Hydrocracking method for high-dry-point high-nitrogen raw oil
Technical Field
The invention relates to a hydrocracking method of high-dry-point high-nitrogen raw oil, in particular to a hydrocracking method of high-dry-point high-nitrogen wax oil, which is a method for producing high-quality products through hydrocracking.
Background
In the modern oil refining technology, hydrocracking refers to hydrogenation processes for converting more than 10% of macromolecular compounds in raw materials into small molecular compounds through hydrogenation reaction, and has the characteristics of strong raw material adaptability, large production scheme flexibility, good product quality and the like, so that hydrocracking becomes one of important process technologies for deep processing of heavy oil. The heart of hydrocracking technology is the catalyst, including pretreatment catalysts and cracking catalysts. The hydrocracking pretreatment catalyst has the main functions of: the raw materials are hydrogenated to remove impurities such as sulfur, nitrogen, oxygen, heavy metals and the like and hydrogenated saturated polycyclic aromatic hydrocarbon, and the property of the oil product is improved. Since the nitrides, especially the basic nitrides, in the feedstock oil can poison the acid center of the cracking catalyst, the hydrodenitrogenation performance is an important measure of the hydrocracking pretreatment catalyst.
CN201310540358.9 discloses a hydrogenation method for producing lubricating oil base oil by using inferior heavy distillate oil. Feeding the inferior heavy distillate oil and hydrogen into a first-stage reaction zone for carrying out hydrofining reaction, separating reaction effluent, and feeding the obtained liquid into a second-stage reaction zone for carrying out hydrofining reaction; the effluent of the second-stage reaction enters a third-stage reaction zone to carry out hydrocracking reaction; separating the hydrocracking effluent, mixing at least partial tail oil with new hydrogen, isodewaxing and post-refining to obtain various kinds of base oil. The method can carry out hydrotreating on the nitrogen-containing impurities in the inferior raw material under the mild condition, so that the inferior raw material meets the hydrocracking feeding requirement, and the raw material source of the lubricating oil base oil is widened; meanwhile, the hydrofining temperature is greatly reduced, so that the operation period of the device can be prolonged, and inferior raw materials can be processed or the processing capacity of the device can be improved under the same operation period. However, the method needs three hydrogenation reaction zones, the investment of equipment is high, the operation is complex, the reaction heat of the hydrogenation reaction cannot be effectively utilized, and the energy consumption is high.
CN201110326424.3 discloses a hydrotreating method of high-acid high-calcium heavy crude oil, which comprises the steps of introducing the high-acid high-calcium heavy crude oil and hydrogen into a low-pressure hydrotreating zone and a high-pressure hydrotreating zone which are connected in series, and sequentially contacting with a hydrogenation protection catalyst bed layer, a hydrodemetallization catalyst bed layer, a hydrodesulfurization catalyst bed layer and a hydrodenitrogenation catalyst bed layer, wherein the hydrogen partial pressure of the low-pressure hydrotreating zone is 1MPa-6.5MPa, and the hydrogen partial pressure of the high-pressure hydrotreating zone is 7MPa-20 MPa. The whole set of device is divided into a low-pressure hydrogenation treatment area and a high-pressure hydrogenation treatment area, so that deacidification and decalcification are effectively realized, high-acid high-calcium heavy crude oil can be processed into qualified catalytic cracking raw materials, the operation process is safe, the long-period stable operation of the device is realized, and the effective utilization of petroleum resources is realized. But the method has high equipment investment and complex operation.
CN201110320460.9 provides a fixed bed hydrotreating method for heavy oil, which comprises, under the hydrotreating reaction condition, sequentially introducing heavy oil and hydrogen into a plurality of serially connected hydrogenation reactors, and contacting with a hydrogenation protection catalyst bed layer, a hydrodemetallization catalyst bed layer, a hydrodesulfurization catalyst bed layer and a hydrodecarbonization catalyst bed layer which are sequentially arranged in the plurality of hydrogenation reactors, wherein one end of a discharge hole of each hydrogenation reactor is also provided with a macroporous hydrotreating catalyst bed layer, thereby avoiding the precipitation and coking of asphaltene and prolonging the service life of the catalyst. The method only aims at the inferior residual oil with higher asphaltene content in the raw material, and can not realize the deep hydrogenation saturation of the raw material.
