CN115725324A - Diesel oil hydrocracking method - Google Patents
Diesel oil hydrocracking method Download PDFInfo
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Abstract
The invention relates to a diesel hydrocracking method, which utilizes a specific catalyst to convert poor diesel into high-octane gasoline and BTX components in a fluidized bed reactor, and the conversion yield of the high-octane gasoline and the BTX components is high.
Description
Technical Field
The disclosure relates to the technical field of petrochemical industry, in particular to a diesel hydrocracking method.
Background
Due to the ever-tightening quality standards for automotive fuel oils and the decreasing demand for automotive diesel fuel in the industry, the use of catalytic diesel fuel as one of the main sources of diesel fuel is increasingly restricted. On one hand, the quality of the catalytic diesel oil is generally poor due to the influence of a clean production process of gasoline, wherein the content of total aromatic hydrocarbon can reach 90 percent at most, and on the other hand, the content of sulfur and nitrogen in the catalytic diesel oil is high, so that the hydrotreating difficulty is caused, and the difficulty in restricting the quality upgrading of the diesel oil is caused.
The hydrocracking technology of the catalytic diesel oil can convert the catalytic diesel oil into gasoline blending components with high added values and chemical raw materials such as BTX and the like under the action of a hydrocracking catalyst, and plays an important role in relieving the problems of upgrading and surplus of poor quality catalytic diesel oil of oil refining enterprises.
However, in the existing catalytic diesel hydrocracking process, the problems of poor conversion rate and low octane number of the obtained gasoline still exist due to the influence of the hydrocracking catalyst.
Disclosure of Invention
The disclosure aims to solve the problems of poor conversion rate and low octane number of the obtained gasoline in the existing catalytic diesel hydrocracking process, and provides a diesel hydrocracking method.
To achieve the above objects, the present disclosure provides a diesel hydrocracking method, comprising:
(1) Preheating a mixture of a diesel raw material and a hydrogen source to obtain a preheated product;
(2) Feeding the preheated product into a fluidized bed reactor, and enabling the preheated product to be in contact with a hydrocracking catalyst to carry out hydrocracking reaction to obtain a cracked product;
(3) Separating the cracked product to obtain reaction oil gas and spent catalyst;
(4) Separating gasoline, liquefied gas, BTX components and unreacted diesel fraction from the reaction oil gas; carrying out regeneration treatment on the spent catalyst to obtain a regenerated catalyst, and feeding the regenerated catalyst into the fluidized bed reactor to be used as the hydrocracking catalyst;
wherein the hydrocracking catalyst comprises a carrier and an active metal component supported on the carrier; the carrier is composed of alumina, amorphous silicon-aluminum and a modified molecular sieve, and the active metal component comprises a metal element in a VIII group and/or a metal element in a VIB group; based on the total weight of the hydrocracking catalyst, the content of the alumina is 30-70 wt%, the content of the amorphous silicon-aluminum is 5-30 wt%, the content of the modified molecular sieve is 10-50 wt%, the content of the VIII group metal element is 0.5-10 wt% calculated by oxide, and the content of the VIB group metal element is 3-40 wt% calculated by oxide.
Optionally, the modified molecular sieve is obtained by modifying a molecular sieve; the molecular sieve comprises at least one of a Y molecular sieve, a USY molecular sieve, a ZSM-5 molecular sieve, a ZRP molecular sieve, a SAPO molecular sieve, an MCM-41 molecular sieve or a Beta molecular sieve; the modification treatment includes at least one of rare earth modification treatment, hydrothermal modification treatment or acid modification treatment.
Optionally, the group viii metal element is cobalt and/or nickel, and the group vib metal element is molybdenum and/or tungsten.
Optionally, the hydrocracking catalyst is in the form of microspheres, the diameter of which is 30 to 500 μm, preferably 40 to 300 μm.
Optionally, the diesel raw material is catalytic diesel and/or hydrocatalytic diesel, and the density of the diesel raw material at 20 ℃ is 0.85-0.98 g/cm 3 The dry point is 300-400 ℃, the total aromatic hydrocarbon content is 30-90 wt%, the sulfur content is 0.0001-2.5%, and the nitrogen content is 0.1-1500 mu g/g;
the hydrogen source comprises at least one of hydrogen gas, hydrogen-containing gas or a hydrogen donor; the hydrogen content in the hydrogen-containing gas is more than 60 volume percent, preferably more than 80 volume percent, and the hydrogen-containing gas is selected from at least one of dry gas produced by the hydrocracking reaction, catalytic cracking dry gas, coking dry gas or thermal cracking dry gas; the hydrogen donor is at least one of tetrahydronaphthalene, decahydronaphthalene or indane.
