CN109705909B - Method for producing bunker fuel oil from coal tar - Google Patents
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Abstract
The invention relates to the field of coal tar hydrogenation, and discloses a method for producing bunker fuel oil from coal tar, which comprises the following steps: introducing the coal tar full-fraction raw material subjected to dehydration and mechanical impurity removal into a slurry bed hydrogenation reactor for hydrogenation treatment; sequentially separating, atmospheric fractionating and vacuum fractionating the effluent of the slurry bed hydrogenation reactor obtained after the hydrotreatment to obtain normal top oil, normal linear oil, reduced linear oil and reduced bottom oil; taking a mixture formed by the normal line oil and part of the reduced bottom oil as a light fuel oil product for the ship, and taking a mixture formed by the reduced line oil and the rest of the reduced bottom oil as a heavy fuel oil product for the ship; the light fuel oil product obtained by the method provided by the invention can be directly used as low-sulfur high-lubricity light marine fuel oil without using an antiwear agent or a lubricity improver; meanwhile, the heavy fuel oil obtained by the method provided by the invention can be directly used as a low-sulfur No. 120 or No. 180 ship fuel blending component.
Description
Technical Field
The invention relates to the field of coal tar hydrogenation, in particular to a method for producing bunker fuel oil from coal tar.
Background
With the continuous and high-speed development of social economy, the demand of China on petroleum products is increasing day by day. However, petroleum is an irrenewable energy source and is facing a crisis of increasing exhaustion. In contrast, Chinese coal reserves are abundant, and therefore, the preparation of liquid fuel from coal has become a fundamental direction for coal processing and utilization.
On the other hand, with the rapid growth of the international and domestic steel industry, the coking industry shows a high growth trend, the yield of the coal tar is larger and larger, and the clean processing and the effective utilization of the coal tar are more and more important.
At present, the conventional processing method of coal tar is to cut various fractions with concentrated components through pretreatment distillation, and then treat the various fractions by methods such as acid-base washing, distillation, polymerization, crystallization and the like to extract pure products; and part of the coal tar is directly combusted as inferior fuel oil after being subjected to acid-base refining, or is directly combusted as emulsified fuel after being directly emulsified.
Impurities such as sulfur, nitrogen and the like in coal tar are changed into oxides of sulfur and nitrogen in the combustion process and released into the atmosphere to cause atmospheric pollution, and a large amount of sewage is generated in the acid-base refining process to seriously pollute the environment. Therefore, from the viewpoint of environmental protection and comprehensive utilization, an effective chemical processing way is expected to be found to improve the quality of the coal tar so as to expand the utilization value of the coal tar. How to reasonably utilize coal tar resources and improve the economic benefits of enterprises becomes more and more important.
CN1903994A discloses a method for producing fuel oil by coal tar hydrogenation modification, which is to mix the whole fraction coal tar from which moisture and ash are removed with diluent oil in proportion, pass through a shallow hydrogenation unit containing a hydrogenation protective agent and a pre-hydrogenation catalyst and a deep hydrogenation unit containing a main hydrogenation catalyst, and separate and fractionate the product to obtain low-sulfur fuel oil. The method reduces the treatment capacity of the device and is easy to cause the precipitation of asphaltene in the coal tar to generate sediment because the coal tar raw material needs to be diluted by adding diluent oil, and the method is limited by the diluent oil in the practical application process.
CN103695031A discloses a method for producing a diesel oil and a bunker fuel oil blending component from a coal tar raw material. The method specifically comprises the steps of mixing a coal tar full-fraction raw material with hydrogen, then feeding the mixture into a slurry bed reactor for a pre-hydrogenation reaction, separating a pre-hydrogenation product into a light component and a heavy component after gas-liquid separation and fractionation, wherein part of the heavy component is used as bunker fuel oil, and the rest of the heavy component and the light component are subjected to hydrogenation upgrading to produce clean diesel. However, the prior art provides a process with high hydrogen consumption and poor lubricity of the diesel component even when the slurry bed product of the prior art is subjected to fractionation to obtain the diesel component.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide the method which has simple process flow and low investment and is used for producing the bunker fuel oil with the grinding crack diameter remarkably reduced by using the coal tar.
