperature, pressure and time are shown in Table 3, 30.2g of black semi-solid product is obtained after the temperature is reduced to normal temperature, the performance tests such as the distillation range distribution of the product are shown in Table 3, and the element composition of the product is shown in Table 4.

Example 3

30mL (30.6g) of distillate oil 1 is added into a high-pressure reaction kettle, the reaction pressure in a reaction system is controlled by introducing a mixture of oxygen and nitrogen (the content of oxygen is 10 vol%), the temperature, the pressure and the time of the reaction are shown in Table 3, 30.0g of solid product is obtained after the temperature is reduced to normal temperature, the performance tests such as the distillation range distribution of the product are shown in Table 3, and the element composition of the product is shown in Table 4.

Example 4

Distillate was treated according to the procedure of example 1 except that distillate 2 was used in place of distillate 1 and cooled to room temperature to give 30.5g of liquid phase product, and the product distillation range distribution and other property tests are shown in Table 3 and the elemental composition of the product is shown in Table 4.

Example 5

30mL (30.6g) of distillate oil 1 is added into a high-pressure reaction kettle, oxygen (pure) is introduced to control the reaction pressure in a reaction system, the temperature, the pressure and the time of the reaction are shown in table 3, 30.2g of solid product is obtained after the temperature is reduced to the normal temperature, the performance tests such as the distillation range distribution of the product are shown in table 3, and the element composition of the product is shown in table 4.

Example 6

30mL (30.6g) of distillate oil 1 was charged into a high pressure autoclave, and 10mL of H was added₂O₂Hydrogen peroxide with the content of 30 weight percent is introduced, nitrogen is introduced, the temperature, the pressure and the time of the reaction are shown in table 3, after the temperature is reduced to normal temperature, a part of water sample at the bottom is separated, 30.5g of black solid product is obtained, the performance tests such as the distillation range distribution of the product are shown in table 3, and the element composition of the product is shown in table 4.

Example 7

30mL (30.6g) of distillate oil 1 is added into a high-pressure reaction kettle, 0.3g of benzoyl peroxide is added, nitrogen is introduced, the temperature, the pressure and the time of the reaction are shown in table 3, 30.1g of solid product is obtained after the temperature is reduced to the normal temperature, the performance tests such as the distillation range distribution of the product are shown in table 3, and the element composition of the product is shown in table 4.

Example 8

30mL (30.6g) of distillate oil 1 is added into a high-pressure reaction kettle, nitrogen is introduced for replacement, a maintaining system is a nitrogen atmosphere, the temperature is raised to the reaction temperature, a mixture of oxygen and nitrogen (the content of oxygen is 5 volume percent) is introduced to control the reaction pressure in the reaction system, the reaction temperature, the reaction pressure and the reaction time are shown in a table 3, 30.3g of semisolid products are obtained after the reaction temperature is reduced to the normal temperature, the performance tests such as the distillation range distribution of the products are shown in the table 3, and the element composition of the products is shown in the table 4.

Example 9

Distillate 1 was treated according to the procedure of example 1, but under different conditions such as temperature (as shown in Table 3), and after cooling to room temperature, 30.5g of liquid product was obtained, and the properties such as distillation range distribution of the product are shown in Table 3, and the elemental composition of the product is shown in Table 4.

Comparative example 1

Distillate 1 was treated in the same manner as in example 1 except that the pressure of the reaction was controlled by nitrogen alone without introducing oxygen, and after cooling to normal temperature, 30.5g of a liquid product was obtained, and the properties such as the distillation range distribution of the product were measured as shown in Table 3 and the elemental composition of the product was shown in Table 4.

Comparative example 2

Distillate 1 was treated according to the procedure of example 1 except that the temperature, pressure and time of the reaction were as shown in Table 3, and after cooling to normal temperature, 30.5g of a liquid product was obtained, and the properties such as the distillation range distribution of the product were measured as shown in Table 3 and the elemental composition of the product was shown in Table 4.

Comparative example 3

Distillate was treated according to the procedure of example 1 except that distillate 3 was used in place of distillate 1 to give 30.5g of liquid phase product after cooling to room temperature, and the product distillation range distribution and other property tests are shown in Table 3 and the elemental composition of the product is shown in Table 4.

TABLE 3

TABLE 4

	C (wt%)	H (wt%)	S (wt%)	N (wt%)
					Example 1	87.25	11.88	0.79	0.08
Example 2	87.25	11.88	0.79	0.08
					Example 3	86.94	12.26	0.73	0.07
Example 4	87.04	12.08	0.80	0.08
					Example 5	87.16	11.98	0.78	0.08
Example 6	87.07	12.07	0.79	0.07
					Example 7	87.32	11.84	0.78	0.06
Comparative example 1	86.94	12.18	0.81	0.07
					Comparative example 2	87.53	11.56	0.84	0.07
Comparative example 3	88.92	10.20	0.85	0.03

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.