CN109722293B - Method for producing aviation kerosene and low-freezing diesel oil - Google Patents
Method for producing aviation kerosene and low-freezing diesel oil Download PDFInfo
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Abstract
The invention relates to the field of heavy raw material processing, and discloses a method for producing aviation kerosene and low-freezing diesel oil at the same time, which comprises the following steps: introducing the raw oil into a hydrofining reaction zone for hydrofining, and separating and fractionating hydrofined material flow to obtain a light kerosene fraction a1 and a diesel fraction b 1; the diesel fraction b1 passes through a hydrodewaxing reaction zone and a post-hydrogenation refining reaction zone in turn, and the obtained material flow is separated and fractionated to obtain a heavy kerosene fraction a2 and a diesel fraction b 2; mixing at least part of said light kerosene fraction a1 and at least part of said heavy kerosene fraction a2 to obtain a aviation kerosene product, and recycling part of said diesel fraction b2 as a low pour point diesel fraction, the remaining diesel fraction b2 back to said hydrodewaxing reaction zone. The method can convert heavy raw materials into high-dry-point aviation kerosene, realizes the production increase of aviation kerosene and simultaneously gives consideration to the production of low-freezing diesel oil, and the production scheme has obviously higher flexibility than the prior art.
Description
Technical Field
The invention relates to the field of heavy raw material processing, in particular to a method for producing aviation kerosene and low-freezing diesel oil at the same time.
Background
Along with the improvement of energy conservation and emission reduction and environmental protection requirements in China, the upgrading pace of the diesel oil quality is accelerated. Meanwhile, the economic speed increase of China is slowed, the apparent consumption of diesel oil in China is reduced year by year, and the trend of surplus of diesel oil is obvious. Oil refining enterprises face the contradiction of increasing the cost for producing high-quality diesel oil products and causing the price to continuously slide down due to the surplus diesel oil resources, and the enterprise operating environment is obviously worsened.
Therefore, it is imperative to improve the enterprise benefits by optimizing the product structure.
With the development of economy, the amount of oil used in winter in alpine regions will increase, which will result in an increase in the proportion of low freezing point diesel in the total consumption of diesel. In addition, in general, the price of the-35 # diesel oil in the northern market in winter is 300-500 yuan/ton higher than that of the 0# diesel oil. Therefore, compared with 0# diesel, the low freezing point diesel is more beneficial to enterprises.
On the other hand, the demand of low freezing point diesel oil is seasonal, the temperature is lower in the northeast, northwest and northwest areas of China in winter, the low freezing point diesel oil needs to be used in about 4-6 months each year, and common diesel oil is used in other times, so that a way for excess diesel oil production is still needed.
Aviation kerosene is one of high value-added products in the oil refining industry. In recent years, with the rapid development of aviation technology and aviation transportation industry, the demand of aviation kerosene in China also tends to rise year by year. However, compared with the consumption, the aviation kerosene production rate of some areas is obviously insufficient, taking north China as an example, the aviation kerosene consumption accounts for 26% of the national aviation kerosene consumption, and the aviation kerosene production rate only accounts for 5% of the national aviation kerosene consumption. With the establishment of new airports in Beijing, the unbalanced supply and demand of aviation kerosene in Beijing city and surrounding areas will become more and more prominent. Therefore, oil refining enterprises around North China have the willingness of increasing the yield of aviation kerosene, improving the product structure and improving the economic benefits of the enterprises.
Although the dry point of the aviation kerosene specified in the 3# jet fuel quality standard is not higher than 300 ℃, the dry point of the aviation kerosene produced by most of domestic enterprises is not higher than 250 ℃, and the space for increasing the yield of the aviation kerosene by a method for improving the dry point is large. From the distillation range, the aviation kerosene and the light fraction of the diesel oil have a large degree of overlap, and the aviation kerosene fraction can be directly cut from the diesel oil or the yield of the aviation kerosene fraction can be improved by adjusting the constant second-line cutting point of the distillation tower. However, raising the cut point of the aviation kerosene fraction can cause problems with unacceptable freezing and smoke points. Therefore, the problem of reducing the freezing point of the high dry point aviation kerosene needs to be researched, and a flexible scheme which can realize the production increase of aviation kerosene and simultaneously realize the production of low-freezing diesel oil is sought.