With the stricter environmental regulations and the stricter restrictions on the sulfur content of marine fuel oil, the lubricity of hydrogenated products is problematic when low-sulfur fuels are produced by a hydrogenation method. At present, the diesel oil for vehicles is mainly used for solving the problems by adding a lubricity improver. The marine fuel is different from the vehicle fuel, the distillation range of the oil product is not limited by the marine fuel, so that the inventor obtains the normal linear oil, the reduced linear oil and the reduced bottom oil by controlling the hydrotreating depth of the coal tar whole fraction raw material, and the light fuel with improved lubricating property can be obtained by reasonably blending the obtained product oil on the premise of not using a lubricity improver, simultaneously, other performance indexes of the product are not influenced, and the production cost of an enterprise can be greatly reduced. Accordingly, the present inventors have completed the technical solution of the present invention.
In order to achieve the above object, the present invention provides a method for producing bunker fuel oil from coal tar, comprising:
(1) introducing the coal tar full-fraction raw material subjected to dehydration and mechanical impurity removal into a slurry bed hydrogenation reactor for hydrogenation treatment in the presence of a heterogeneous slurry bed hydrogenation catalyst;
(2) sequentially separating, atmospheric fractionating and vacuum fractionating the effluent of the slurry bed hydrogenation reactor obtained after the hydrotreatment to obtain normal top oil, normal linear oil, reduced linear oil and reduced bottom oil;
(3) taking a mixture formed by the normal line oil and part of the reduced bottom oil as a light fuel oil product for the ship, and taking a mixture formed by the reduced line oil and the rest of the reduced bottom oil as a heavy fuel oil product for the ship;
wherein the depth of the hydrotreatment in the step (1) is controlled so that the content of aromatic hydrocarbons above dicyclic rings in the normal line oil obtained in the step (2) is not higher than 15 wt%, and the total content of aromatic hydrocarbons and naphthenic hydrocarbons is not lower than 85 wt%; and the total content of aromatic hydrocarbon above four rings in the bottom reducing oil is not higher than 5 weight percent, and the total content of tricyclic aromatic hydrocarbon and tetracyclic aromatic hydrocarbon is not lower than 20 weight percent.
The light fuel oil product obtained by the method provided by the invention can be directly used as low-sulfur high-lubricity light marine fuel oil with the sulfur content of less than 200 mu g/g and the wear scar diameter of less than 300 mu m without using an antiwear agent or a lubricity improver; meanwhile, the heavy fuel oil obtained by the method provided by the invention can be directly used as a low-sulfur No. 120 or No. 180 ship fuel blending component.
The process of the invention also has the advantage of low hydrogen consumption.
Drawings
FIG. 1 is a schematic flow chart of a method for producing bunker fuel oil from coal tar according to a preferred embodiment of the present invention.
Description of the reference numerals
1. Slurry bed hydrogenation reactor 2, separation and filtration system
3. Atmospheric tower 4, vacuum tower
5. Coal tar whole fraction raw material 6 and hydrogen
7. Solid residue 8 and separated gas
9. Constant top oil 10, constant line oil
11. Reduced linear oil 12 and reduced bottom oil
13. Marine heavy fuel oil product 14 and marine light fuel oil product
15. Vacuum system
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.
As previously mentioned, the present invention provides a method for producing bunker fuel oil from coal tar, comprising:
(1) introducing the coal tar full-fraction raw material subjected to dehydration and mechanical impurity removal into a slurry bed hydrogenation reactor for hydrogenation treatment in the presence of a heterogeneous slurry bed hydrogenation catalyst;
(2) sequentially separating, atmospheric fractionating and vacuum fractionating the effluent of the slurry bed hydrogenation reactor obtained after the hydrotreatment to obtain normal top oil, normal linear oil, reduced linear oil and reduced bottom oil;
(3) taking a mixture formed by the normal line oil and part of the reduced bottom oil as a light fuel oil product for the ship, and taking a mixture formed by the reduced line oil and the rest of the reduced bottom oil as a heavy fuel oil product for the ship;
wherein the depth of the hydrotreatment in the step (1) is controlled so that the content of aromatic hydrocarbons above dicyclic rings in the normal line oil obtained in the step (2) is not higher than 15 wt%, and the total content of aromatic hydrocarbons and naphthenic hydrocarbons is not lower than 85 wt%; and the total content of aromatic hydrocarbon above four rings in the bottom reducing oil is not higher than 5 weight percent, and the total content of tricyclic aromatic hydrocarbon and tetracyclic aromatic hydrocarbon is not lower than 20 weight percent.
