CN1752182A - Method for producing aromatic hydrocarbon rubber filling oil - Google Patents

Abstract

A process for preparing the arylhydrocarbon-type filling oil for rubber includes such steps as mixing tar fraction with H2, hydrogenating reaction on hydromodifying catalyst Mo-Ni-P for removing S, N, colloid and asphalt from tar fraction, separating out H2, dry gas, H2S, NH4 and liquefied gas to obtain liquid, fractionating, and cutting.

Description

A kind of production method of aromatic hydrocarbon type rubber extender oil

technical field

The invention belongs to the field of coal chemical industry and relates to a production method of aromatic hydrocarbon type rubber filler oil.

Background technique

Rubber extender oil is a special oil used in the production of oil-extended rubber. After the rubber is filled with oil, the processability and use performance can be improved, while increasing the output of rubber and reducing the cost. The output of natural rubber in my country is limited, and synthetic rubber occupies a large proportion in the rubber industry. With the advancement of my country's synthetic rubber technology and the increase in output, the output of oil-extended rubber is also increasing rapidly, so the demand for rubber extender oil is also increasing day by day; among them, aromatic hydrocarbon-type rubber extender oil has good compatibility with various types of rubber and is full of energy. The amount of oil is large, so the amount is also the largest.

At present, only a few oil refineries in China directly use straight-run extracted oil as aromatic rubber extension oil. The quantity is limited and the quality is unstable. It is difficult to meet the different requirements of different rubber factories, which affects the production of oil-extended rubber, causing some rubber The production plant needs to import filler oil. CN1022844C discloses a method for producing high-value products from wax oil, which uses solvent extraction and other technology optimization combinations to process inferior wax oil to produce aromatic hydrocarbon rubber filler oil. A method disclosed in CN87105674A is to use the clarified oil obtained after sedimentation, clarification and filtration of catalytic cracking heavy distillate oil as aromatic hydrocarbon rubber extension oil. Although these methods have mature technology and simple production process, the output is limited and it is not easy to form a scale. At the same time, due to the continuous reduction of oil resources, in order to make full and reasonable use of oil resources, major oil refineries have taken the lightening of heavy oil as a research topic, and maximized the production of light fuels to increase the production capacity of the refinery. Therefore, the use of part of the heavy oil produced by the refinery to produce aromatic rubber extender oil is far from meeting the market demand. Therefore, it is of great practical significance to seek new sources of raw materials to produce qualified aromatic rubber extender oils.

my country is a country rich in coal resources. The coal tar produced by the coal chemical process has the characteristics of natural crude oil. How to effectively use coal tar is an important link in the comprehensive utilization of coal. The usual method is to produce chemical products such as benzene and pyridine by chemical methods, but this method is difficult to separate or purify, and it is not easy to form a large scale; there are also coal tars that are used as fuel oil after pickling and alkali washing, but the method produces Acid slag and alkali slag are difficult to deal with, causing serious pollution, and fuel oil does not meet environmental protection standards. Therefore, it is very important to make full and rational use of abundant coal tar fractions to produce high-value products.

Contents of the invention

The technical problem to be solved by the present invention is: the existing method of producing aromatic hydrocarbon rubber filler oil by using petroleum processed products and by-products has the problems of insufficient raw materials, limited output and unstable product quality.

In order to solve the above problems, the technical solution adopted in the present invention is: a production method of aromatic hydrocarbon type rubber extender oil, which is characterized in that it consists of the following steps:

A. The coal tar fraction and hydrogen are mixed and then enter the hydrogenation reactor, and react with the Mo-Ni-P hydrogenation modification catalyst to remove sulfur, nitrogen impurities, colloids, and asphaltenes in the coal tar fraction. The reaction conditions are: : Hydrogen partial pressure is 8.0-14.0MPa, reaction temperature is 370-390℃, volume space velocity is 0.6-1.0h ^-1 , hydrogen-oil volume ratio is 1000-1200, and the reaction product is exported to the hydrogenation reactor;