From the production process, the technology for reducing the condensation point of the diesel oil is mature at present, and an isomeric pour point depressing process and a hydrodewaxing process are mainly adopted. The isomerization pour point depressing process usually adopts two-stage flow of noble metal catalyst, the catalyst is easy to be poisoned and deactivated, the requirement on feeding is strict, the investment of the device and the operation cost are high, and the operation flexibility is poor. The hydrodewaxing technology adopts a molecular sieve with a shape selective cracking function and loads a small amount of metal as a catalyst, and can crack long-chain normal paraffins and other high condensation point components in diesel oil fractions into micromolecular low condensation point liquid or gas, so that the condensation point of the diesel oil is reduced, the process is simpler, and the equipment investment cost is low.
CN1743431A discloses a pour point depressing method for improving the yield and quality of diesel oil products, which divides raw oil into two components of a light diesel oil fraction section and a heavy diesel oil fraction section, and then carries out pour point depressing and refining treatment respectively in a targeted manner, thereby reducing the loss of the yield of the diesel oil in the pour point depressing process to the utmost extent.
CN102051232A discloses a diesel hydrodewaxing method adopting a metal auxiliary agent and a silicon modified catalyst, which has the characteristics of high liquid yield, high low-freezing-point diesel selectivity and good pour point depressing effect.
CN103805266A discloses a method for producing low freezing point diesel oil by a grading technology, which carries out grading on a mixed catalyst which is compositely filled with hydro-upgrading heterogeneous pour point depressing and a hydro-upgrading heterogeneous pour point depressing catalyst, reasonably combines and utilizes the temperature drop in the hydro-upgrading pour point depressing process and the temperature rise in the hydro-upgrading process, improves the yield of the diesel oil while producing low freezing point low sulfur diesel oil, reduces the hot point temperature of a device, and prolongs the running period.
The method comprises the main directions of diesel pour point depression research, namely process research, catalyst modification and catalyst grading technologies, but all aims to produce diesel oil without producing aviation kerosene from the viewpoints of improving the quality and yield of the diesel oil, reducing the reaction severity and reducing the operation cost.
The process for producing aviation kerosene mainly comprises a straight-run-hydrofining process, a deep hydrotreating process and a hydrocracking process. The straight-run hydrofining process is mainly used for reducing acid value and improving indexes of oil such as smell, color, thermal oxidation stability and the like, but does not change the freezing point and smoke point of the oil. The deep hydrogenation treatment process takes the straight-run kerosene fraction with high aromatic hydrocarbon content or the kerosene fraction obtained by secondary processing as raw material to produce qualified aviation kerosene, the deep desulfurization, denitrification and olefin saturation reaction occur in the process, the aromatic hydrocarbon is obviously reduced, the combustion performance index of the oil product is obviously improved, but the freezing point of the oil product is not changed. The hydrocracking process produces the aviation kerosene by taking vacuum distillate oil as a raw material through high-pressure hydrocracking, has little restriction on the raw material, and the produced aviation kerosene has the characteristics of low olefin content and good stability, but has the problems of high investment and operation cost and lower aviation kerosene yield.
In the prior art, the research on the freezing point depression of aviation kerosene with high dry point cut from diesel oil fraction is rarely reported.
CN102170968A discloses a method for carrying out hydrotreating and isodewaxing on kerosene raw materials by adopting a 10-membered ring one-dimensional molecular sieve catalyst, which is used for producing aviation kerosene with high flash point and low condensation point.
CN103059930A discloses a method for preparing jet fuel, which comprises the steps of mixing heavy fraction with boiling point of above 260 ℃ and C8～C24The jet fuel is obtained by taking a mixture of normal alkanes as a raw material through a method of hydroisomerization, hydrofining and fractionation. The method for preparing the aviation kerosene by adopting the isodewaxing method of the noble metal catalyst has strict requirements on the contents of sulfur and nitrogen in the feed; the hydrotreating and isodewaxing catalysts need to be respectively filled in two reactors, and a stripping tower needs to be arranged between the reactors, so that the equipment investment is large, and the operation is complex. And the heavy fraction and the normal alkane are mixed intoAlthough the material can meet the feeding requirement of an isomerization section and a hydrotreating section is not required to be arranged, the yield of the aviation kerosene obtained by the method is low.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a production scheme which can convert heavy raw materials into high-dry-point aviation kerosene, realizes aviation kerosene yield increase and has high flexibility in low-freezing diesel oil production.