The normal pressure of the invention refers to: one standard atmosphere is 101 KPa.
The method provided by the invention can produce the low-sulfur high-lubricity marine fuel oil with the sulfur content of less than 200 mu g/g and the wear scar diameter of less than 300 mu m without using an antiwear agent or a lubricity improver, and the fuel oil is particularly suitable for ships with offshore and inland medium-high speed engines.
In the invention, the specific operation method of firstly carrying out primary pretreatment on the coal tar whole fraction raw material, settling, and carrying out centrifugal separation to remove water, mechanical impurities and the like is not particularly limited, as long as the purpose of primarily removing water and mechanical impurities in the coal tar whole fraction raw material can be achieved.
In the method, the coal tar full-fraction raw material subjected to preliminary water and mechanical impurity removal is uniformly mixed with a heterogeneous slurry bed hydrogenation catalyst, and then enters a slurry bed hydrogenation reactor together with hydrogen for hydrogenation treatment.
In the method, the coal tar whole fraction raw material is subjected to hydrogenation treatment in a slurry bed hydrogenation reactor to achieve the purposes of removing metals, mechanical impurities, sulfur, nitrogen and the like, and the generation of by-products such as dry gas, liquefied gas, coke and the like in the slurry bed hydrogenation process is reduced by controlling the proper hydrogenation depth.
In step (2) of the present invention, the effluent of the slurry bed hydrogenation reactor obtained after the hydrotreatment is separated to remove solid slag and gas therein (hereinafter referred to as separation gas). The separation may be performed, for example, in a system containing gas-liquid separation and liquid-solid separation.
In the step (2), fractionating the effluent of the slurry bed hydrogenation reactor obtained after the hydrotreating comprises sequentially carrying out atmospheric fractionation and vacuum fractionation. The atmospheric overhead and the atmospheric bottoms are obtained by atmospheric fractionation, and the distillate from the bottom of the atmospheric fractionation column is introduced into, for example, a vacuum column to be subjected to vacuum fractionation to obtain the reduced overhead and the reduced bottoms.
Preferably, the depth of the hydrotreatment in the step (1) is controlled so that the content of aromatics above the bicyclo ring in the normal line oil obtained in the step (2) is not higher than 10% by weight and the total content of aromatics and naphthenes is not lower than 90% by weight; and the total content of aromatic hydrocarbon above four rings in the bottom reducing oil is not higher than 3 weight percent, and the total content of tricyclic aromatic hydrocarbon and tetracyclic aromatic hydrocarbon is not lower than 25 weight percent. The adoption of the hydrotreating depth in the preferred case can lead to lower hydrogen consumption on the premise of obtaining a marine fuel oil product with better performance.
The method provided by the invention realizes the removal of metals, impurities, sulfur, nitrogen and the like by adopting a slurry bed hydrogenation reactor, and controls the proper hydrotreating reaction depth to ensure that the content of aromatic hydrocarbon above double rings in the normal line oil is not higher than 15 wt%, preferably not higher than 10 wt%, and the total content of aromatic hydrocarbon and naphthenic hydrocarbon is not lower than 85 wt%, preferably not lower than 90 wt%; the total content of aromatic hydrocarbon with more than four rings in the bottom reducing oil is not higher than 5 weight percent, preferably not higher than 3 weight percent, and the total content of tricyclic aromatic hydrocarbon and tetracyclic aromatic hydrocarbon is not lower than 20 weight percent, preferably not lower than 25 weight percent.
When the hydrogenation depth is controlled within the above range of the present invention, particularly within the preferable range, the miscibility and stability of the mixed oil can be improved, and the sufficient lubricity and the sufficient stability of the product can be ensured at the same time.