Optionally, the operating conditions in the fluidized bed reactor comprise:
the temperature is 350-600 ℃, preferably 350-550 ℃; the pressure is 0.5 to 10MPa, preferably 2 to 8MPa; the weight hourly space velocity is 0.5 to 10h -1 Preferably 0.5 to 5 hours -1 (ii) a The hydrogen-oil volume ratio is 300 to 6000, preferably 400 to 3000, more preferably 500 to 2500.
Optionally, a feeding distribution disc is arranged at the lower part of the fluidized bed reactor, and the preheated product flows through the feeding distribution disc and then enters the fluidized bed reactor.
Optionally, the regenerating the spent catalyst to obtain a regenerated catalyst includes:
and carrying out hydrogen stripping and nitrogen purging on the catalyst to be regenerated, then contacting with oxygen-containing gas for regeneration, and then carrying out inactive gas stripping and hydrogen replacement to obtain the regenerated catalyst.
Optionally, the regeneration conditions during the regeneration in contact with the oxygen-containing gas include: the regeneration temperature is 300-800 ℃, preferably 350-600 ℃, and the regeneration pressure is 0.01-3.0 MPa, preferably 0.1-1.0 MPa;
the oxygen-containing gas comprises at least one of oxygen, air, a mixed gas of oxygen and an inert gas or a mixed gas of air and an inert gas;
the inert gas comprises N 2 And/or CO 2 。
Optionally, before feeding the regenerated catalyst into the fluidized bed reactor, the operation of contacting the regenerated catalyst with a presulfurization medium to perform presulfurization treatment is further included;
the temperature of the pre-vulcanization treatment is 130-450 ℃, preferably 150-400 ℃, the time is 0.5-30 h, preferably 1-20 h, and the pressure is 0.5-10 MPa, preferably 2-8 MPa.
Through the technical scheme, in the diesel hydrocracking method disclosed by the invention, the poor diesel can be subjected to hydro-conversion in the fluidized bed reactor to generate the high-octane gasoline and the BTX component by using the specific catalyst, and the conversion yield of the high-octane gasoline and the BTX component is higher.
Additional features and advantages of the present disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:
FIG. 1 schematically illustrates a system configuration schematic that may be used in the diesel hydrocracking process of the present disclosure.
Description of the reference numerals
1. Pipeline 2 fluidized bed reactor
3. Line 4 line
5. Reactor receiver 6 line
7. Lock hopper 8 pipeline
9. Line 10 regenerator feeder
11. Line 12 line
13. Regenerator 14 line
15. Line 16 regenerator receiver
17. Line 18 line
19. Reactor feeder 20 line
Detailed Description
The following detailed description of specific embodiments of the present disclosure is provided in connection with the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The present disclosure provides a diesel hydrocracking process, comprising:
(1) Preheating a mixture of a diesel raw material and a hydrogen source to obtain a preheated product;
(2) Feeding the preheated product into a fluidized bed reactor, and contacting the preheated product with a hydrocracking catalyst to perform a hydrocracking reaction to obtain a cracked product;
(3) Separating the cracked product to obtain reaction oil gas and spent catalyst;
(4) Separating gasoline, liquefied gas, BTX components and unreacted diesel fraction from the reaction oil gas; carrying out regeneration treatment on the spent catalyst to obtain a regenerated catalyst, and feeding the regenerated catalyst into the fluidized bed reactor to be used as the hydrocracking catalyst;
wherein the hydrocracking catalyst comprises a carrier and an active metal component supported on the carrier; the carrier is composed of alumina, amorphous silicon-aluminum and a modified molecular sieve, and the active metal component comprises a metal element in a VIII group and/or a metal element in a VIB group; based on the total weight of the hydrocracking catalyst, the content of the alumina is 30-70 wt%, the content of the amorphous silicon-aluminum is 5-30 wt%, the content of the modified molecular sieve is 10-50 wt%, the content of the VIII group metal element is 0.5-10 wt% calculated by oxide, and the content of the VIB group metal element is 3-40 wt% calculated by oxide.
Preferably, the content of the alumina may be 30 to 50 wt%, the content of the amorphous silicon-aluminum may be 5 to 20 wt%, the content of the modified molecular sieve may be 15 to 45 wt%, the content of the group viii metal element may be 1 to 8 wt% in terms of oxide, and the content of the group vib metal element may be 5 to 30wt% in terms of oxide, based on the total weight of the hydrocracking catalyst.
In the present disclosure, specifically, the temperature of the preheated product may vary within a certain range, for example, the temperature of the preheated product may be 300 to 500 ℃, the preheated product enters the fluidized bed reactor from the bottom thereof, flows in the fluidized bed reactor from bottom to top, and contacts with the hydrocracking catalyst disposed in the fluidized bed reactor during the flow.