In order to achieve the above object, the present invention provides a method for producing both aviation kerosene and low-freezing diesel oil, comprising:
(1) in the presence of hydrogen, raw oil is introduced into a hydrofining reaction zone for hydrofining, and the obtained hydrofined material flow is separated and fractionated to obtain a light kerosene fraction a1 and a diesel oil fraction b 1;
(2) the diesel fraction b1 passes through a hydrodewaxing reaction zone and a post-hydrogenation refining reaction zone in turn, and the obtained material flow is separated and fractionated to obtain a heavy kerosene fraction a2 and a diesel fraction b 2;
(3) mixing at least part of said light kerosene fraction a1 and at least part of said heavy kerosene fraction a2 to obtain a aviation kerosene product, and recycling part of said diesel fraction b2 as a low pour point diesel fraction, the remaining part of said diesel fraction b2 back to said hydrodewaxing reaction zone.
The method can convert heavy raw materials into high-dry-point aviation kerosene, realizes the production increase of aviation kerosene and simultaneously gives consideration to the production of low-freezing diesel oil, and the production scheme has obviously higher flexibility than the prior art.
Drawings
FIG. 1 is a process flow diagram of a preferred embodiment of the present invention for a combined aviation kerosene and low pour point diesel production process.
Description of the reference numerals
1. Raw oil 2, hydrofining reaction zone
3. First fractionation system 4, light kerosene fraction a1
5. Diesel oil fraction b 16, hydrodewaxing reaction zone
7. Refining reaction zone 8 after hydrogenation and second fractionation system
9. Heavy kerosene fraction a 210 and diesel fraction b2
11. Aviation kerosene product 12, low freezing point diesel oil fraction
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 mentioned above, the invention provides a method for producing aviation kerosene and low-freezing diesel oil at the same time, which comprises the following steps:
(1) in the presence of hydrogen, raw oil is introduced into a hydrofining reaction zone for hydrofining, and the obtained hydrofined material flow is separated and fractionated to obtain a light kerosene fraction a1 and a diesel oil fraction b 1;
(2) the diesel fraction b1 passes through a hydrodewaxing reaction zone and a post-hydrogenation refining reaction zone in turn, and the obtained material flow is separated and fractionated to obtain a heavy kerosene fraction a2 and a diesel fraction b 2;
(3) mixing at least part of said light kerosene fraction a1 and at least part of said heavy kerosene fraction a2 to obtain a aviation kerosene product, and recycling part of said diesel fraction b2 as a low pour point diesel fraction, the remaining part of said diesel fraction b2 back to said hydrodewaxing reaction zone.
Preferably, in step (3), the diesel fraction b2 recycled to the hydrodewaxing reaction zone represents 5 to 95 wt% of the total diesel fraction b2 obtained in step (3), and particularly preferably, the diesel fraction b2 recycled to the hydrodewaxing reaction zone represents 20 to 90 wt% of the total diesel fraction b2 obtained in step (3).
According to a preferred embodiment, in step (3), the heavy kerosene fraction a2 mixed with said light kerosene fraction a1 to obtain a aviation kerosene product accounts for 0.5 to 100% by volume of the total heavy kerosene fraction a2 obtained in step (2).
Preferably, the raw oil is a straight-run diesel fraction and/or a secondary processing diesel fraction.
Preferably, the distillation range of the raw oil is 130-400 ℃, and the condensation point is not lower than-10 ℃.
Preferably, the raw oil is at least one selected from straight-run diesel oil, straight-run light wax oil, catalytic diesel oil, coker diesel oil and hydrotreated diesel oil.
Preferably, the conditions under which the hydrofinishing stream is subjected to separation and fractionation are controlled so that the dry point of the light kerosene fraction a1 is no more than 260 ℃. Preferably, indexes such as the freezing point and the smoke point of the light kerosene fraction a1 of the invention meet the quality requirement of No. 3 jet fuel.
Preferably, the conditions for separating and fractionating the material flow obtained after the post-hydrogenation refining reaction zone are controlled so that the dry point of the heavy kerosene fraction a2 is no more than 300 ℃. Preferably, indexes such as the freezing point and the smoke point of the heavy kerosene fraction a2 of the invention meet the quality requirement of No. 3 jet fuel.