Preferably, the content of the bottom-reducing oil in the mixture forming the light fuel oil product for the ship is controlled so that the total content of the tricyclic aromatic hydrocarbon and the tetracyclic aromatic hydrocarbon in the light fuel oil product for the ship is 2.5-5.0 wt%. More preferably, the content of the reduced bottom oil in the mixture forming the light fuel oil product for the ship is controlled so that the total content of the tricyclic aromatic hydrocarbon and the tetracyclic aromatic hydrocarbon in the light fuel oil product for the ship is 3.0-4.5 wt%.
The heterogeneous slurry bed hydrogenation catalyst of the present invention may be a highly dispersed catalyst. According to a preferred embodiment, the heterogeneous slurry bed hydrogenation catalyst contains at least one of pulverized coal, coke powder and activated carbon as a dispersion medium, and an active component selected from at least one of group VIB non-noble metals and group VIII non-noble metals as a dispersion phase. More preferably, the active component is at least one of iron, cobalt, nickel, molybdenum and tungsten. For example, the heterogeneous slurry bed hydrogenation catalyst is a supported catalyst.
Preferably, the content of the active component calculated by element is 2-20 wt% based on the total weight of the heterogeneous slurry bed hydrogenation catalyst. More preferably, the content of the active component calculated by element is 5-18 wt% based on the total weight of the heterogeneous slurry bed hydrogenation catalyst.
Preferably, the addition amount of the heterogeneous slurry bed hydrogenation catalyst is 1.0-3.0 wt% based on the total weight of the coal tar full-fraction raw material subjected to dehydration and mechanical impurity removal, and more preferably, the addition amount of the heterogeneous slurry bed hydrogenation catalyst is 1.0-2.0 wt%.
According to a preferred embodiment, the conditions of the hydrotreatment in step (1) comprise: the reaction temperature is 360-440 ℃, the hydrogen partial pressure is 5.0-10.0 MPa, and the volume space velocity is 0.1-1.5 h-1The volume ratio of hydrogen to oil is 200-1000 Nm3/m3。
According to another more preferred embodiment, the conditions of the hydrotreatment in step (1) include: the reaction temperature is 380-420 ℃, the hydrogen partial pressure is 5.0-8.0 MPa, and the volume space velocity is 0.5-1.2 h-1The volume ratio of hydrogen to oil is 300-800.
Preferably, the fractionation point of the normal overhead oil and the normal line oil is 150-170 ℃, the fractionation point of the normal line oil and the reduced line oil is 340-360 ℃, and the fractionation point of the reduced line oil and the reduced bottom oil is 390-400 ℃. For example, the common overhead oil and the common line oil have a fractionation point of 165 ℃, the common line oil and the reduced line oil have a fractionation point of 350 ℃, and the reduced line oil and the reduced bottoms have a fractionation point of 390 ℃.
Preferably, the water content in the coal tar whole fraction raw material after dehydration and mechanical impurity removal is less than 0.05 weight percent, and the mechanical impurity content is less than 0.20 weight percent. More preferably, the coal tar whole fraction raw material after dehydration and mechanical impurity removal has a water content of less than 0.03 wt% and a mechanical impurity content of less than 0.10 wt%.
The coal tar of the invention refers to coal tar produced by coal pyrolysis or coal gas making or other processes. Therefore, the coal tar can be low-temperature coal tar generated by coal gas production, and can also be low-temperature coal tar or medium-temperature coal tar generated by coal pyrolysis processes (including low-temperature coking, medium-temperature coking and high-temperature coking processes) or a whole-fraction raw material of high-temperature coal tar. Preferably, the coal tar whole fraction raw material is at least one of low-temperature coal tar, medium-temperature coal tar and high-temperature coal tar.