The top of the fluidized bed reactor can be provided with a settling section, a separation section and a reactor filter, cracked products are sequentially separated into reaction oil gas and a spent catalyst in the reactor filter after passing through the settling section and the separation section, and the reaction oil gas is led out from the top of the reactor for subsequent treatment to obtain gasoline, liquefied gas, BTX components and unreacted diesel fraction.
In the diesel hydrocracking method disclosed by the invention, the poor diesel can be subjected to hydro-conversion in the fluidized bed reactor by using the specific catalyst to generate the high-octane gasoline and the BTX component, and the conversion yield of the high-octane gasoline and the BTX component is higher.
In addition, the fluidized bed reactor is utilized to carry out hydrocracking treatment on the diesel raw material, the preheated diesel raw material and hydrogen form a uniform gas phase in the fluidized bed reactor, and a liquid phase circulating oil pump is not required to be arranged, so that the maintenance cost is low, and the fault tolerance rate is high; the gas phase diesel raw material and the hydrocracking catalyst have good contact, the heat generated by the reaction can be taken away and dispersed in time, the problem of local temperature runaway does not exist, and the pressure drop of a bed layer is small; the spent catalyst with reduced activity after reaction can be continuously discharged for regeneration and then is supplemented back to the reactor, so that the stability of the activity of the catalyst can be ensured, and the long-term and stable operation of the device can be realized; the preheated diesel raw material forms a uniform gas phase under the action of hydrogen, so that the condition of catalyst coking caused by long-time contact of the liquid diesel raw material and the catalyst can be effectively avoided, the catalyst can keep higher catalytic activity, and the efficiency of diesel raw material hydrocracking and the yield of a hydrocracking product can be improved.
According to the disclosure, the modified molecular sieve can be obtained by modifying a molecular sieve; the molecular sieve may comprise at least one of a Y molecular sieve, a USY molecular sieve, a ZSM-5 molecular sieve, a ZRP molecular sieve, a SAPO molecular sieve, an MCM-41 molecular sieve or a Beta molecular sieve; the modification treatment may include at least one of rare earth modification treatment, hydrothermal modification treatment, or acid modification treatment.
In accordance with the present disclosure, the group VIII metal element and the group VIB metal element may be selected from a range of values, for example, the group VIII metal element may be cobalt and/or nickel and the group VIB metal element may be molybdenum and/or tungsten.
According to the present disclosure, the hydrocracking catalyst may be in the form of microspheres, and the diameter of the microspheres may be 30 to 500 μm, preferably 40 to 300 μm.
In the present disclosure, in particular, the hydrocracking catalyst is prepared by the following method:
pulping alumina, amorphous silicon-aluminum and modified molecular sieve in the presence of inorganic acid, then forming by adopting a spray granulation method, and drying and roasting to prepare a carrier; and loading the metal active component on a carrier by adopting a spraying method, and then drying and roasting to obtain the hydrocracking catalyst. Wherein, the drying can be drying at 80-150 ℃ for 0.5-12 hours, and the roasting can be roasting at 450-600 ℃ for 0.5-12 hours.
According to the present disclosure, the diesel feedstock may be selected within a range, for example, the diesel feedstock may be a catalytic diesel and/or a hydrocatalytic diesel, and may have a density of 0.85 to 0.98g/cm at 20 ℃ 3 The dry point can be 300-400 ℃, the total aromatic hydrocarbon content can be 30-90 wt%, the sulfur content can be 0.0001-2.5%, and the nitrogen content can be 0.1-1500 mug/g.
Preferably, the density of the diesel fuel raw material at 20 ℃ can be 0.89-0.95 g/cm 3 The dry point can be 320-365 ℃, the total aromatic hydrocarbon content can be 50-85 wt%, the sulfur content can be 0.1-1.5%, and the nitrogen content can be 10-1000 mug/g.
According to the present disclosure, the hydrogen source may be selected within a range, for example, the hydrogen source may include at least one of hydrogen, a hydrogen-containing gas, or a hydrogen donor; the hydrogen content in the hydrogen-containing gas can be more than 60 vol%, preferably more than 80 vol%, and the hydrogen-containing gas can be at least one of dry gas produced by the hydrocracking reaction, catalytic cracking dry gas, coking dry gas or thermal cracking dry gas; the hydrogen donor may be selected from at least one of tetrahydronaphthalene, decahydronaphthalene, or indane.