The diesel fraction b1 is a heavy fraction obtained by cutting a small amount of naphtha and light kerosene fraction a1 from a hydrofined stream.
According to a preferred embodiment, in step (1), the conditions of the hydrofinishing reaction zone include: the hydrogen partial pressure is 1-20 MPa, the reaction temperature is 240-400 ℃, and the volume space velocity is 0.3-10 h-1The volume ratio of hydrogen to oil is (100-3000): 1; more preferably, the conditions of the hydrofinishing reaction zone include: the hydrogen partial pressure is 4-18 MPa, the reaction temperature is 260-360 ℃, and the volume space velocity is 0.5-8 h-1The volume ratio of hydrogen to oil is (300-1000): 1.
according to another preferred embodiment, in step (2), the reaction conditions of the hydrodewaxing reaction zone include: the hydrogen partial pressure is 1-20 MPa, the reaction temperature is 260-400 ℃, and the volume space velocity is 0.3-10 h-1The volume ratio of hydrogen to oil is (100-3000): 1; more preferably, the reaction conditions of the hydrodewaxing reaction zone include: the hydrogen partial pressure is 4-18 MPa, the reaction temperature is 260-380 ℃,the volume airspeed is 0.5-8 h-1The volume ratio of hydrogen to oil is (300-1000): 1.
preferably, the hydrodewaxing reaction zone is charged with a hydrodewaxing catalyst.
The hydrodewaxing catalyst can crack long-chain normal paraffins and other high condensation point components in diesel oil fractions into micromolecular low-condensation-point liquid or gas, thereby playing a role in lowering the condensation point of diesel oil and the freezing point of aviation kerosene. The hydrodewaxing catalyst of the invention can be selected from one or more of any catalyst capable of realizing the function in the prior art. They may be commercially available or prepared by any conventional method. For example, CN102051232A discloses a hydrodewaxing catalyst modified by metal promoter and silicone oil, which has higher catalytic activity and target product selectivity. CN103805266A discloses a diesel hydro-pour point depressing catalyst and a preparation method thereof. CN1952074A discloses a hydrodewaxing catalyst containing a carrier of a modified molecular sieve and a preparation method thereof. These catalysts disclosed in the above prior art are all useful in the present invention as hydrodewaxing catalysts. The more detailed preparation method of the catalyst is described in the above publications, and the contents of the present invention are incorporated herein by reference.
In order to increase the yield of the aviation kerosene of the present invention, it is preferable that the hydrodewaxing catalyst of the present invention has the following characteristics:
preferably, the hydrodewaxing catalyst contains a molecular sieve, a matrix and a hydrogenation active metal component, wherein the matrix is a heat-resistant inorganic oxide, and the hydrogenation active metal component is at least one of VIB group metal elements and VIII group metal elements.
Preferably, in the hydrodewaxing catalyst, in the matrix, the refractory inorganic oxide is at least one selected from the group consisting of alumina, silica, titania, magnesia, silica-alumina, alumina-magnesia, silica-magnesia and clay; more preferably, the heat-resistant inorganic oxide is alumina.
Preferably, the content of the heat-resistant inorganic oxide in the matrix of the hydrodewaxing catalyst is 0.5-85 wt%, more preferably 5-75 wt%.
Preferably, in the hydrodewaxing catalyst, the molecular sieve is selected from at least one of ZSM-3, ZSM-5, ZSM-11, ZSM-12, ZSM-20, ZSM-35, ZSM-48, ZSM-57, SAPO-5, SAPO-11, SAPO-37, MCM-68, beta, USY and mordenite.
Preferably, in the hydrodewaxing catalyst, the content of the molecular sieve is 10-90 wt%, more preferably 20-80 wt%, based on the total weight of the hydrodewaxing catalyst.
Preferably, in the hydrodewaxing catalyst, the hydrogenation-active metal component is at least one selected from Fe, Co, Ni, Mo and W.
Preferably, in the hydrodewaxing catalyst, the content of the hydrogenation active metal component in terms of oxide is 0.1-20 wt%, more preferably 0.2-10 wt%, based on the total weight of the hydrodewaxing catalyst.
