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CN-117844526-B - Low-sulfur heavy marine fuel oil and preparation method thereof

CN117844526BCN 117844526 BCN117844526 BCN 117844526BCN-117844526-B

Abstract

The invention relates to the technical field of marine fuel oil, and discloses low-sulfur heavy marine fuel oil and a preparation method thereof. The preparation method comprises the steps of carrying out mild catalytic cracking reaction on inferior residual oil I, separating an obtained mild catalytic cracking reaction product to obtain catalytic cracking heavy oil, carrying out hydrodesulfurization reaction on the catalytic cracking heavy oil, separating an obtained hydrodesulfurization reaction product to obtain hydrogenated heavy oil, and mixing the hydrogenated heavy oil with oil components to obtain the low-sulfur heavy marine fuel oil. The preparation method combines the catalytic cracking heavy oil hydrotreatment and the catalytic cracking, and mixes the obtained hydrogenated heavy oil with oil components, so that the low-sulfur marine fuel oil can be produced to the maximum extent by using inferior residual oil, the source of the marine fuel oil is enlarged, the low-sulfur heavy marine fuel oil has low sulfur content and low kinematic viscosity at 50 ℃, and each index meets the RMG180 or RMG380 product standard.

Inventors

  • YAN RUI
  • YANG HE
  • TAO ZHIPING
  • LIU TAO
  • LI YAN
  • TIAN HUAYU

Assignees

  • 中国石油化工股份有限公司
  • 中石化石油化工科学研究院有限公司

Dates

Publication Date
20260505
Application Date
20220930

Claims (14)

  1. 1. A method for preparing low-sulfur heavy marine fuel oil, which is characterized by comprising the following steps: (1) In the presence of a catalytic cracking catalyst, carrying out mild catalytic cracking reaction on inferior residual oil I to obtain a mild catalytic cracking reaction product, wherein the mass content of sulfur element in the inferior residual oil I is 0.78-3.0%, the 20 ℃ density of the inferior residual oil I is not more than 0.97g/cm 3 , the 100 ℃ kinematic viscosity of the inferior residual oil I is 3500mm 2 /s-5000mm 2 /s, the mass content of carbon residue is 6-50%, the mass content of nitrogen element is 0.32-2.0%, the mass content of asphaltene is 1.2-10.0%, the mass content of nickel element is 13.5ppm-200ppm, and the mass content of vanadium element is 5.3ppm-200ppm; (2) Separating the mild catalytic cracking reaction product to obtain catalytic cracking gasoline, catalytic cracking diesel oil and catalytic cracking heavy oil; (3) In the presence of a selective hydrodesulfurization catalyst, carrying out hydrodesulfurization reaction on the catalytic cracking heavy oil to obtain a hydrodesulfurization reaction product; (4) The hydrogenation and desulfurization reaction products are separated to obtain hydrogenated heavy oil and hydrogenated gasoline, the separation conditions are controlled to ensure that the cutting point of the hydrogenated gasoline and the hydrogenated heavy oil is 160-210 ℃, and the separation conditions are controlled to ensure that the final distillation point of the hydrogenated heavy oil is 240-380 ℃; (5) The hydrogenated heavy oil and an oil component are mixed to obtain the low-sulfur heavy marine fuel oil, wherein the density of the oil component at 20 ℃ is 0.93-0.97g/cm 3 , the mass content of sulfur element is 0.5-0.59%, the oil component is at least two of vacuum residue, hydrogenated diesel oil, catalytic diesel oil and de-solidified slurry oil, the density of the hydrogenated heavy oil at 20 ℃ is 0.955-0.97g/cm 3 , the kinematic viscosity of the hydrogenated heavy oil at 50 ℃ is 6-9mm 2 /s, the mass content of sulfur element in the hydrogenated heavy oil is 0.02-0.07%, and the total mass content of silicon element and aluminum element is 25-50ppm.
  2. 2. The production process according to claim 1, wherein in the step (5), the mass ratio of the hydrogenated heavy oil to the oil component is 1 (1-1000); and/or the mixing conditions are at least satisfied that the temperature is 20-100 ℃, the time is 20-40min, and the rotating speed is 50-500rpm.
  3. 3. The production method according to claim 2, wherein the mass ratio of the hydrogenated heavy oil to the oil component is 1 (1-200).
  4. 4. The production method according to claim 2, wherein the mass ratio of the hydrogenated heavy oil to the oil component is 1 (1.5 to 20).
  5. 5. The process according to claim 1, wherein the conditions for moderating the catalytic cracking reaction in the step (1) are at least satisfied that the volume space velocity is 25h -1 -100h -1 and the reaction temperature is 450 ℃ to 600 ℃; and/or the catalytic cracking catalyst is at least one of zeolite, inorganic oxide and clay; And/or the catalytic cracking catalyst is a waste equilibrium catalyst with a cracking activity not lower than 45.
  6. 6. The production process according to any one of claims 1 to 3, wherein in step (2), the conditions of the separation are controlled so that the cut point of the catalytically cracked diesel oil and the catalytically cracked heavy oil is 260 to 380 ℃.
  7. 7. The process according to any one of claims 1 to 3, wherein the hydrodesulfurization reaction conditions in step (3) are at least satisfied by a reaction temperature of 330 ℃ to 430 ℃, a reaction pressure of 0.5MPa to 8.0MPa, a volume space velocity of 0.1h -1 -5.0h -1 , and a hydrogen-oil volume ratio of 200 to 2000:1.
  8. 8. The production process according to any one of claims 1 to 3, wherein in the step (3), the selective hydrodesulfurization catalyst comprises a support and an active metal component supported on the support, wherein the active metal component is a combination of at least one of group VIB metal elements and at least one of group VIII metal elements, and the support is at least one selected from alumina, silica and amorphous silica alumina.
  9. 9. The production method according to claim 8, wherein in the selective hydrodesulfurization catalyst, the active metal element is molybdenum element and cobalt element, and the carrier is alumina.
  10. 10. The production process according to any one of claims 1 to 3, wherein in step (3), the desulfurization selectivity of the selective hydrodesulfurization catalyst is higher than 90%, and the desulfurization selectivity= (sulfur content in inferior residuum I-sulfur content in hydrodesulfurization reaction product) × (hydrogen content in hydrodesulfurization reaction product-hydrogen content in inferior residuum I)/sulfur content in inferior residuum I) × 100%.
  11. 11. The process of claim 10, wherein the selective hydrodesulfurization catalyst has a desulfurization selectivity of greater than 95%.
  12. 12. The production process according to any one of claims 1 to 3, wherein in step (3), the process further comprises subjecting the catalytically cracked heavy oil to a filtration treatment to obtain a pretreated catalytically cracked heavy oil having a solid content of less than 100ppm before the hydrodesulfurization reaction is carried out, and then subjecting the pretreated catalytically cracked heavy oil to the hydrodesulfurization reaction.
  13. 13. The method of claim 12, wherein the filtering is performed using a flexible deaggregation technique.
  14. 14. A low sulfur heavy marine fuel oil produced by the production process of any one of claims 1 to 13.