According to the present disclosure, the operating conditions in the fluidized bed reactor may include: the temperature is 350-600 ℃, preferably 350-550 ℃; the pressure is 0.5 to 10MPa, preferably 2 to 8MPa; the weight hourly space velocity is 0.5 to 10h -1 Preferably 0.5 to 5 hours -1 (ii) a The hydrogen-oil volume ratio is 300 to 6000, preferably 400 to 3000, more preferably 500 to 2500.
According to the present disclosure, a feeding distribution plate may be disposed at a lower portion of the fluidized bed reactor, and the preheated product flows through the feeding distribution plate and then enters the fluidized bed reactor. The arrangement of the feeding distribution disc can ensure that the preheated product is in good contact with the hydrocracking catalyst, thereby being beneficial to the hydrocracking reaction.
According to the present disclosure, when the spent catalyst is subjected to regeneration treatment to obtain a regenerated catalyst, the spent catalyst may be subjected to hydrogen stripping and nitrogen purging, then is brought into contact with an oxygen-containing gas for regeneration, and then is subjected to inactive gas stripping and hydrogen replacement to obtain the regenerated catalyst.
In the present disclosure, in particular, hydrogen stripping may further remove residual reaction oil gas in the spent catalyst, nitrogen purging may convert the spent catalyst from a high-pressure hydrogen-hydrocarbon environment to a low-pressure nitrogen environment, inactive gas stripping may reduce or remove oxygen carried by the regenerated catalyst, and hydrogen replacement may convert the regenerated catalyst from a low-pressure nitrogen or oxygen-containing environment to a high-pressure hydrogen-hydrocarbon environment.
Wherein the hydrogen stripping can be performed in the reactor receiver or in the lock hopper; the nitrogen purge may be performed in a lock hopper; the inert gas stripping can be performed in the regenerator receiver or in the lock hopper; the hydrogen replacement may be performed in a lock hopper.
According to the present disclosure, the regeneration conditions in the regenerator may vary within a certain range, for example, the regeneration conditions may include: the regeneration temperature is 300-800 ℃, preferably 350-600 ℃, and the regeneration pressure is 0.01-3.0 MPa, preferably 0.1-1.0 MPa.
The oxygen-containing gas may include at least one of oxygen, air, a mixture of oxygen and an inert gas, or a mixture of air and an inert gas; the inert gas comprises N 2 And/or CO 2 。
According to the present disclosure, before feeding the regenerated catalyst into the fluidized bed reactor, an operation of contacting the regenerated catalyst with a presulfurization medium to perform a presulfurization treatment may be further included; the temperature of the pre-vulcanization treatment can be 130-450 ℃, preferably 150-400 ℃, the time can be 0.5-30 h, preferably 1-20 h, and the pressure can be 0.5-10 MPa, preferably 2-8 MPa.
In the present disclosure, in particular, the presulfiding medium can be H-containing 2 Reducing gas of S, wherein H 2 The volume fraction of S can be 0.01 to 30 percent, preferably 0.1 to 10 percent; the presulfiding medium can also contain available H 2 Mixtures of hydrocarbon oils of S with hydrogen, e.g. CS 2 Mixtures with hydrogen and hydrocarbon oils, mixtures of DMDS with hydrogen and hydrocarbon oils, and the like are known in the art as media that can be used for presulfiding catalysts.
FIG. 1 schematically illustrates a system configuration schematic that may be used in the diesel hydrocracking process of the present disclosure. As shown in fig. 1, the mixture of the preheated diesel raw material and hydrogen enters the fluidized bed reactor 2 through a pipeline 1, and contacts with the hydrocracking catalyst in the fluidized bed reactor 2 to perform a hydrocracking reaction. The reacted reaction oil gas is separated from the catalyst to be generated by the reactor filter at the upper part of the fluidized bed reactor 2 and then is sent to a subsequent separation stabilizing system for treatment through a pipeline 3. The spent catalyst separated from the reaction oil gas is transported to a reactor receiver 5 through a pipeline 4 and then transported to a lock hopper 7 through a pipeline 6. The spent catalyst in lock hopper 7 is hydrogen stripped and nitrogen purged, then switched from a high pressure hydrogen ambient to a low pressure nitrogen ambient, and then sent via line 9 to regenerator feed 10, with the rate of spent catalyst transfer to regenerator 13 being controlled by a slide valve on line 11. The spent catalyst is mixed with oxygen-containing gas from a pipeline 12 in a regenerator 13 and then regenerated by high-temperature sulfur burning and carbon burning to obtain a regenerated catalyst. The regenerated catalyst is transferred via line 15 to regenerator receiver 16 and then via line 17 to lock hopper 7. In lock hopper 7, the regenerated catalyst is purged with nitrogen and replaced with hydrogen, switched from a low pressure oxygen-containing environment to a high pressure hydrogen-containing environment, and then transferred via line 18 to reactor feeder 19, where the regenerated catalyst is presulfided in reactor feeder 19 and then returned to fluidized bed reactor 2 via line 20.