According to a preferred embodiment, in step (2), the reaction conditions of the hydrofinishing reaction zone include: the hydrogen partial pressure is 1-20 MPa, the reaction temperature is 200-380 ℃, and the volume space velocity is 0.3-10 h-1The volume ratio of hydrogen to oil is (100-3000): 1; more preferably, the reaction conditions of the hydrofinishing reaction zone include: the hydrogen partial pressure is 4-18 MPa, the reaction temperature is 240-360 ℃, and the volume space velocity is 0.5-8 h-1The volume ratio of hydrogen to oil is (100-3000): 1.
preferably, in the step (2), the hydrofining reaction zone is filled with a hydrofining catalyst II, and the hydrofining catalyst II is used for removing the olefin of the hydrodewaxing produced oil and decoloring the produced oil. The hydrogenation saturation of olefins in oils and the hydrogenation discoloration are well known to those skilled in the art. The hydrofining catalyst II can be selected from one or more of any catalyst capable of realizing the function in the prior art. They may be commercially available or prepared by any conventional method. For example, CN1085934A discloses a hydrorefining catalyst composed of magnesium oxide, nickel oxide, tungsten oxide and aluminum oxide. CN1872960A discloses a phosphorus-containing hydrogenation catalyst using alumina as a carrier. CN1840618A discloses a hydrogenation catalyst using silica-alumina as carrier and its preparation method. The catalysts disclosed in the above prior art can be used in the present invention as the hydrorefining catalyst II. The more detailed preparation method of the catalyst is described in the above publications, and the contents of the present invention are incorporated herein by reference.
Preferably, in the step (1), a hydrofining catalyst I is filled in the hydrofining reaction zone, and the hydrofining catalyst I is used for removing sulfur and nitrogen compounds in the raw oil and can also saturate part of aromatic hydrocarbons, so that on one hand, the hydrofining catalyst I is used for reducing the acid value and improving the indexes of the oil product such as smell, color, thermal oxidation stability and the like, and the light kerosene fraction obtained by fractionation can meet the quality standard of # 3 jet fuel; on the other hand, the reaction severity of the subsequent hydrodewaxing catalyst is obviously reduced, and the method plays an important role in reducing the reaction temperature, reducing the probability of cracking reaction at high temperature, improving the product yield and prolonging the service life of the hydrodewaxing catalyst. The hydrofining catalyst can be selected from one or more of any catalyst capable of realizing the function in the prior art. They may be commercially available or prepared by any conventional method. For example, CN1362485A discloses a distillate oil hydrorefining catalyst and a preparation method thereof, wherein the catalyst has high hydrodesulfurization and hydrodenitrogenation activities at the same time, and is suitable for hydrorefining distillate oil containing more sulfur and nitrogen at the same time. CN1648214A discloses a distillate oil hydrofining catalyst with higher hydrodesulfurization activity. CN1626279A discloses a hydrorefining catalyst containing an alumina carrier and molybdenum, nickel and tungsten metal components loaded on the carrier and a preparation method thereof. These catalysts disclosed in the above prior art can be used in the present invention as the hydrorefining catalyst I. The more detailed preparation method of the catalyst is described in the above publications, and the contents of the present invention are incorporated herein by reference.
Preferably, the loading volume ratio of the hydrofining catalyst I, the hydrodewaxing catalyst and the hydrofining catalyst II is (0.1-10): 1: (0.1-10).
In the process of the present invention, the type and number of reactors in which the diesel fraction b1 passes through the hydrodewaxing reaction zone and the post-hydrotreating reaction zone in this order are not particularly limited. For example, in the method of the present invention, the hydrodewaxing reaction zone and the post-hydrogenation refining reaction zone may be placed in the same reactor in sequence, or may be placed in different reactors in sequence.
In the process of the present invention, the separation and fractionation may be carried out in a fractionation system, the fractionation process in a fractionation system being well known in the art and generally including one or more flash, atmospheric and vacuum distillation operating units as necessary to accomplish the desired separation.
The pressures in the present invention are gauge pressures unless otherwise specified.
