CN112852484B

CN112852484B - Production method of low-sulfur marine fuel oil blending component

Info

Publication number: CN112852484B
Application number: CN202110008671.2A
Authority: CN
Inventors: 杨涛; 扈广法; 黄传峰; 李伟; 韩信有; 焦有军; 张轩; 刘亚青; 张小琴; 张生娟; 任彩玲
Original assignee: Shaanxi Yanchang Petroleum Group Co Ltd
Current assignee: Shaanxi Yanchang Petroleum Group Co Ltd
Priority date: 2021-01-05
Filing date: 2021-01-05
Publication date: 2023-03-31
Anticipated expiration: 2041-01-05
Also published as: CN112852484A

Abstract

A method for producing a low-sulfur marine fuel oil blending component comprises the following steps; the method comprises the following steps of carrying out atmospheric and vacuum fractionation on raw materials to obtain naphtha fraction, diesel fraction, wax oil fraction and vacuum residue oil, feeding a reaction product flowing out of an emulsion bed hydrogenation reactor into a first thermal high fraction, feeding the first thermal high fraction product into a fixed bed hydrogenation reactor, feeding the first thermal high fraction product into a first thermal low fraction, feeding the first thermal low fraction product into a vacuum tower, feeding the first thermal low fraction product into a pipe network, obtaining the wax oil fraction at the lateral line of the vacuum tower, and obtaining tail oil at the bottom of the vacuum tower; the product of the fixed bed hydrogenation reactor enters a second hot high-temperature separator, the second hot high-temperature separator enters a cold high-temperature separator, the cold high-temperature separator enters a cold low-temperature separator, the cold low-temperature separator enters a fractionation unit, and the cold low-temperature separator enters a pipe network; and the second thermal high-molecular product enters a second thermal low-molecular product, the second thermal low-molecular product enters a fractionation unit, and the second thermal low-molecular product enters a pipe network. The invention realizes the characteristics of deep hydrogenation, high-efficiency conversion and low cost of the heavy inferior oil.

Description

Production method of low-sulfur marine fuel oil blending component

Technical Field

The invention relates to the technical field of heavy oil hydrotreatment, in particular to a production method of a low-sulfur marine fuel oil blending component.

Background

Petroleum remains a major global energy source and is also a scarce resource. The trend of continuously aggravating crude oil quality in a global range, china also faces a severe situation that the dependence of crude oil import is continuously increased, the imported crude oil is mostly sulfur-containing and high-sulfur crude oil, the properties are poor, the processing is difficult, and the utilization of high added value of the heavy and inferior oil becomes a difficult problem to be solved urgently in the refining industry of China, so that the method is not only beneficial to transformation upgrading of the traditional refinery, but also beneficial to ensuring the energy strategic safety of China. Meanwhile, the oil quality is continuously upgraded in the world, the bunker fuel oil gradually develops low sulfur, and the production technology of the bunker fuel oil with low cost is lacked in the world at present.

Patent CN1335371A discloses a heavy hydrocarbon feed hydrotreating method organically combining residual oil hydrocracking and fixed bed residual oil hydrotreating technologies, which can carry out hydrocracking reaction on residual oil under the condition of not causing coking of a reactor, remove metal and carbon residue in the residual oil to the maximum extent, reduce the operation severity of the pretreated residual oil subjected to fixed bed hydrogenation, prolong the operation life of a residual oil fixed bed hydrogenation device, but have limited conversion depth on the residual oil. Patent CN1609176A discloses a process for producing high-quality heavy oil catalytic cracking raw material by combining suspension bed hydrocracking and fixed bed hydrotreating, the suspension bed hydrocracking enlarges the raw material source of the fixed bed hydrogenation process, and the fixed bed hydrogenation can obtain high-quality catalytic cracking feed, but the product quality is relatively low.