The invention provides a preferred embodiment of the method for producing bunker fuel oil by coal tar in combination with figure 1, which comprises the following steps:
mixing a coal tar whole fraction raw material 5 subjected to dehydration and mechanical impurity removal with hydrogen 6, introducing the mixture into a slurry bed hydrogenation reactor 1, and contacting the mixture with a heterogeneous slurry bed hydrogenation catalyst contained in the slurry bed hydrogenation reactor to carry out hydrogenation treatment; introducing the effluent of the slurry bed hydrogenation reactor obtained after the hydrotreatment into a separation and filtration system 2 for separation to respectively obtain separated gas 8 and solid residues 7, introducing the separated liquid phase into an atmospheric tower 3 for atmospheric fractionation to respectively obtain atmospheric top oil 9 and atmospheric linear oil 10, introducing the material at the bottom of the atmospheric tower 3 into a vacuum tower 4 for vacuum fractionation to respectively obtain minus linear oil 11 and minus bottom oil 12, and introducing the gas at the top of the vacuum tower 4 into a subsequent vacuum system 15 for further treatment; taking a mixture of the normal line oil 10 and part of the reduced bottom oil 12 as a marine light fuel oil product 14, and taking a mixture of the reduced line oil 11 and the rest of the reduced bottom oil 12 as a marine heavy fuel oil product 13; wherein, the depth of the hydrogenation treatment is controlled to ensure that the content of aromatic hydrocarbon above double rings in the obtained normal line oil is not higher than 15 weight percent, and the total content of aromatic hydrocarbon and naphthenic hydrocarbon is not lower than 85 weight percent; and the total content of aromatic hydrocarbon above four rings in the bottom reducing oil is not higher than 5 weight percent, and the total content of tricyclic aromatic hydrocarbon and tetracyclic aromatic hydrocarbon is not lower than 20 weight percent.
The method provided by the invention also has the following specific advantages:
1. the method fully utilizes the characteristics of hydrocarbons in different fractions of the coal tar to realize the property complementation of different fractions, and produces the low-sulfur high-lubricity marine fuel by a simple method under the condition of not using a lubricity improver;
2. the method provided by the invention has the characteristics of strong raw material adaptability and long device running period.
The present invention will be described in detail below by way of examples. The following examples are carried out according to the flow chart shown in fig. 1 without being particularly described.
The properties of the coal tar whole cut feedstock used in the following examples are shown in table 1.
A high-dispersion heterogeneous slurry bed hydrogenation catalyst is adopted in a slurry bed hydrogenation reactor, and the high-dispersion heterogeneous slurry bed catalyst is a high-dispersion iron-based carbon-based supported catalyst and comprises the following components: the active carbon is used as a carrier, and the active components are Fe and Mo. And the weight ratio of Fe and Mo in the high-dispersion iron-based carbon-based supported catalyst is 1: 0.2, the content of the active component by element is 15% by weight based on the total weight of the highly dispersed iron-based carbon-based supported catalyst.
Table 1: properties of coal tar whole-cut feedstock
| Coal tar whole fraction raw material | |
| Density (20 ℃ C.)/(g/cm)3) | 0.9998 |
| Carbon residue/%) | 4.97 |
| Nitrogen content/(μ g/g) | 6100 |
| Sulfur content/(μ g/g) | 2200 |
| C content/weight% | 83.34 |
| H content/weight% | 9.61 |
| Asphaltene content/weight% | 13.5 |
| Distillation Range ASTM D-1160/. degree.C | |
| IBP | 172 |
| 50％ | 370 |
| 95％ | 505 |
| Metal content/(μ g/g) | |
| Fe | 46.9 |
| Ni | ＜0.1 |
| V | ＜0.1 |
| Na | 13.3 |
| Ca | 130.7 |
| Al | 8.1 |
Example 1
The coal tar full fraction in table 1 is used as a raw material, after water and mechanical impurities are preliminarily removed, the coal tar full fraction and the highly dispersed heterogeneous slurry bed hydrogenation catalyst are uniformly mixed, and then the mixture and hydrogen enter a slurry bed hydrogenation reactor for hydrogenation treatment. The heterogeneous slurry bed hydrogenation catalyst was used in an amount of 1.0 wt% based on the total weight of the coal tar feedstock, calculated as the active metal element contained therein. And (3) separating the hydrogenation product flow by a separation and fractionation system to obtain <165 ℃ common top oil, 165-350 ℃ common linear oil, 350-390 ℃ reduced linear oil and >390 ℃ bottom oil.