The present disclosure is further illustrated by the following examples, but is not to be construed as being limited thereby. Instruments, equipment, raw materials and reagents mentioned in the examples of the present disclosure may be purchased without specific reference.
The hydrocracking catalyst involved in the examples of the present disclosure may be prepared by the following method:
mixing and pulping USY zeolite (produced by Changling catalyst factory and having sodium oxide content of 0.5 wt%), perlite, pseudo-boehmite (dry basis is 70 wt%) and dilute nitric acid, then carrying out spray granulation to obtain microspheres with particle size of 50-200 microns, drying the microspheres at 120 ℃ for 4 hours, and roasting at 450 ℃ for 4 hours to obtain the carrier. And (2) adding the carrier into a precursor solution of the VIB group metal element and/or the VIII group metal element at normal temperature under the stirring condition, fully stirring, drying at 120 ℃ for 5 hours, and roasting at 400 ℃ for 3 hours in an air atmosphere to obtain the intermediate catalyst. Taking the intermediate catalyst, uniformly spraying the intermediate catalyst twice by using a precursor solution of a VIB group metal element and/or a VIII group metal element, drying the intermediate catalyst for 2 hours at 120 ℃, and roasting the intermediate catalyst for 3 hours at 450 ℃ to obtain the hydrocracking catalyst.
Example 1
This example was used to hydrocrack diesel feedstock 1.
(1) Carrying out temperature programming pre-vulcanization on the hydrocracking catalyst A by utilizing dimethyl disulfide (DMDS), wherein the pre-vulcanization conditions comprise that: 2 hours at 150 ℃,3 hours at 250 ℃,3 hours at 300 ℃, the hydrogen flow is 200L/h, the DMDS feeding flow is 3mL/h, and the pressure is 3.5MPa;
wherein, the hydrocracking catalyst A is a microspherical catalyst with the grain diameter of 50-150 mu m and consists of a carrier and an active metal component loaded on the carrier; the carrier consists of alumina, amorphous silicon-aluminum and a modified molecular sieve, and the active metal components comprise molybdenum elements and tungsten elements; based on the total weight of the hydrocracking catalyst a, the content of alumina was 32.17 wt%, the content of amorphous silicon-aluminum was 7.78 wt%, the content of modified molecular sieve was 39.04 wt%, the content of molybdenum element was 7.85 wt% in terms of oxide, and the content of tungsten element was 13.16 wt% in terms of oxide;
(2) Filling the pre-vulcanized hydrocracking catalyst A into a fluidized bed reactor, wherein the filling amount is 200g;
(3) Preheating a mixture of a diesel raw material 1 and hydrogen to obtain a preheated product with the temperature of 300-500 ℃, wherein the property of the diesel raw material 1 is shown in table 1;
(4) Feeding the preheated product into the fluidized bed reactor from the bottom of the fluidized bed reactor, and contacting the preheated product with a pre-vulcanized hydrocracking catalyst A for hydrocracking reaction to obtain a cracked product, wherein the hydrocracking conditions comprise: the temperature is 450 ℃, the pressure is 3.5MPa, and the weight hourly space velocity is 1.8h -1 The volume ratio of hydrogen to oil is 1200;
(5) The cracked product was separated in a reactor filter to obtain a reaction oil gas and a spent catalyst, and gasoline, liquefied gas, BTX components, and unreacted diesel fraction were separated from the reaction oil gas, with the results shown in table 2.
Example 2
Diesel feedstock 1 was subjected to hydrocracking using the method of example 1, except that: the hydrocracking catalyst used in this example is a hydrocracking catalyst B, which is a microspherical catalyst having a particle size of 50 to 150 μm, and is composed of a carrier and an active metal component supported on the carrier; the carrier consists of alumina, amorphous silicon-aluminum and a modified molecular sieve, and the active metal components comprise molybdenum elements and nickel elements; based on the total weight of the hydrocracking catalyst B, the content of alumina was 34.21 wt%, the content of amorphous silicon-aluminum was 17.64 wt%, the content of modified molecular sieve was 34.02 wt%, the content of molybdenum element was 8.68 wt% in terms of oxide, and the content of nickel element was 5.45 wt% in terms of oxide.
The hydrocracking results of this example are shown in table 2.
Example 3
This example is for hydrocracking a diesel feedstock 2.