The Mo-Ni-P hydrogenation modification catalyst, based on the dry basis of oxides, MoO ₃ accounts for 15-25w% of the total catalyst weight, NiO accounts for 2-6w% of the total catalyst weight, P ₂ O ₅ accounts for the total catalyst weight 3-8w% of the weight, and the rest is amorphous aluminum silicate carrier;

B. The reaction product obtained in step A enters the gas separation and stabilization system after heat exchange and cooling, and after separating out hydrogen, dry gas, hydrogen sulfide and ammonia and liquefied gas, a liquid product is obtained;

C. The liquid product obtained in step B is fractionated and cut in a fractionating tower to obtain a fraction above 360°C, which is the aromatic hydrocarbon rubber extension oil product.

Adopting the present invention has the following beneficial effects: (1) the present invention utilizes the conventional fixed bed hydrogenation device and process flow in the petroleum processing industry, the process technology is mature, and the production process is simple; (2) the present invention has no special requirements for raw materials , can make full use of the coal tar fraction produced by the industrial coal dry distillation device, the raw material source is wide, and the processing capacity is large; (3) the aromatic hydrocarbon type rubber filler oil produced by the method of the present invention has a sulfur content lower than 500 μg/g and a low nitrogen content At 1000μg/g, the content of aromatic hydrocarbons is not less than 90w% (w% means weight percentage); good stability, non-toxic, no peculiar smell, no adverse effects on the environment; (4) The demand for aromatic hydrocarbon rubber filler oil is constantly increasing And under the situation that oil supply becomes increasingly tense, the present invention opens up a new raw material source for the production of aromatic hydrocarbon type rubber extender oil. The method of the invention is suitable for large-scale production of aromatic hydrocarbon type rubber extender oil, and can solve the problem of insufficient output of aromatic hydrocarbon type rubber extender oil. In addition, it is a brand-new train of thought to produce qualified aromatic hydrocarbon type rubber extender oil by hydrogenation modification of coal tar distillates, and no relevant reports have been seen so far; therefore, the present invention provides a new method for the comprehensive utilization of coal tar way.

The present invention will be further described in detail below in combination with specific embodiments and examples. The detailed description and examples do not limit the scope of protection of the present invention.

Detailed ways

The production method of aromatic hydrocarbon type rubber extender oil of the present invention is made up of the following steps:

A. The coal tar fraction is mixed with hydrogen and enters the hydrogenation reactor, where it reacts with the Mo-Ni-P hydrogenation modification catalyst to remove sulfur, nitrogen impurities, colloids, and asphaltenes in the coal tar fraction. Coal tar fraction refers to the coal tar after separation of phenol, naphthalene and tar pitch in the existing industrial coal dry distillation device in the coal chemical industry. The sulfur content is generally 0.3-1.0w%, and the nitrogen content is generally 0.4-1.2w%. , the initial boiling point is generally not lower than 150°C, the dry point is generally not more than 530°C, the content of aromatics is generally 75-90w%, and the content of gum and asphaltenes is generally 5-15w%. The hydrogenation reactor adopts a conventional fixed-bed hydrogenation reactor, and adopts a single-pass operation mode. After the coal tar fraction and hydrogen are mixed, they are generally preheated to 330-350°C by a heat exchanger and a heating furnace, and then enter the hydrogenation reactor from the upper part of the hydrogenation reactor, and flow downwards in the hydrogenation reactor. The reaction conditions of coal tar fraction and hydrogen in the hydrogenation reactor are: hydrogen partial pressure 8.0-14.0MPa, reaction temperature 370-390°C, volume space velocity 0.6-1.0h-1, hydrogen-oil volume ratio 1000-1200. After the reaction, the reaction product is exported from the lower part of the hydrogenation reactor to the hydrogenation reactor.