The process flow of a preferred embodiment of the method for producing both aviation kerosene and low-freezing diesel oil according to the present invention is provided below with reference to fig. 1:
(1) in the presence of hydrogen, raw oil 1 is introduced into a hydrofining reaction zone 2 for hydrofining, and the obtained hydrofined material flow is introduced into a first fractionation system 3 for separation and fractionation to obtain a light kerosene fraction a14 and a diesel fraction b 15;
(2) the diesel fraction b15 passes through a hydrodewaxing reaction zone 6 and a post-hydrogenation refining reaction zone 7 in sequence, and the obtained material flow is introduced into a second fractionation system 8 to be separated and fractionated to obtain a heavy kerosene fraction a29 and a diesel fraction b 210;
(3) mixing at least part of said light kerosene fraction a14 and at least part of said heavy kerosene fraction a29 to obtain a aviation kerosene product 11, and recycling part of said diesel oil fraction b210 as a low freezing point diesel oil fraction 12, the remaining part of said diesel oil fraction b210 back to said hydrodewaxing reaction zone 6.
The invention provides a flexible scheme which can convert heavy raw materials into high-dry-point aviation kerosene and can realize the production increase of aviation kerosene and the production of low-freezing diesel oil. Compared with the prior art, the method for producing the aviation kerosene provided by the invention has the following obvious advantages:
1) the method can produce the aviation kerosene by using the diesel oil fraction as the raw material, and compared with the conventional method for producing the aviation kerosene, the method has the advantages that the distillation range of the adopted raw material is obviously widened, and the yield of the aviation kerosene can be effectively increased;
2) the method has flexible process design, can realize product structure optimization by preferably adjusting the cutting point of the aviation kerosene and diesel oil fraction and the circulation ratio of the heavy diesel oil fraction, can timely adjust the output ratio of the aviation kerosene and the diesel oil in compliance with market requirements, can overcome the problem of unqualified freezing point after the aviation kerosene is cut to be heavy, and can ensure that the aviation kerosene meets the quality requirement of a 3# jet fuel product.
3) The method adopts non-noble metal catalyst, the hydrodewaxing catalyst and the post-hydrogenation refining catalyst can be filled in the same reactor or different reactors, and a stripper is not required to be arranged between different reaction zones, so that the method has the characteristics of simple flow and simple and convenient operation.
4) The method can utilize the existing devices of the refinery to organize the production to the maximum extent, only needs to adjust the process, and has small equipment investment.
The present invention will be described in detail below by way of examples.
The hydrofining catalyst I, the hydrodewaxing catalyst and the hydrofining catalyst II used in the examples 1 to 3 respectively adopt RN-10, RDW-1 and RJW-3 developed by the research institute of petrochemical engineering science, and the filling volume ratio of the catalysts is 0.6: 1: 0.4, the heavy kerosene fraction a2 obtained in the following example was all mixed with the light kerosene fraction a1 to obtain a aviation kerosene product.
Properties of the feed oil used in the examples of the present invention are shown in Table 1.
The yields in tables 3, 5 and 6 below are defined as the percentage of the desired product produced as a function of the liquid reactant feed.
Example 1
The present example was carried out by the process flow shown in FIG. 1, the properties of the feed oil are shown in Table 1, the operating conditions are shown in Table 2, the dry point of the light kerosene fraction a1 is 240 ℃, the dry point of the heavy kerosene fraction is 260 ℃, and 30% by weight of the heavy diesel fraction b2 is recycled to the hydrodewaxing reaction zone. The product properties obtained are shown in Table 3.
Example 2
The present example was carried out by the process flow shown in FIG. 1, the properties of the feed oil are shown in Table 1, the operating conditions are shown in Table 4, the dry point of the light kerosene fraction a1 is 240 ℃, the dry point of the heavy kerosene fraction is 270 ℃, and 50% by weight of the heavy diesel fraction b2 is recycled to the hydrodewaxing reaction zone. The product properties obtained are shown in Table 5.
Example 3
The present example was carried out by the process flow shown in FIG. 1, the properties of the feed oil are shown in Table 1, the operating conditions are shown in Table 4, the dry point of the light kerosene fraction a1 is 250 ℃, the dry point of the heavy kerosene fraction is 300 ℃ and 90% by weight of the heavy diesel fraction b2 is recycled to the hydrodewaxing reaction zone. The product properties obtained are shown in Table 6.
Example 4
This example was carried out in the same manner as in example 1, except that:
this example uses the same volume of hydrodewaxing catalyst N1 as in example 1, instead of RDW-1, and is otherwise the same as example 1, with the hydrodewaxing catalyst N1 being derived from the catalyst obtained in example 1 of CN 102051232A.