CN201510046362.9 discloses a heavy oil hydrotreating catalyst grading loading method, wherein a reaction system comprises two or more hydrogenation reactors connected in series, and the activity and the possible pore diameters of the catalyst are in a descending trend in the same reactor from the second reactor according to the contact sequence with reactant flow; in the adjacent two reactors, according to the contact sequence with the reactant flow, the activity of the catalyst at the bottom of the previous reactor is lower than that of the catalyst at the top of the next reactor, and the pore diameter of the catalyst at the bottom of the previous reactor can be not more than that of the catalyst at the top of the next reactor; meanwhile, the activity of the catalyst at the bottom of the former reactor is lower than that of the catalyst at the bottom of the latter reactor, and the diameter of the catalyst at the bottom of the former reactor can be larger than that of the catalyst at the top of the latter reactor.
CN201210171553.4 discloses a hydrogenation method for producing middle distillate to the maximum extent, fresh raw oil is introduced into a hydrofining reactor and a hydrocracking reactor simultaneously in a cocurrent mode; the hydrofining reactor is sequentially filled with a hydrofining catalyst and an amorphous hydrocracking catalyst; sequentially filling an amorphous hydrocracking catalyst and a molecular sieve hydrocracking catalyst into the hydrocracking reactor; all or part of the tail oil fraction enters a hydrocracking reactor, and the reaction effluent of the hydrocracking reactor and part of the raw oil enter a hydrofining reactor together. The method provided by the invention can treat heavy distillate oil and produce middle distillate oil to the maximum extent.
CN201410108689.X discloses a hydrotreating method of a hydrocarbon oil raw material with high iron and calcium contents, which comprises the step of sequentially contacting heavy raw oil with a catalyst combination comprising a hydrotreating protection catalyst I, a hydrotreating catalyst II and a hydrotreating catalyst III under a hydrotreating reaction condition, wherein the hydrotreating protection catalyst I contains a carrier and a hydrogenation active metal component loaded on the carrier, the carrier is an alumina forming product characterized by a mercury intrusion method, the pore volume of the forming product is 0.3-0.8 ml/g, and the specific surface area is 70-220m2The volume of pores with diameter of 6-10nm accounts for 8-25% of the total pore volume, and the volume of pores with diameter of 85-160nm accounts for 40-75% of the total pore volume. Compared with the prior art, the method has better inferior raw oil hydrotreating performance.
CN200910086744.9 discloses a grading combination of hydrogenation catalysts; the reactor is respectively filled with hydrodemetallization and hydrodesulfurization catalysts from top to bottom; the raw material flow is from top to bottom, the catalyst activity is gradually increased, the pore diameter is gradually reduced, the particle size is gradually reduced, and the porosity is gradually reduced along the material flow direction; the demetallization catalyst and the hydrodesulfurization catalyst consist of one or more demetallization catalysts; the concentration distribution of the active metal component and the acidic auxiliary agent is not uniform, the concentration gradient of the active metal component and the acidic auxiliary agent of the hydrodemetallization catalyst is increased from the surface to the center of the catalyst particles, and the concentration gradient of the active metal component and the acidic auxiliary agent of the hydrodemetallization catalyst is reduced; the demetallization catalyst accounts for 15-80% by weight; the desulfurization catalyst accounts for 20-85%; the catalyst is used for hydrogenation catalysis of heavy distillate oil and residual oil, has better activity and stability of demetalization, carbon residue removal and desulfurization, controls the temperature rise of a catalyst bed layer, and slows down the deactivation speed of the catalyst.
The method carries out grading on the catalysts with different pore diameters, the pore diameters of the catalysts are gradually reduced along the material flow direction, the method can effectively relieve the pressure drop increasing speed of the device and prolong the operation period of the device, but the method cannot process the high-dry-point and high-nitrogen raw oil.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the hydrocracking method for the high-dry-point and high-nitrogen raw oil, which can effectively treat the high-dry-point and high-nitrogen raw oil and has the advantages of simple process, easy operation and the like.