The heavy inferior oil hydrogenation combined process has a room for improving the hydrogenation reaction depth and the product quality, and a low-cost low-sulfur marine fuel oil production method is not formed.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention aims to provide a production method of a low-sulfur marine fuel oil blending component, which couples hydrogenation of an emulsion bed with hydrogenation of a fixed bed, limits the dry point value of the wax oil fraction in hydrogenation feeding of the fixed bed by adjusting the content of the wax oil fraction in hydrogenation feeding of the emulsion bed, arranging a hydrogen distributor and utilizing a high-activity transition metal catalyst, weakens external diffusion resistance, enhances hydrogenation activity, improves the depth of a main reaction and reduces side reactions, thereby realizing deep hydrogenation and high-efficiency conversion of heavy and inferior oil and forming the low-sulfur marine fuel oil production method with low cost.

In order to achieve the purpose, the invention adopts the technical scheme that:

a method for producing a low-sulfur marine fuel oil blending component comprises the following steps;

step (1): performing atmospheric and vacuum fractionation on the raw material to obtain naphtha fraction, diesel fraction, wax oil fraction and vacuum residue, wherein the dry point of the wax oil fraction is less than 565 ℃, mixing the vacuum residue with a catalyst, mixing and heating the mixture with hydrogen, and feeding the mixture into an emulsion bed hydrogenation reactor for hydrogenation and lightening;

step (2): enabling a reaction product flowing out of the top of the hydrogenation reactor of the emulsion bed to enter a first thermal high-temperature reactor, enabling the top product of the first thermal high-temperature reactor to enter a fixed bed hydrogenation reactor, enabling the bottom product of the first thermal high-temperature reactor to enter a first thermal low-temperature reactor, enabling the bottom product of the first thermal low-temperature reactor to enter a pressure reducing tower, enabling the top product of the first thermal low-temperature reactor to enter a pipe network, enabling the side line of the pressure reducing tower to obtain a wax oil fraction, enabling the dry point of the wax oil fraction obtained by measuring the line of the pressure reducing tower to be less than 565 ℃, and enabling the bottom of the pressure reducing tower to obtain tail oil;

(3) The bottom product of the fixed bed hydrogenation reactor enters a second hot high-temperature separator, the top product of the second hot high-temperature separator enters a cold high-temperature separator, the bottom product of the cold high-temperature separator enters a cold low-temperature separator, the bottom product of the cold low-temperature separator enters a fractionating unit, and the top product of the cold low-temperature separator enters a pipe network;

(4) And the bottom product of the second thermal high-pressure separation enters a second thermal low-pressure separation unit, the bottom product of the second thermal low-pressure separation enters a fractionation unit, and the top product of the second thermal low-pressure separation enters a pipe network.

The emulsion bed reactor and the fixed bed reactor are internally provided with a hydrogen distributor before or at an inlet or in the reactor, and the hydrogen distributor can crush the size of hydrogen bubbles to micron-sized or below.

The reaction conditions in the emulsion bed reactor are that the reaction pressure is 6-10MPa, the reaction temperature is 430-455 ℃, and the total feeding is carried outThe volume space velocity is 0.5-1.0h ^-1 The hydrogen-oil ratio is 800-1600NL/kg, and the dosage of the additive is 0.1-1.5% of the feeding quantity of the vacuum residue.

The reaction conditions in the fixed bed reactor are that the reaction pressure is 6-10MPa, the inlet temperature of the reactor is 360-385 ℃, and the total volume airspeed of the feeding material is 0.5-1.5h ^-1 The hydrogen-oil ratio is 300-800NL/kg.

The mass fraction content of the fraction of less than 525 ℃ in the vacuum residue is more than 10 percent.

The catalyst is a liquid catalyst, and the active metal of the liquid catalyst is one or the combination of more of Mo and Ni.

The catalyst is a solid particle type catalyst, and the solid particle type catalyst is a Mo catalyst taking a carbonaceous material as a carrier or a Mo/Co catalyst taking the carbonaceous material as a carrier.