The properties of the product obtained in this example are shown in Table 7. TABLE 1
| Raw oil | |
| Density at 20 ℃ in kg/m3 | 839.7 |
| Freezing point, deg.C | 0 |
| Sulfur, wt.% | 0.45 |
| Nitrogen, mg/kg | 142 |
| Mercaptane sulfur, mg/kg | 55 |
| Bromine number, gBr/100mL | 0.7 |
| Distillation range (D86), deg.C | |
| Initial boiling point | 177 |
| 10％ | 247 |
| 30％ | 275 |
| 50％ | 295 |
| 70％ | 313 |
| 90％ | 336 |
| Dried cake | 368 |
TABLE 2
| Process conditions | Hydrofining reaction zone | Hydrodewaxing reaction zone | Post-hydrogenation refining reaction zone |
| Partial pressure of hydrogen/MPa | 6.4 | 6.4 | 6.4 |
| Reaction temperature/. degree.C | 320 | 340 | 340 |
| Volume space velocity/h-1 | 3.3 | 2.0 | 5.0 |
| Hydrogen to oil ratio/(v/v) | 500:1 | 500:1 | 500:1 |
TABLE 3
| Fraction range, C | 150～260 | >260 |
| Density at 20 ℃ in kg/m3 | 826.8 | 836.5 |
| Sulfur, mg/ |
6 | 9 |
| Nitrogen, mg/ |
3 | 5 |
| Freezing point, DEG C | -52 | / |
| Smoke point, mm | 25.0 | / |
| Freezing point, deg.C | / | -45 |
| Cetane number | / | 50 |
| Yield and content of | 55 | 40 |
TABLE 4
| Process conditions | Hydrofining reaction zone | Hydrodewaxing reaction zone | Post-hydrogenation refining reaction zone |
| Partial pressure of hydrogen/ |
10 | 10 | 10 |
| Reaction temperature/. degree.C | 340 | 360 | 300 |
| Volume space velocity/h-1 | 5.0 | 3.0 | 7.5 |
| Hydrogen to oil ratio/(v/v) | 500:1 | 500:1 | 500:1 |
TABLE 5
| Fraction range, C | 150～270 | >270 |
| Density at 20 ℃ in kg/m3 | 827.9 | 838.1 |
| Sulfur, mg/ |
5 | 7 |
| Nitrogen, mg/ |
2 | 5 |
| Freezing point, DEG C | -51 | / |
| Smoke point, mm | 26.0 | / |
| Freezing point, deg.C | / | <-50 |
| Cetane number | / | 47 |
| Yield and content of | 65 | 26 |
TABLE 6
| Fraction range, C | 150～300 | >300 |
| Density at 20 ℃ in kg/m3 | 828.2 | 838.3 |
| Sulfur, mg/ |
5 | 5 |
| Nitrogen, mg/kg | <1 | 2 |
| Freezing point, DEG C | -58 | / |
| Smoke point, mm | 25.0 | / |
| Freezing point, deg.C | / | -40 |
| Cetane number | / | 49 |
| Yield and content of | 78 | 11 |
TABLE 7
| Fraction range, C | 150～260 | >260 |
| Density at 20 ℃ in kg/m3 | 827.3 | 836.9 |
| Sulfur, mg/ |
6 | 9 |
| Nitrogen, mg/ |
3 | 5 |
| Freezing point, DEG C | -52 | / |
| Smoke point, mm | 25.0 | / |
| Freezing point, deg.C | / | -45 |
| Cetane number | / | 50 |
| Yield and content of | 50 | 38 |
The results in tables 3 and 5-7 show that the distillation range of the raw materials adopted by the method is obviously widened, compared with the existing aviation kerosene products, the dry point of the obtained aviation kerosene is greatly improved, the problem that the freezing point is unqualified after the aviation kerosene is cut heavily can be overcome, the freezing point of the aviation kerosene product can meet the requirement that the freezing point is not more than 47 ℃ in the 3# jet fuel standard under the condition that the dry point is close to 300 ℃, and the yield of the aviation kerosene is increased.
Meanwhile, the obtained diesel oil fraction can meet the standard of No. 35 or No. 50 low freezing point diesel oil. The output ratio of the aviation kerosene and the diesel oil can be adjusted in time by adjusting the cutting point of the refined product in the refining reaction zone after hydrogenation and the circulation amount of the heavy diesel oil fraction b2, so that the method has great flexibility.