The Mo-Ni-P hydrogenation modification catalyst is a Mo-Ni-P hydrogenation modification catalyst loaded on an amorphous aluminum silicate carrier; in terms of oxide dry basis, MoO ₃ accounts for the total weight of the catalyst 15-25w%, NiO accounts for 2-6w% of the total catalyst weight, _P2O5 accounts for 3-8w% of the total catalyst weight _, and the rest is amorphous aluminum silicate carrier. The pore volume of the catalyst is generally 0.3-0.5ml/g, the specific surface is generally 330-400m ² /g; the shape is spherical, and the diameter is generally φ1.5-3mm. The catalyst has strong desulfurization and denitrogenation capabilities, and can remove colloids and asphaltenes in coal tar fractions. The catalyst is prepared by a conventional hydrogenation upgrading catalyst preparation method in the petroleum processing industry.

B. The reaction product obtained in step A enters the gas separation and stabilization system after heat exchange and cooling, and after separating hydrogen, dry gas, hydrogen sulfide, ammonia and liquefied gas, a liquid product is obtained. Among them, the gas separation and stabilization system includes a high-pressure separator, a low-pressure separator and a stabilization tower connected in sequence. The reaction product obtained in step A is exchanged and cooled to normal temperature (30-50°C) in the heat exchange and cooling equipment, and then enters the high-pressure separator to separate most of the hydrogen and most of the dry gas (C ₁ -C ₂ group ), most of hydrogen sulfide and ammonia, and a small amount of liquefied gas (C ₃ ~C ₄ components), and then enter the low-pressure separator; in the low-pressure separator, most of the remaining liquefied gas, most of hydrogen sulfide and ammonia, The residual hydrogen and dry gas then enter the stabilization tower; in the stabilization tower the residual liquefied gas, hydrogen sulfide and ammonia are separated. In the above process, the hydrogen-rich gas separated by the high-pressure separator after removing most of the hydrogen sulfide and ammonia impurities is recycled. The above-mentioned gas separation and stabilization system and its operating process and operating conditions are conventional, and are the same as those in conventional fixed-bed hydrogenation units for petroleum processing.

C. The liquid product obtained in step B (C5 and above components, flowing out from the stabilizing tower) is fractionated and cut in a fractionating tower, and fractions at and below 360°C are separated to obtain fractions above 360°C and sent to the product tank. The fraction above 360°C is the aromatic hydrocarbon type rubber extender oil product. The above-mentioned fraction above 360°C refers to the fraction of the liquid product above 360°C to its final boiling point. The fractionation tower is an atmospheric fractionation tower, and its operating conditions adopt conventional operating conditions.

The above-mentioned aromatic hydrocarbon rubber filler oil produced by the process of the present invention has a sulfur content of less than 500 μg/g, a nitrogen content of less than 1000 μg/g, an aromatic hydrocarbon content of not less than 90w%, and a colloid and asphaltene content of not more than 2w%. ; The initial boiling point is higher than 360°C, and the dry point is not more than 550°C; it has good stability, is non-toxic, has no peculiar smell, and has no adverse effects on the environment.

Example

Example 1

Tested on a small pilot rig. The hydrogenation reactor of the device is a 100ml fixed-bed hydrogenation reactor, and the fractionation tower is a real boiling point distillation device with 17 theoretical trays. The coal tar fraction processed in the test is coal tar (phenol, naphthalene and tar pitch have been separated) produced by an industrial coal dry distillation unit, and its main properties are shown in Table 1. The 100ml fixed-bed hydrogenation reactor is filled with amorphous Mo-Ni- _P hydrogenation modification catalyst on aluminum silicate carrier, its _MoO3 content is 22.8w%, NiO content is 3.4w%, _P2O5 content is 4.8w%, and the rest is amorphous aluminum silicate carrier. The catalyst has a pore volume of 0.38ml/g, a specific surface of 363m ² /g, a spherical shape and a diameter of φ2.0mm. The catalyst is presulfurized by a conventional presulfurization process before use, and after the activity of the catalyst is stable, the process condition investigation test is carried out (the following examples are the same).