The invention has the beneficial effects that:

(1) The combined method provided by the invention limits the dry point of wax oil fraction fed into the fixed bed to be less than 565 ℃, ensures that metals such as Ni, V and the like cannot enter a fixed bed hydrogenation reactor excessively, and avoids rapid adsorption and deposition on the surface of a catalyst to cause catalyst inactivation or bed layer blockage, thereby prolonging the fixed bed hydrogenation operation period.

(2) In the combination method provided by the invention, a hydrogen distributor capable of crushing hydrogen into hydrogen bubbles with micron-sized and below sizes is arranged in the front of or at the inlet of the hydrogenation reactor of the emulsion bed and the hydrogenation reactor of the fixed bed or in the reactor, and the hydrogen distributor exists in raw oil, the raw oil and the hydrogen form an emulsified mixture, and an emulsified bed layer is formed in the reactor, so that the area of an oil-gas mass transfer interface is greatly increased, the resistance of external diffusion is weakened, and the three-pass-one-reverse reaction is promoted.

(3) In the combination method provided by the invention, the wax oil fraction content in the feed of the emulsion bed is adjusted to be more than or equal to 10 percent, the part of raw materials contains more alkane or olefin relative to heavy components, the aromaticity is low, the free radical reaction performance and the carbonium ion reaction performance are good, and the reaction depth can be increased in a reaction system.

(4) The combined method provided by the invention adopts a liquid catalyst, a Mo catalyst taking a carbonaceous material as a carrier or a Mo/Co catalyst taking a carbonaceous material as a carrier, the catalysts are all transition metal catalysts and are all external surface reaction catalysts, and the active state metals after vulcanization are all on the external surfaces, so that the reaction does not involve an internal diffusion process, the resistance of the internal diffusion is avoided, the reaction activity is improved, the reaction speed is accelerated, and the reaction depth is enhanced.

(5) The combined method provided by the invention realizes deep hydrogenation and high-efficiency conversion of heavy inferior oil, has good product quality, and can produce low-sulfur marine oil at low cost.

Drawings

Fig. 1 is a schematic flow chart of embodiment 1 and embodiment 2 provided in the present invention.

Detailed Description

The present invention will be described in further detail with reference to the accompanying drawings.

The properties of the raw materials used in the following examples are as follows:

density (20 ℃ C.) g/cm3	0.9478
		Viscosity (50 ℃ C.)	122.52mm2/S
Toluene insolubles (wt%)	0.076
		Ash content (wt%)	0.087
Carbon residue (wt%)	10.86
		Carbon element (wt%)	83.895
Hydrogen element (wt%)	10.558
		Nitrogen element (wt%)	0.937
Elemental sulfur (wt%)	2.81
		Saturated parts (wt%)	36.45
Aromatic component (wt%)	37.26
		Colloid (wt%)	15.67
Asphaltenes (wt%)	7.2
		Ni(μg/g)	27.06
Fe(μg/g)	5.12
		V(μg/g)	87.68
Fraction content > 525 DEG C	40.50％

Example 1 (as shown in FIG. 1)