The invention relates to a hydrocracking method of high-dry-point high-nitrogen raw oil, which comprises the following steps:
(1) under the condition of a hydrofining process, mixing high-nitrogen high-dry-point raw oil and hydrogen to enter a hydrofining reactor for hydrofining reaction, wherein the hydrofining reactor at least comprises two hydrofining catalyst beds, the upper part of each hydrofining catalyst bed is filled with a hydrofining catalyst A, the lower part of each hydrofining catalyst bed is filled with a hydrofining catalyst B, the aperture of the hydrofining catalyst A is smaller than that of the hydrofining catalyst B, and the granularity of the hydrofining catalyst A is higher than that of the hydrofining catalyst B;
(2) enabling the hydrogenation reaction effluent obtained in the step (1) to enter a hydrocracking reactor for hydrocracking reaction, wherein the hydrocracking reactor is filled with a hydrocracking catalyst;
(3) and (3) introducing the hydrocracking reaction effluent obtained in the step (2) into a separation system, and separating to obtain one or more of gas, naphtha, aviation kerosene and diesel oil and tail oil.
In the method, the initial boiling point of the high-nitrogen high-dry-point raw oil is generally 220-450 ℃, and is preferably 330-390 ℃; the final distillation point is generally 500-650 deg.C, preferably 550-600 deg.C, and nitrogen content is not less than 1500 ug/g.
In the method, the density of the high-nitrogen high-dry-point raw oil is not less than 0.9g/cm3, C7Insoluble substances are not more than 300ug/g, and the sum of the contents of Fe, Ca, Ni and V is not more than 10.0 ug/g.
In the method, the aperture of the hydrofining catalyst A is 4-9 nm, preferably 6-8 nm, and the aperture of the hydrofining catalyst B is 1.2-4 times that of the hydrofining catalyst A.
In the method, the hydrofining catalysts A and B can be in the shapes of strip or ball, if a strip catalyst is selected, the granularity of the catalyst A is 5-10 mm, if a ball catalyst is selected, the granularity of the catalyst A is 3-6 mm, and the granularity of the catalyst A is 1.3-3 times that of the hydrofining catalyst B.
In the above process, the hydrorefining reactor operating conditions include: the reaction pressure is 5.0-35.0 MPa, preferably 6.0-19.0 MPa; the average reaction temperature is 200-480 ℃, preferably 270-450 ℃; the volume space velocity is 0.1-15.0 h-1Preferably 0.2 to 3.0 hours-1(ii) a The volume ratio of hydrogen to oil is 100: 1-2500: 1, preferably 400: 1-2000: 1.
in the method, the inlet of each bed layer of the hydrocracking pretreatment reactor is connected with TnIs represented by, and n is ≧ 2, wherein Tn≥Tn-1,Tn-Tn-1≤20℃。
In the method, the filling volume ratio of the hydrofining catalyst A and the hydrofining catalyst B in the previous hydrofining catalyst bed layer along the material flow direction is lower than that of the hydrofining catalyst A and the hydrofining catalyst B in the next hydrofining catalyst bed layer.
In the method, the filling volume of the hydrofining catalyst A in the first hydrofining catalyst bed layer accounts for 1-80 v%, preferably 10-50 v%, of the first hydrofining catalyst bed layer; the hydrofining catalyst B filled in the second hydrofining catalyst bed layer is 5-60% higher than the hydrofining catalyst B filled in the first hydrofining catalyst bed layer, and the preferred range is 10-50%.