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 method for producing aviation kerosene and low-freezing diesel oil at the same time comprises the following steps:
(1) in the presence of hydrogen, raw oil is introduced into a hydrofining reaction zone for hydrofining, and the obtained hydrofined material flow is separated and fractionated to obtain a light kerosene fraction a1 and a diesel oil fraction b 1;
(2) the diesel fraction b1 passes through a hydrodewaxing reaction zone and a post-hydrogenation refining reaction zone in turn, and the obtained material flow is separated and fractionated to obtain a heavy kerosene fraction a2 and a diesel fraction b 2;
(3) mixing at least part of said light kerosene fraction a1 and at least part of said heavy kerosene fraction a2 to obtain a aviation kerosene product, and recycling part of said diesel fraction b2 as a low pour point diesel fraction, the remaining part of said diesel fraction b2 back to said hydrodewaxing reaction zone.
2. The process according to claim 1, wherein in step (3) the diesel fraction b2 recycled to the hydrodewaxing reaction zone represents from 5 to 95% by weight of the total diesel fraction b2 obtained in step (3).
3. A process according to claim 2, wherein in step (3) the diesel fraction b2 recycled to the hydrodewaxing reaction zone represents from 20 to 90% by weight of the total diesel fraction b2 obtained in step (3).
4. A process according to any one of claims 1 to 3, wherein in step (3), the heavy kerosene fraction a2, which is mixed with the light kerosene fraction a1 to obtain a aviation kerosene product, is from 0.5 to 100% by volume of the total heavy kerosene fraction a2 obtained in step (2).
5. The process according to claim 1, wherein the raw oil is a straight-run diesel fraction and/or a secondary process diesel fraction.
6. The method according to claim 5, wherein the distillation range of the feedstock oil is 130 to 400 ℃ and the condensation point is not less than-10 ℃.
7. The method according to claim 5, wherein the raw oil is selected from at least one of straight-run diesel oil, straight-run light wax oil, catalytic diesel oil, coker diesel oil, and hydrotreated diesel oil.
8. The process according to any one of claims 1 to 3, wherein the conditions under which the hydrofinished stream is subjected to separation and fractionation are controlled so that the dry point of the light kerosene fraction a1 is not more than 260 ℃.
9. The process as claimed in any one of claims 1 to 3, wherein the conditions for separating and fractionating the stream obtained after the post-hydrogenation refining reaction zone are controlled so that the dry point of the heavy kerosene fraction a2 is not more than 300 ℃.
10. The process of any one of claims 1-3, wherein in step (1), the conditions of the hydrofinishing reaction zone comprise: the hydrogen partial pressure is 1-20 MPa, the reaction temperature is 240-400 ℃, and the volume space velocity is 0.3-10 h-1The volume ratio of hydrogen to oil is (100-3000): 1.
11. the process of any one of claims 1 to 3, wherein in step (2), the reaction conditions of the hydrodewaxing reaction zone comprise: the hydrogen partial pressure is 1-20 MPa, the reaction temperature is 260-400 ℃, and the volume space velocity is 0.3-10 h-1The volume ratio of hydrogen to oil is (100-3000): 1.
12. the process of any one of claims 1-3, wherein the hydrodewaxing reaction zone is packed with a hydrodewaxing catalyst comprising a molecular sieve, a matrix which is a refractory inorganic oxide, and a hydroactive metal component selected from at least one of group VIB and group VIII metal elements.
13. The process of claim 12, wherein the molecular sieve is selected from at least one of ZSM-3, ZSM-5, ZSM-11, ZSM-12, ZSM-20, ZSM-35, ZSM-48, ZSM-57, SAPO-5, SAPO-11, SAPO-37, MCM-68, beta, USY and mordenite.
14. The method of claim 12, wherein the hydrogenation active metal component is selected from at least one of Fe, Co, Ni, Mo, and W.
15. The process of any one of claims 1-3, wherein in step (2), the reaction conditions of the hydrofinishing reaction zone comprise: the hydrogen partial pressure is 1-20 MPa, the reaction temperature is 200-380 ℃, and the volume space velocity is 0.3-10 h-1The volume ratio of hydrogen to oil is (100-3000): 1.
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