The reaction conditions of example 1 are shown in Table 2. The reaction hydrogen consumption and the composition of the normal line oil and the reduced bottom oil hydrocarbons are shown in table 3, 3 wt% (based on the normal line oil) of the reduced bottom oil is added into the normal line oil to obtain a high-lubricity light bunker fuel oil product, and the reduced line oil and the residual reduced bottom oil are mixed to obtain a low-sulfur heavy bunker fuel oil product. The properties of the resulting light bunker fuel oil product and heavy bunker fuel oil product are shown in Table 4.
As can be seen from Table 4, the hydrogen consumption was only 1.50% by weight with the process of the present invention, and the hydrogen consumption was low; the obtained light marine fuel oil product can be used as No. 4 light fuel oil with low sulfur and high lubricity; the produced heavy bunker fuel oil product can be used as a high-quality low-sulfur No. 120 bunker fuel oil blending component.
Table 2: operating conditions of example 1
| Partial pressure of hydrogen/MPa | 6.0 |
| Reaction temperature/. degree.C | 400 |
| Hydrogen to oil ratio/(Nm)3/m3) | 600 |
| Volume space velocity/h-1 | 1.0 |
Table 3: hydrogen consumption and product Hydrocarbon composition of example 1
Table 4: EXAMPLE 1 product Properties
Example 2
The coal tar full fraction in table 1 is used as a raw material, after water and mechanical impurities are preliminarily removed, the coal tar full fraction and the highly dispersed heterogeneous slurry bed hydrogenation catalyst are uniformly mixed, and then the mixture and hydrogen enter a slurry bed hydrogenation reactor for hydrogenation treatment. The heterogeneous slurry bed hydrogenation catalyst was used in an amount of 1.5 wt% based on the total weight of the coal tar feedstock, calculated as the active metal element contained therein. And (3) separating the hydrogenation product flow by a separation and fractionation system to obtain constant top oil at the temperature of <170 ℃, constant linear oil at the temperature of 170-355 ℃, reduced linear oil at the temperature of 355-395 ℃ and bottom oil at the temperature of >395 ℃.
The reaction conditions of example 2 are shown in Table 5. The reaction hydrogen consumption and the composition of the normal line oil and the bottom reducing oil hydrocarbons are shown in Table 6, 6 wt% (based on the normal line oil) of the bottom reducing oil is added into the normal line oil to obtain a high-lubricity light bunker fuel oil product, and the normal line oil and the residual bottom reducing oil are mixed to obtain a low-sulfur heavy bunker fuel oil product. The properties of the resulting light bunker fuel oil product and heavy bunker fuel oil product are shown in Table 7.
As can be seen from Table 7, the hydrogen consumption was only 1.21% by weight with the process of the present invention, and the hydrogen consumption was low; the obtained light marine fuel oil product can be used as No. 4 light fuel oil with low sulfur and high lubricity; the produced heavy bunker fuel oil product can be used as a high-quality low-sulfur No. 120 bunker fuel oil blending component.
Table 5: operating conditions of example 2
| Partial pressure of hydrogen/MPa | 8.0 |
| Reaction temperature/. degree.C | 390 |
| Hydrogen to oil ratio/(Nm)3/m3) | 400 |
| Volume space velocity/h-1 | 0.55 |
Table 6: hydrogen consumption and product Hydrocarbon composition of example 2
Table 7: EXAMPLE 2 product Properties
Example 3
The coal tar full fraction in table 1 is used as a raw material, after water and mechanical impurities are preliminarily removed, the coal tar full fraction and the highly dispersed heterogeneous slurry bed hydrogenation catalyst are uniformly mixed, and then the mixture and hydrogen enter a slurry bed hydrogenation reactor for hydrogenation treatment. The heterogeneous slurry bed hydrogenation catalyst was used in an amount of 0.9 wt% based on the total weight of the coal tar feedstock, calculated as the active metal element contained therein. And (3) separating the hydrogenation product flow by a separation and fractionation system to obtain constant top oil at the temperature of less than 155 ℃, constant linear oil at the temperature of 155-345 ℃, reduced linear oil at the temperature of 345-390 ℃ and bottom oil at the temperature of more than 390 ℃.