In the above process, the hydrocracking reactor operating conditions include: the reaction pressure is 5.0-35.0 MPa, preferably 6.0-19.0 MPa; the average reaction temperature is 200-480 ℃, preferably 270-450 ℃; the volume space velocity is 0.1-15.0 h-1Preferably 0.2 to 3.0 hours-1(ii) a The volume ratio of hydrogen to oil is 100: 1-2500: 1, preferably 400: 1-2000: 1.
in the above method, the hydrofining catalyst in step (1) can be a commercially available catalyst or prepared by a method existing in the art. The carrier adopted by the catalyst is generally alumina, amorphous silicon-aluminum, silicon oxide, titanium oxide and the like, other auxiliary agents such as P, Si, B, Ti, Zr and the like can be contained in the carrier, and the hydrogenation active component can be noble metal or non-noble metal. In the noble metal catalyst, the active component is generally Pt and/or Pt, and the weight content of the active component is generally 0.1-3%. The active component in the non-noble metal catalyst is one or more of W, Mo, Ni and Co, the active component can be in an oxidation state or a reduction state, and the content is generally 15-45% by weight of oxides. When a noble metal catalyst or a reduced non-noble metal catalyst is selected, hydrogen is used for treatment at the temperature of 200-500 ℃, preferably 220-450 ℃ before use; at any time, a medium containing sulfur and nitrogen is strictly injected into the system, so that the catalyst poisoning is avoided. The oxidation state non-noble metal catalyst is selected to be subjected to conventional vulcanization treatment before use, so that the hydrogenation active component is converted into a vulcanization state. The non-noble metal catalyst mainly comprises hydrogenation catalysts such as 3926, 3936, CH-20, FF-14, FF-18, FF-24, FF-26, FF-36, FH-98, FH-UDS and FZC-41 developed by the Fushu petrochemical research institute (FRIPP), hydrogenation catalysts such as HR-416 and HR-448 of IFP company, hydrogenation catalysts such as ICR174, ICR178 and ICR 179 of CLG company, hydrogenation catalysts such as HC-P, HC-K UF-210/220, hydrogenation catalysts such as TK-525, TK-555 and TK-557 of Topsor company, hydrogenation catalysts such as KF-752, KF-840, KF-848, KF-901 and KF-907 of AKZO company; the noble metal catalyst is developed and developed by HDO-18 catalyst such as Nashu petrochemical research institute (FRIPP), and can also be prepared by the method of CN00123141.3 and the like.
In the process of the present invention, the hydrocracking catalyst generally comprises a cracking component, a hydrogenation component and a binder. Such as any suitable hydrocracking catalyst including those known in the art. The cracking component typically comprises amorphous silica-alumina and/or molecular sieves, typically molecular sieves such as Y-type or USY-type molecular sieves. The binder is typically alumina or silica. The hydrogenation component is a metal, a metal oxide or a metal sulfide of a metal in a VI group, a VII group or a VIII group, and more preferably one or more of iron, chromium, molybdenum, tungsten, cobalt, nickel or sulfides or oxides thereof. The hydrogenation component content is usually 5 to 40wt% based on the weight of the catalyst. Specifically, the existing hydrocracking catalyst may be selected, or a specific hydrocracking catalyst may be prepared as required. Commercial hydrocracking catalysts are mainly: HC-12, HC-14, HC-24, HC-39, etc. by UOP, 3905, 3955, FC-12, FC-16, FC-24, FC-32, 3971, 3976, FC-26, FC-28, etc. by FRIPP, and ICR126, ICR210, etc. by CHEVRON.
In the prior art, a hydrofining catalyst with the same pore diameter or the pore diameter of the catalyst gradually increasing along the material flow direction is generally adopted in the hydrofining process, and in order to enable the catalyst to have higher specific surface area, the average pore diameter of the hydrofining catalyst is smaller, so that macromolecular hydrocarbons of high-dry-point and high-nitrogen raw oil cannot enter a catalyst pore channel, and the macromolecular substances still cannot be effectively removed in an adjusting operation mode; although the macromolecular hydrocarbons can enter the catalyst pore channel by adopting the grading mode of decreasing the aperture of the catalyst, the macromolecular hydrocarbons cannot be effectively removed due to the poor activity of the macromolecular hydrocarbons and the low-temperature zone of the reactor. According to the invention, the large-aperture hydrofining catalyst is filled at the bottom of each bed layer of the reactor, and the reaction heat generated by the small-aperture high-activity catalyst in the reaction process is fully utilized, so that the large-aperture catalyst is positioned in the high-temperature region of each catalyst bed layer, the hydrogenation activity of the large-aperture catalyst is fully exerted, macromolecular hydrocarbons in heavy distillate oil are effectively removed, and the product quality of effluent of the hydrofining reactor is improved.