The raw material is subjected to atmospheric and vacuum fractionation to obtain 7.8% of naphtha fraction, 18.2% of diesel oil fraction, 29.00% of wax oil fraction and 45.00% of vacuum residue, wherein the dry point of the wax oil fraction is less than 565 ℃, the content of the fraction in the vacuum residue at the temperature of less than 525 ℃ is more than 10%, the vacuum residue is mixed with a Mo catalyst which takes a carbonaceous material as a carrier and has the mass of 1.5%, the mixture is mixed and heated with hydrogen, the mixture enters an emulsion bed hydrogenation reactor for hydrogenation and lightening, and a hydrogen distributor which can crush the size of hydrogen bubbles to micron and below is arranged in front of the inlet of the emulsion bed hydrogenation reactor. The reaction conditions in the hydrogenation reactor of the emulsion bed are as follows: the reaction pressure is 10MPa, the reaction temperature is 455 ℃, and the space velocity of the total volume of the feeding materials is 1.0h ^-1 The hydrogen-oil ratio was 1600N/kg. The method comprises the following steps of enabling a reaction product flowing out of the top of an emulsion bed reactor to enter a first thermal high fraction, enabling a first thermal high fraction top product to enter a fixed bed hydrogenation reactor, enabling a first thermal high fraction bottom product to enter a first thermal low fraction, enabling a first thermal low fraction bottom product to enter a pressure reduction tower, enabling the first thermal low fraction top product to enter a pipe network, obtaining a wax oil fraction from the lateral line of the pressure reduction tower, enabling the dry point of the wax oil fraction to be less than 565 ℃, and obtaining tail oil from the bottom of the pressure reduction tower. The fixed bed hydrogenation reactor is a micro-interface hydrogenation reactor, and the reaction conditions are as follows: the reaction pressure is 10MPa, the reactor inlet temperature is 360 ℃, and the space velocity of the total feeding volume is 1.5h ^-1 The hydrogen-oil ratio is 300NL/kg, and a protective agent, a demetallizing agent and a desulfurizing agent are respectively filled in the fixed bed hydrogenation reactor from top to bottom. The bottom product of the fixed bed hydrogenation reactor enters a second hot high-temperature separator, the top product of the second hot high-temperature separator enters a cold high-temperature separator, the bottom product of the cold high-temperature separator enters a cold low-temperature separator, the bottom product of the cold bottom separator enters a fractionation unit, and the top product of the cold low-temperature separator enters a pipe network; the bottom product of the second thermal high-pressure separation enters a second thermal low-pressure separation, the bottom product of the second thermal low-pressure separation enters a fractionation unit, and the top product of the second thermal low-pressure separation enters a pipe network; the fractionating unit sequentially fractionates to obtain a gas product, a naphtha fraction, a marine distillate fuel oil blending component and a marine residual fuel oil blending component, wherein the marine distillate marine fuel oil blending component has a sulfur content of less than 0.1%, and the marine residual marine fuel oil has a sulfur content of less than 0.5%。

Example 2

The raw material is subjected to atmospheric and vacuum fractionation to obtain 7.8% of naphtha fraction, 18.2% of diesel oil fraction, 29.00% of wax oil fraction and 45.00% of vacuum residue, wherein the dry point of the wax oil fraction is less than 565 ℃, the content of the fraction in the vacuum residue at the temperature of less than 525 ℃ is more than 10%, the vacuum residue is mixed with a Mo/Co catalyst which takes a carbonaceous material as a carrier and has the mass of 0.5%, the mixture is mixed and heated with hydrogen and enters an emulsion bed hydrogenation reactor for hydrogenation and lightening, and a bubble generating piece which can crush the size of hydrogen bubbles to micron and below is arranged at the inlet of the emulsion bed hydrogenation reactor. The reaction conditions in the hydrogenation reactor of the emulsion bed are as follows: the reaction pressure is 6MPa, the reaction temperature is 430 ℃, and the space velocity of the total volume of the feeding materials is 0.5h ^-1 The hydrogen-oil ratio was 800N/kg. The method comprises the following steps of enabling a reaction product flowing out of the top of an emulsion bed reactor to enter a first thermal high-pressure separator, enabling the first thermal high-pressure separator top product to enter a fixed bed hydrogenation reactor, enabling the first thermal high-pressure separator bottom product to enter a first thermal low-pressure separator, enabling the first thermal low-pressure separator bottom product to enter a vacuum tower, enabling the first thermal low-pressure separator top product to enter a pipe network, obtaining a wax oil fraction at the lateral line of the vacuum tower, enabling the dry point of the wax oil fraction to be less than 565 ℃, and obtaining tail oil at the bottom of the vacuum tower. The fixed bed hydrogenation reactor is a micro-interface hydrogenation reactor, and the reaction conditions are as follows: the reaction pressure is 6MPa, the reactor inlet temperature is 370 ℃, and the total feeding volume space velocity is 0.5h ^-1 The hydrogen-oil ratio is 500NL/kg, and a protective agent, a demetallizing agent and a desulfurizing agent are respectively filled in the fixed bed hydrogenation reactor from top to bottom. Enabling the bottom product of the fixed bed hydrogenation reactor to enter a second hot high-temperature separator, enabling the top product of the second hot high-temperature separator to enter a cold high-temperature separator, enabling the bottom product of the cold high-temperature separator to enter a cold low-temperature separator, enabling the bottom product of the cold bottom separator to enter a fractionating unit, and enabling the top product of the cold low-temperature separator to enter a pipe network; the bottom product of the second thermal high-pressure separation enters a second thermal low-pressure separation, the bottom product of the second thermal low-pressure separation enters a fractionation unit, and the top product of the second thermal low-pressure separation enters a pipe network; and sequentially fractionating by a fractionating unit to obtain a gas product, a naphtha fraction, a marine distillate fuel oil blending component and a marine residual fuel oil blending component, wherein the sulfur content of the marine distillate fuel oil blending component is less than 0.1%, and the sulfur content of the marine residual fuel oil blending component is less than 0.1%.