(1) Carrying out temperature programming pre-vulcanization on the hydrocracking catalyst B by utilizing dimethyl disulfide (DMDS), wherein the pre-vulcanization conditions comprise that: 2 hours at 150 ℃,3 hours at 250 ℃,3 hours at 300 ℃, the hydrogen flow is 200L/h, the DMDS feeding flow is 3mL/h, and the pressure is 3.5MPa; wherein the composition of hydrocracking catalyst B was the same as in example 2;
(2) Filling the pre-vulcanized hydrocracking catalyst B into a fluidized bed reactor, wherein the filling amount is 300g;
(3) Preheating a mixture of a diesel raw material 2 and hydrogen to obtain a preheated product with the temperature of 300-500 ℃, wherein the property of the diesel raw material 2 is shown in table 1;
(4) Sending the preheated product into the fluidized bed reactor from the bottom of the fluidized bed reactor, and enabling the preheated product to be in contact with a pre-vulcanized hydrocracking catalyst B for hydrocracking reaction to obtain a cracked product, wherein the hydrocracking conditions comprise: the temperature is 520 ℃, the pressure is 3.5MPa, and the weight hourly space velocity is 1.0h -1 The volume ratio of hydrogen to oil is 1200;
(5) The cracked product was separated in a reactor filter to obtain a reaction oil gas and a spent catalyst, and gasoline, liquefied gas, BTX components, and unreacted diesel fraction were separated from the reaction oil gas, with the results shown in table 2.
Example 4
Diesel feedstock 1 was subjected to hydrocracking treatment using example 1, except that: the hydrocracking catalyst used in this example is a hydrocracking catalyst C, which is a microspherical catalyst having a particle size of 80 to 200 μm and is composed of a carrier and an active metal component supported on the carrier; the carrier is composed of alumina, amorphous silicon-aluminum and a modified molecular sieve, and the active metal components comprise molybdenum elements and cobalt elements; based on the total weight of the hydrocracking catalyst C, the content of alumina was 45.92 wt%, the content of amorphous silicon-aluminum was 15.27 wt%, the content of the modified molecular sieve was 16.80 wt%, the content of molybdenum element was 14.86 wt% in terms of oxide, and the content of cobalt element was 7.15 wt% in terms of oxide.
The hydrocracking results of this example are shown in table 2.
Example 5
Diesel feedstock 1 was subjected to hydrocracking using example 1, except that: the hydrocracking catalyst used in this example is a hydrocracking catalyst D, which is a microspherical catalyst having a particle size of 80 to 200 μm, and is composed of a carrier and an active metal component supported on the carrier; the carrier is composed of alumina, amorphous silicon-aluminum and a modified molecular sieve, and the active metal components comprise tungsten elements and nickel elements; based on the total weight of the hydrocracking catalyst D, the content of alumina was 36.48 wt%, the content of amorphous silica-alumina was 7.39 wt%, the content of the modified molecular sieve was 42.53 wt%, the content of tungsten element was 5.27 wt% in terms of oxide, and the content of nickel element was 8.36 wt% in terms of oxide.
The hydrocracking results of this example are shown in table 2.
Example 6
Diesel feedstock 1 was subjected to hydrocracking treatment using example 1, except that: the hydrocracking conditions in step (4) include: the temperature is 350 ℃, the pressure is 0.5MPa, and the weight hourly space velocity is 0.5h -1 The volume ratio of hydrogen to oil was 300.
The hydrocracking results of this example are shown in table 2.
Example 7
Diesel feedstock 1 was subjected to hydrocracking using example 1, except that: the hydrocracking conditions in step (4) include: the temperature is 600 ℃, the pressure is 10MPa, and the weight hourly space velocity is 10h -1 The hydrogen-oil volume ratio was 6000.
The hydrocracking results of this example are shown in table 2.
Example 8
Diesel feedstock 1 was subjected to hydrocracking treatment using example 1, except that: the hydrocracking conditions in step (4) include: the temperature is 350 ℃, the pressure is 2MPa, and the weight hourly space velocity is 0.5h -1 The volume ratio of hydrogen to oil was 400.
The hydrocracking results of this example are shown in table 2.
Example 9
Diesel feedstock 1 was subjected to hydrocracking treatment using example 1, except that: the hydrocracking conditions in the step (4) include: the temperature is 550 ℃, the pressure is 8MPa, and the weight hourly space velocity is 5h -1 The hydrogen-oil volume ratio was 3000.
The hydrocracking results of this example are shown in table 2.
Example 10
Diesel feedstock 1 was subjected to hydrocracking using the method of example 1, except that: the hydrocracking catalyst a in this example was directly packed into a fluidized bed reactor without presulfiding for preheating the hydrocracking reaction of the product.