The reaction conditions of example 3 are shown in Table 8. The reaction hydrogen consumption and the composition of the normal line oil and the reduced bottom oil hydrocarbons are shown in Table 9, 8 wt% (based on the normal line oil) of the reduced bottom oil is added to the normal line oil to obtain a high-lubricity light bunker fuel oil product, and the reduced line oil and the residual reduced bottom oil are mixed to obtain a low-sulfur heavy bunker fuel oil product. The properties of the resulting light bunker fuel oil product and heavy bunker fuel oil product are shown in Table 10.
As can be seen from Table 10, the hydrogen consumption was only 1.86% by weight with the process of the present invention, and the hydrogen consumption was low; the obtained light marine fuel oil product can be used as No. 4 light fuel oil with low sulfur and high lubricity; the produced heavy bunker fuel oil product can be used as a high-quality low-sulfur No. 180 bunker fuel oil blending component.
Table 8: operating conditions of example 3
| Partial pressure of hydrogen/MPa | 5.0 |
| Reaction temperature/. degree.C | 420 |
| Hydrogen to oil ratio/(Nm)3/m3) | 800 |
| Volume space velocity/h-1 | 1.2 |
Table 9: hydrogen consumption and product Hydrocarbon composition of example 3
Table 10: EXAMPLE 3 product Properties
Comparative example 1
This comparative example was carried out using the same starting materials as in example 1.
The catalyst, the amount of catalyst used, and the operating conditions of the reaction section of this comparative example were the same as in example 2. Only the process flow differs from that in example 2, specifically: according to the comparative example, the hydrogenation product flow is separated into constant overhead oil at the temperature of <170 ℃, constant linear oil at the temperature of 170-355 ℃ and heavy oil at the temperature of >355 ℃ through a separation and fractionation system.
Meanwhile, the main properties of the normal line oil and heavy oil obtained by the present comparative example are given by table 11.
Table 11: product Properties of comparative example 1
| Constant line oil | Heavy oil | |
| Density (20 ℃ C.)/(g/cm)3) | 0.8822 | 0.9253 |
| Kinematic viscosity (40 ℃ C.)/(mm)2/s) | 3.886 | / |
| Kinematic viscosity (50 ℃ C.)/(mm)2/s) | / | 17.35 |
| Carbon residue/weight% | ＜0.1 | 0.65 |
| Ash content/weight% | ＜0.002 | 0.01 |
| Sulfur content/(μ g/g) | 143 | 433 |
| Grinding crack diameter/mum | 486 | |
| Distillation Range ASTM D-1160/. degree.C | ||
| IBP | 170 | 362 |
| 50％ | 272 | 408 |
| 95％ | 358 | 489 |
As can be seen from Table 11, the normal line oil obtained in this comparative example had a wear scar diameter of 486 μm, which is much higher than the wear scar diameters of the light fuel oil products for ships in the examples of the present invention, indicating that the present invention has a significant effect of improving the wear scar diameters of the light fuel oil products for ships.
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.
Claims (15)
1. A process for producing bunker fuel oil from coal tar, the process comprising:
(1) introducing the coal tar full-fraction raw material subjected to dehydration and mechanical impurity removal into a slurry bed hydrogenation reactor for hydrogenation treatment in the presence of a heterogeneous slurry bed hydrogenation catalyst;
(2) sequentially separating, atmospheric fractionating and vacuum fractionating the effluent of the slurry bed hydrogenation reactor obtained after the hydrotreatment to obtain normal top oil, normal linear oil, reduced linear oil and reduced bottom oil;
(3) taking a mixture formed by the normal line oil and part of the reduced bottom oil as a light fuel oil product for the ship, and taking a mixture formed by the reduced line oil and the rest of the reduced bottom oil as a heavy fuel oil product for the ship;
wherein the depth of the hydrotreatment in the step (1) is controlled so that the content of aromatic hydrocarbons above dicyclic rings in the normal line oil obtained in the step (2) is not higher than 15 wt%, and the total content of aromatic hydrocarbons and naphthenic hydrocarbons is not lower than 85 wt%; and the total content of aromatic hydrocarbon above four rings in the bottom reducing oil is not higher than 5 weight percent, and the total content of tricyclic aromatic hydrocarbon and tetracyclic aromatic hydrocarbon is not lower than 20 weight percent.