/>

Claims

1. The production method of the low-sulfur marine fuel oil blending component is characterized by comprising the following steps;

step (1): the method comprises the following steps of (1) carrying out atmospheric and vacuum fractionation on a raw material to obtain naphtha fraction, diesel oil fraction, wax oil fraction and vacuum residue, wherein the dry point of the wax oil fraction is less than 565 ℃, mixing the vacuum residue with a catalyst, mixing and heating the mixture with hydrogen, and feeding the mixture into an emulsion bed hydrogenation reactor for hydrogenation and lightening;

and (3): the bottom product of the fixed bed hydrogenation reactor enters a second hot high-temperature separator, the top product of the second hot high-temperature separator enters a cold high-temperature separator, the bottom product of the cold high-temperature separator enters a cold low-temperature separator, the bottom product of the cold low-temperature separator enters a fractionation unit, and the top product of the cold low-temperature separator enters a pipe network;

and (4): the bottom product of the second thermal high-pressure separation enters a second thermal low-pressure separation, the bottom product of the second thermal low-pressure separation enters a fractionation unit, and the top product of the second thermal low-pressure separation enters a pipe network;

the mass fraction content of the fraction below 525 ℃ in the vacuum residue is more than 10 percent;

the catalyst is a solid particle type catalyst, and the solid particle catalyst is a Mo catalyst taking a carbonaceous material as a carrier or a Mo/Co catalyst taking the carbonaceous material as a carrier.

2. The method of claim 1, wherein the emulsion bed hydrogenation reactor and the fixed bed hydrogenation reactor are provided with a hydrogen distributor prior to or at the inlet or within the reactors, said hydrogen distributor being capable of reducing hydrogen bubble size to micron and below.

3. The method for producing the low-sulfur bunker fuel oil blending component of claim 1, wherein the reaction conditions in the emulsion bed hydrogenation reactor are that the reaction pressure is 6-10MPa, the reaction temperature is 430-455 ℃, and the total volume space velocity of the feeding materials is 0.5-1.0h ^-1 The hydrogen-oil ratio is 800-1600NL/kg, and the dosage of the catalyst is 0.1-1.5% of the feeding quantity of the vacuum residue.

4. The method for producing the low-sulfur marine fuel oil blending component according to claim 1, wherein the reaction conditions in the fixed bed hydrogenation reactor are 6-10MPa of reaction pressure, 360-385 ℃ of reactor inlet temperature and 0.5-1.5h of total feeding volume space velocity ^-1 And the hydrogen-oil ratio is 300-800NL/kg.

5. The method of claim 1, wherein the catalyst is a liquid catalyst and the liquid catalyst active metal is one or more of Mo and Ni in combination.