The hydrocracking results of this example are shown in table 2.
Comparative example 1
The diesel feedstock 1 was subjected to hydrocracking treatment using the following method:
(1) Carrying out temperature programming pre-vulcanization on the hydrocracking catalyst E by utilizing dimethyl disulfide (DMDS), wherein the pre-vulcanization conditions comprise that: 2 hours at 150 ℃,3 hours at 250 ℃ and 3 hours at 300 ℃, and the hydrogen flow is 16L/h;
wherein, the hydrocracking catalyst E is a trefoil-shaped catalyst with the circumscribed circle diameter of 1.6mm, and consists of a carrier and an active metal component loaded on the carrier; the carrier is composed of alumina, amorphous silicon-aluminum and a modified molecular sieve, and the active metal components comprise molybdenum elements and tungsten elements; based on the total weight of the hydrocracking catalyst E, the content of alumina was 32.56 wt%, the content of amorphous silicon-aluminum was 7.61 wt%, the content of the modified molecular sieve was 39.26 wt%, the content of molybdenum element was 7.75 wt% in terms of oxide, and the content of tungsten element was 12.82 wt% in terms of oxide;
(2) Filling the pre-vulcanized hydrocracking catalyst E on a fixed bed reactor, wherein the filling amount is 16g;
(3) Preheating a mixture of a diesel raw material 1 and hydrogen to obtain a preheated product with the temperature of 300-500 ℃, wherein the property of the diesel raw material 1 is shown in table 1;
(4) Sending the preheated product into a fixed bed reactor, and enabling the preheated product to be in contact with a presulfurized hydrocracking catalyst E for hydrocracking reaction to obtain a cracked product, wherein the hydrocracking conditions comprise: the temperature is 450 ℃, the pressure is 3.5MPa, and the weight hourly space velocity is 1.8h -1 The volume ratio of hydrogen to oil is 1200;
(5) The cracked product was separated in a reactor filter to obtain a reaction oil gas and a spent catalyst, and gasoline, liquefied gas, BTX components and unreacted diesel fraction were separated from the reaction oil gas, with the results shown in table 2.
Comparative example 2
Diesel feedstock 1 was subjected to hydrocracking using the method of comparative example 1, except that: the hydrocracking catalyst used in the comparative example is a hydrocracking catalyst F, and the hydrocracking catalyst F is a trilobe-shaped catalyst with the circumscribed circle diameter of 1.6mm and consists of a carrier and an active metal component loaded on the carrier; the carrier consists of alumina, amorphous silicon-aluminum and a modified molecular sieve, and the active metal components comprise molybdenum elements and nickel elements; based on the total weight of the hydrocracking catalyst F, the content of alumina was 35.14 wt%, the content of amorphous silicon-aluminum was 16.85 wt%, the content of modified molecular sieve was 34.51 wt%, the content of molybdenum element was 8.46 wt% in terms of oxide, and the content of nickel element was 5.04 wt% in terms of oxide.
The hydrocracking results of this comparative example are shown in table 2.
TABLE 1
| Properties of | Diesel feedstock 1 | |
| Density at 20 ℃ in kg/m -3 | 966.8 | 894.3 |
| Sulfur content, wt.% | 0.748 | 0.001 |
| Nitrogen content, mg/kg | 578 | 3 |
| Total aromatic hydrocarbons in wt.% | 89.7 | 62.5 |
TABLE 2
Note: the yield is the mass percent of the product mass to the feed amount of the raw material.
As can be seen from table 2, the diesel hydrocracking method disclosed by the present disclosure can effectively improve the efficiency of generating high-octane gasoline and BTX components by diesel hydrocracking, and improve the conversion yield of the high-octane gasoline and BTX components, and particularly, after the hydrocracking catalyst is subjected to the pre-vulcanization treatment, the above effects are more significant.
The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.
Claims (10)
1. A diesel hydrocracking process, characterized in that it comprises:
(1) Preheating a mixture of a diesel raw material and a hydrogen source to obtain a preheated product;
(2) Feeding the preheated product into a fluidized bed reactor, and contacting the preheated product with a hydrocracking catalyst to perform a hydrocracking reaction to obtain a cracked product;
(3) Separating the cracked product to obtain reaction oil gas and spent catalyst;
(4) Separating gasoline, liquefied gas, BTX components and unreacted diesel fraction from the reaction oil gas; carrying out regeneration treatment on the spent catalyst to obtain a regenerated catalyst, and feeding the regenerated catalyst into the fluidized bed reactor to be used as the hydrocracking catalyst;
wherein the hydrocracking catalyst comprises a carrier and an active metal component supported on the carrier; the carrier is composed of alumina, amorphous silicon-aluminum and a modified molecular sieve, and the active metal component comprises a VIII group metal element and/or a VIB group metal element; based on the total weight of the hydrocracking catalyst, the content of the alumina is 30-70 wt%, the content of the amorphous silicon-aluminum is 5-30 wt%, the content of the modified molecular sieve is 10-50 wt%, the content of the VIII group metal element is 0.5-10 wt% calculated by oxide, and the content of the VIB group metal element is 3-40 wt% calculated by oxide.