2. The process according to claim 1, wherein the depth of the hydrotreatment of step (1) is controlled so that the content of aromatics above bicyclo ring in the normal line oil obtained in step (2) is not higher than 10% by weight and the total content of aromatics and naphthenes is not lower than 90% by weight; and the total content of aromatic hydrocarbon above four rings in the bottom reducing oil is not higher than 3 weight percent, and the total content of tricyclic aromatic hydrocarbon and tetracyclic aromatic hydrocarbon is not lower than 25 weight percent.
3. The method according to claim 1 or 2, wherein the content of the reduced bottom oil in the mixture forming the marine light fuel oil product is controlled such that the total content of tricyclic aromatic hydrocarbons and tetracyclic aromatic hydrocarbons in the marine light fuel oil product is 2.5 to 5.0 wt.%.
4. The method according to claim 3, wherein the amount of reduced bottoms in the mixture forming the marine light fuel oil product is controlled such that the total tricyclic aromatic hydrocarbon and tetracyclic aromatic hydrocarbon content of the marine light fuel oil product is from 3.0 to 4.5 wt.%.
5. The method according to claim 1 or 2, wherein the heterogeneous slurry bed hydrogenation catalyst contains at least one of pulverized coal, coke powder and activated carbon as a dispersion medium and an active component selected from at least one of group VIB non-noble metals and group VIII non-noble metals as a dispersion phase.
6. The method of claim 5, wherein the active component is at least one of iron, cobalt, nickel, molybdenum, and tungsten.
7. The process according to claim 5, wherein the active component is present in an amount of 2 to 20% by weight, calculated as element, based on the total weight of the heterogeneous slurry bed hydrogenation catalyst.
8. The method according to claim 1, wherein the heterogeneous slurry bed hydrogenation catalyst is added in an amount of 1.0-3.0 wt% based on the total weight of the coal tar whole fraction raw material after dehydration and mechanical impurity removal.
9. The method according to claim 8, wherein the heterogeneous slurry bed hydrogenation catalyst is added in an amount of 1.0-2.0 wt% based on the total weight of the coal tar whole fraction raw material after dehydration and mechanical impurity removal.
10. The process of claim 1, wherein the hydrotreating conditions in step (1) comprise: the reaction temperature is 360-440 ℃, the hydrogen partial pressure is 5.0-10.0 MPa, and the volume space velocity is 0.1-1.5 h-1The volume ratio of hydrogen to oil is 200-1000.
11. The process of claim 10, wherein the hydrotreating conditions in step (1) comprise: the reaction temperature is 380-420 ℃, the hydrogen partial pressure is 5.0-8.0 MPa, and the volume space velocity is 0.5-1.2 h-1The volume ratio of hydrogen to oil is 300-800.
12. The process of claim 1, wherein the fractionation point of the constant overhead oil and the constant line oil is from 150 to 170 ℃, the fractionation point of the constant line oil and the reduced line oil is from 340 to 360 ℃, and the fractionation point of the reduced line oil and the reduced bottom oil is from 390 to 400 ℃.
13. The process of claim 1, wherein the coal tar whole cut feedstock after dehydration and mechanical impurity removal has a water content of less than 0.05 wt.% and a mechanical impurity content of less than 0.20 wt.%.
14. The process of claim 13, wherein the coal tar whole cut feedstock after dehydration and mechanical impurity removal has a water content of less than 0.03 weight percent and a mechanical impurity content of less than 0.10 weight percent.
15. The method of claim 1, wherein the coal tar whole cut feedstock is at least one of low temperature coal tar, medium temperature coal tar, and high temperature coal tar.
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| CN112980484B (en) * | 2021-03-01 | 2022-02-22 | 内蒙古晟源科技有限公司 | Method for producing special marine heavy fuel oil by using coal tar as raw material |
| CN115651703B (en) * | 2022-11-11 | 2023-09-22 | 陕西延长石油（集团）有限责任公司 | Method for preparing low-sulfur marine fuel oil base oil from coal tar |
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