In Embodiment 1 (and in Embodiment 2 and Embodiment 3 below), the gas separation and stabilization system of the test device is only provided with a high-pressure separator, and no low-pressure separator and stabilization tower are provided.

During the operation, the above-mentioned coal tar fraction and hydrogen are mixed and then enter the hydrogenation reactor from the upper part of the hydrogenation reactor, and react with the Mo-Ni-P hydrogenation modification catalyst in contact. The test adopts the single-pass operation method to carry out hydrogenation upgrading of the coal tar fraction. After the reaction, the reaction product is exported from the lower part of the hydrogenation reactor, cooled to room temperature, and enters the high-pressure separator, where most of the hydrogen, dry gas, hydrogen sulfide, ammonia and a small amount of liquefied gas are separated. Then it enters the buffer tank and is stripped with nitrogen under normal operating conditions to separate the remaining liquefied gas, hydrogen, dry gas, hydrogen sulfide and ammonia. The liquid product ( _C5 and above components) obtained after separating the above gas flows out from the buffer tank and is sent to the true boiling point distillation device for fractionation. The light fraction at or below 360°C is cut out in the true boiling point distillation device to obtain a fraction above 360°C; the fraction above 360°C is the aromatic hydrocarbon type rubber filler oil product of the present invention.

In the above separation process, the hydrogen-rich gas separated by the high-pressure separator is not recycled.

In Example 1, the hydrogenation upgrading process conditions (that is, the reaction conditions of the hydrogenation reactor) and the fraction above 360°C (referring to the fraction above 360°C to the final boiling point, that is, the aromatic hydrocarbon rubber extension oil of the present invention; the following implementation For example, see Table 2 for product properties. For comparison, Table 2 lists the corporate standards for aromatic rubber extender oil formulated and implemented by China Petroleum & Chemical Corporation. It can be seen from Table 2 that the sulfur content of the aromatic hydrocarbon type rubber extender oil obtained in Example 1 is 368 μg/g, the nitrogen content is 826 μg/g, the aromatic hydrocarbon content is 94.1w%, and the colloid and asphaltene content are 1.7w%. ; Good stability, non-toxic, no peculiar smell, no adverse effects on human body and environment.

Example 2

According to Example 1, the difference is the hydro-upgrading process conditions and the component content and physical parameters of the Mo-Ni-P hydro-upgrading catalyst. See Table 2 for the process conditions of hydrogenation upgrading and the product properties of fractions above 360°C. The _MoO3 content of the Mo-Ni-P hydrogenation modification catalyst used is 20.5w%, the NiO content is 4.6w%, _{the P2O5} content is 5.9w%, and the rest is an amorphous aluminum silicate carrier. The catalyst has a pore volume of 0.40ml/g, a specific surface of 375m ² /g, a spherical shape, and a diameter of φ2.5mm.

The used test apparatus of embodiment 2, coal tar fraction, processing steps and other unillustrated operation process, all are identical with embodiment 1.

It can be seen from Table 2 that the sulfur content of the aromatic hydrocarbon type rubber extender oil obtained in Example 2 is 352 μg/g, the nitrogen content is 786 μg/g, the aromatic hydrocarbon content is 93.5w%, and the colloid and asphaltene content are 1.5w%. ; Good stability, and no smell, is an environmentally friendly product.

Example 3

According to Example 1, the difference is the hydro-upgrading process conditions and the component content and physical parameters of the Mo-Ni-P hydro-upgrading catalyst. See Table 2 for the process conditions of hydrogenation upgrading and the product properties of fractions above 360°C. The MoO ₃ content of the Mo-Ni-P hydrogenation modification catalyst used is 18.1w%, the NiO content is 5.4w%, the P ₂ O ₅ content is 6.8w%, and the rest is an amorphous aluminum silicate carrier. The catalyst has a pore volume of 0.42ml/g, a specific surface of 388m ² /g, a spherical shape and a diameter of φ2.8mm.