Description

Low-sulfur heavy marine fuel oil and preparation method thereof Technical Field The invention relates to the technical field of marine fuel oil, in particular to low-sulfur heavy marine fuel oil and a preparation method thereof. Background With the increasing global environmental problems, the related environmental regulations tend to be strict. The international maritime organization (International Maritime Organization, hereinafter referred to as IMO) requires that the upper limit of sulfur content in marine fuel oil (hereinafter referred to as marine fuel) is reduced to 0.5g/kg from 3/1/2020. In the face of the trend of low sulphur of marine fuel oils, low sulphur heavy marine fuel oils will be the main solution. However, in combination with the existing capacity, low-sulfur heavy marine fuel oils still have a large gap. The existing blending components are difficult to directly produce the residue type marine fuel oil with the sulfur content lower than 0.5 percent, and the low-sulfur residue oil must be used for blending production. However, if a large amount of high-price low-sulfur straight-run residual oil is adopted for blending to produce the heavy marine fuel oil, the production cost of the heavy marine fuel oil can be greatly increased. In order to produce low-sulfur marine combustion, most of oil refining enterprises remove sulfur in residual oil through residual oil hydrogenation at present so as to obtain a blending component of the low-sulfur marine combustion. However, the residual oil hydrogenation device belongs to a high-pressure hydrogenation device, so that the investment is large, the operation cost is high, and the low-sulfur ship combustion production cost is high. After the high-sulfur residual oil is hydrotreated, the hydrogenated slag can be used for producing low-sulfur ship combustion or a blending component of the low-sulfur ship combustion. For example, CN112300833a discloses a method for producing low sulfur residue type marine combustion, which is to sequentially charge a hydrogenation protecting catalyst, a hydrodemetallization catalyst and a hydrodemetallization desulfurizing protecting agent in a stream direction in a residuum hydrotreater. The method has good hydrogenation activity and better reaction stability, and can produce high-quality low-sulfur ship combustion for a long period. The catalytic slurry oil is rich in polycyclic aromatic hydrocarbon, has high carbon content and low hydrogen content, and can be used as a blending component of low-sulfur ship combustion after being subjected to solid removal and desulfurization pretreatment. For example, CN111088068A discloses a production method of low-sulfur marine fuel oil, which comprises the steps of mixing catalytic slurry oil with a first auxiliary agent, carrying out sedimentation separation after mixing treatment, obtaining a first material and residues after separation, enabling the first material to enter a hydrotreating unit, carrying out hydrogenation reaction under the action of a hydrotreating catalyst and hydrogen, enabling liquid phase effluent obtained by reaction to enter a clarification unit, further carrying out solid-liquid separation on clarified oil obtained after separation to obtain purified slurry oil, and mixing the purified slurry oil with high-sulfur raw material hydrogenated tail oil to obtain the low-sulfur marine fuel oil. As another example, CN101531923a discloses a combined catalytic cracking and hydrogenation process for poor quality feedstock. The poor raw oil is hydrotreated, and the obtained hydrogenated residual oil is catalytically cracked to obtain propylene, gasoline, catalytically cracked heavy oil and other products. The catalytic cracking heavy oil enters a hydrotreatment device, and the hydrogenated catalytic cracking heavy oil is circulated to the catalytic cracking device for further reaction to obtain target products of propylene and gasoline. The method adopts mild catalytic cracking technology, can reduce the yield of coke and dry gas in the catalytic cracking process, and can generate partial unconverted catalytic cracking heavy oil. The catalytic cracking heavy oil is also rich in polycyclic aromatic hydrocarbon, but has lower viscosity and lower sulfur content compared with catalytic slurry oil, is easier to carry out solid removal treatment, and can be used as a blending component of low-sulfur marine combustion without desulfurization operation. In the prior art, residual oil desulfurization is mostly realized through a residual oil hydrogenation device so as to obtain main blending components of low-sulfur heavy ship combustion. However, the residual oil hydrogenation device has high pressure, large investment and high operation cost, can cause the increase of the production cost of low-sulfur heavy ship combustion, and the residual oil hydrogenation device is mostly matched with a downstream catalytic cracking device at present, so that the processing capacity o