2. The method of claim 1, wherein the modified molecular sieve is obtained by modifying a molecular sieve; the molecular sieve comprises at least one of a Y molecular sieve, a USY molecular sieve, a ZSM-5 molecular sieve, a ZRP molecular sieve, a SAPO molecular sieve, an MCM-41 molecular sieve or a Beta molecular sieve; the modification treatment includes at least one of rare earth modification treatment, hydrothermal modification treatment or acid modification treatment.
3. The method as claimed in claim 1, wherein the group VIII metal element is cobalt and/or nickel, and the group VIB metal element is molybdenum and/or tungsten.
4. The process according to claim 1, characterized in that the hydrocracking catalyst is in the form of microspheres having a diameter of 30 to 500 μm, preferably 40 to 300 μm.
5. The process according to claim 1, wherein the diesel feedstock is a catalytic diesel and/or hydrocatalytic diesel having a density of 0.85 to 0.98g/cm at 20 ℃ 3 The dry point is 300-400 ℃, the total aromatic hydrocarbon content is 30-90 wt%, the sulfur content is 0.0001-2.5%, and the nitrogen content is 0.1-1500 mu g/g;
the hydrogen source comprises at least one of hydrogen gas, hydrogen-containing gas or a hydrogen donor; the hydrogen content in the hydrogen-containing gas is more than 60 volume percent, preferably more than 80 volume percent, and the hydrogen-containing gas is selected from at least one of dry gas produced by the hydrocracking reaction, catalytic cracking dry gas, coking dry gas or thermal cracking dry gas; the hydrogen donor is at least one of tetrahydronaphthalene, decahydronaphthalene or indane.
6. The method of claim 1, wherein the operating conditions in the fluidized bed reactor comprise:
the temperature is 350-600 ℃, and preferably 350-550 ℃; the pressure is 0.5 to 10MPa, preferably 2 to 8MPa; the weight hourly space velocity is 0.5 to 10h -1 Preferably 0.5 to 5 hours -1 (ii) a The hydrogen-oil volume ratio is 300 to 6000, preferably 400 to 3000, more preferably 500 to 2500.
7. The method as claimed in claim 1, characterized in that a feed distributor tray is arranged in the lower part of the fluidized bed reactor, through which the preheated product flows before entering the fluidized bed reactor.
8. The method according to claim 1, wherein the regenerating the spent catalyst to obtain a regenerated catalyst comprises:
and carrying out hydrogen stripping and nitrogen purging on the spent catalyst, then contacting with oxygen-containing gas for regeneration, and then carrying out inactive gas stripping and hydrogen replacement to obtain the regenerated catalyst.
9. The process of claim 8, wherein the regeneration conditions during regeneration in contact with an oxygen-containing gas comprise: the regeneration temperature is 300-800 ℃, preferably 350-600 ℃, and the regeneration pressure is 0.01-3.0 MPa, preferably 0.1-1.0 MPa;
the oxygen-containing gas comprises at least one of oxygen, air, a mixed gas of oxygen and an inert gas or a mixed gas of air and an inert gas;
the inert gas comprises N 2 And/or CO 2 。
10. The method according to claim 1, characterized by further comprising an operation of contacting the regenerated catalyst with a presulfiding medium for presulfiding treatment before feeding the regenerated catalyst into the fluidized bed reactor;
the temperature of the pre-vulcanization treatment is 130-450 ℃, preferably 150-400 ℃, the time is 0.5-30 h, preferably 1-20 h, and the pressure is 0.5-10 MPa, preferably 2-8 MPa.
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| CN105618123A (en) * | 2014-11-03 | 2016-06-01 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
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| CN109705910A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | The method and system that heavy raw oil is hydrocracked |
| CN109722292A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of method for hydrogen cracking producing thick white oil |
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| CN105618123A (en) * | 2014-11-03 | 2016-06-01 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN107987878A (en) * | 2016-10-27 | 2018-05-04 | 中国石油化工股份有限公司 | A kind of method for producing high-knock rating gasoline |
| CN109705910A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | The method and system that heavy raw oil is hydrocracked |
| CN109718760A (en) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | A method of light aromatics is produced by raw material of catalytic cracking diesel oil |
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