The test apparatus used in embodiment 3, the coal tar fraction, the processing steps and other undescribed operating procedures are all the same as in embodiment 1.

It can be seen from Table 2 that the sulfur content of the aromatic hydrocarbon type rubber extender oil obtained in Example 3 is 375 μg/g, the nitrogen content is 844 μg/g, the aromatic hydrocarbon content is 94.8w%, and the colloid and asphaltene content are 1.8w%. ; Product quality is good, and non-toxic, no smell, with the characteristics of environmentally friendly products.

Table 1 The main properties of coal tar fractions

(Example 1 to Example 3) project Density, 20℃, kg/ ^m3 1135.2 Charcoal residue, w% 1.41 Pour point, °C 1 Viscosity, 100℃, mm ² /s 3.926 Sulfur content, μg/g 7147 Nitrogen content, μg/g 9036 Aromatic content, w% 82.1 Resin and asphaltene content, w% 9.3 Distillation range (D2887), ℃ IBP/10% 154/242 50%/90% 340/429 95%/FBP 464/513 odor irritating odor

           Table 2 Hydrogenation upgrading process conditions and product properties of fractions above 360°C

(Example 1 to Example 3) project Example 1 Example 2 Example 3 Aromatic rubber extender oil enterprise standard Hydrogenation upgrading process conditions Hydrogen partial pressure, MPa 9.0 11.0 13.0 Reaction temperature, °C 390 370 380 Volumetric space velocity, h ^-1 0.8 0.6 1.0 Hydrogen oil volume ratio 1000 1100 1200 Product properties of fractions above 360°C Boiling range, °C 362～520 363～521 364～523 / Density, 20℃, kg/ ^m3 1084.5 1082.8 1088.6 ≮985.0 Open flash point, °C 233 231 235 ≮220 Pour point, °C 19 18 20 ≯25 Viscosity, 100℃, mm ² /s 23.04 22.86 23.25 20.0～26.0 Refractive index, n _D ²⁰ 1.5792 1.5768 1.5826 1.55～1.60 Sulfur/nitrogen content, μg/g 368/826 352/786 375/844 / Aromatic content, w% 94.1 93.5 94.8 ≮85.0 Resin and asphaltene content, w% 1.7 1.5 1.8 / Moisture, v% (v% means volume percentage) none none none ≯0.05 odor odorless odorless odorless /

Claims (1)

1, a kind of production method of aromatic hydrocarbon type rubber extender oil, it is characterized in that being made up of following steps: A. The coal tar fraction and hydrogen are mixed and then enter the hydrogenation reactor, and react with the Mo-Ni-P hydrogenation modification catalyst to remove sulfur, nitrogen impurities, colloids, and asphaltenes in the coal tar fraction. The reaction conditions are: : Hydrogen partial pressure is 8.0-14.0MPa, reaction temperature is 370-390℃, volume space velocity is 0.6-1.0h ^-1 , hydrogen-oil volume ratio is 1000-1200, and the reaction product is exported to the hydrogenation reactor; The Mo-Ni-P hydrogenation modification catalyst, based on the dry basis of oxides, MoO ₃ accounts for 15-25w% of the total catalyst weight, NiO accounts for 2-6w% of the total catalyst weight, P ₂ O ₅ accounts for the total catalyst weight 3-8w% of the weight, and the rest is amorphous aluminum silicate carrier; B. The reaction product obtained in step A enters the gas separation and stabilization system after heat exchange and cooling, and after separating out hydrogen, dry gas, hydrogen sulfide and ammonia and liquefied gas, a liquid product is obtained; C. The liquid product obtained in step B is fractionated and cut in a fractionating tower to obtain a fraction above 360°C, which is the aromatic hydrocarbon rubber extension oil product.