Drawings
FIG. 1 is a schematic diagram of a principle flow of the process of the present invention.
Mixing high dry point and high nitrogen raw oil 1 and hydrogen 2, feeding the mixture into a hydrofining reactor 3, feeding a hydrofining reaction effluent 4 into a hydrocracking reactor 5, feeding a hydrocracking reaction effluent 6 into a separator 7, recycling a separated gas phase 8, and feeding a liquid phase 9 into a fractionating tower 10 to separate the gas phase into gas 11, naphtha 12, aviation kerosene 13, diesel oil 14 and tail oil 15.
Detailed Description
The following examples further illustrate specific aspects of the present invention. The hydrocracking catalyst used in the process shown in FIG. 1 was a commercial catalyst FC-32 developed and produced by Dain petrochemical research institute.
TABLE 1 Primary Properties of the base oils
Raw oil name
|
Mixing the raw materials
|
Density (20 ℃ C.)/g-cm-3 |
0.9249
|
Distillation range/. degree.C
|
|
IBP/10%
|
252.8/390.1
|
30%/50%
|
426.1/454.8
|
70%/90%
|
485.7/530.1
|
95%/EBP
|
549.6/575.2
|
Acid value, mg. KOH/g
|
0.51
|
Residual carbon content%
|
0.22
|
S,%
|
0.75
|
N/ ug·g-1 |
2400
|
C,%
|
86.36
|
H,%
|
12.42
|
Metal, ppm
|
|
Fe
|
1.7
|
Na
|
2.92
|
Ni
|
0.07
|
V
|
0.07 |
TABLE 2 Main physicochemical Properties of the hydrorefining and hydrocracking catalysts
Catalyst and process for preparing same
|
Catalyst A
|
Catalyst B
|
FC-32
|
Chemical composition
|
Mo-Ni
|
Mo-Ni
|
W-Ni
|
Physical properties:
|
|
|
|
pore volume, mL/g
|
≮0.32
|
≮0.30
|
>0.32
|
Specific surface area, m2/g
|
≮160
|
≮160
|
>240
|
Shape of
|
Tooth ballModel (III)
|
Tooth ball type
|
Cylindrical bar
|
Average pore diameter, nm
|
8
|
11
|
|
Particle size
|
3.5
|
2.0
|
|
Table 3 example process conditions and test results
Test number
|
Example 1
|
Example 2
|
Example 3
|
Refining reactor
|
|
|
|
The first bed is filled with the proportion%
|
|
|
|
Catalyst A
|
80
|
50
|
90
|
Catalyst B
|
20
|
50
|
10
|
Second bed filling ratio%
|
|
|
|
Catalyst A
|
70
|
40
|
90
|
Catalyst B
|
30
|
60
|
10
|
Reaction pressure/MPa
|
16.0
|
16.0
|
16.0
|
First bed inlet temperature/. degree.C
|
340
|
330
|
340
|
Second bed inlet temperature/. degree.C
|
345
|
350
|
340
|
Volume space velocity/h-1 |
1.0
|
1.0
|
1.0
|
Volume ratio of hydrogen to oil
|
800
|
800
|
800
|
Refined oil containing nitrogen/ug.g-1 |
5.6
|
16
|
11.2
|
Cracking reactor
|
|
|
|
Average reaction temperature/. degree.C
|
375
|
383
|
379
|
Volume space velocity/h-1 |
1.5
|
1.5
|
1.5
|
Conversion rate%
|
75
|
73
|
70 |
Comparative example 1
The hydrofining reactor is completely filled with hydrofining catalyst A by adopting the prior art.
Comparative example 2
In the prior art, a hydrofining catalyst B and a hydrofining catalyst A are sequentially filled between beds of a hydrofining reactor.
Table 4 examples process conditions and test results
Test number
|
Example 1
|
Comparative example 1
|
Comparative example 2
|
Refining reactor
|
|
|
|
The first bed is filled with the proportion%
|
|
|
|
Catalyst A
|
80
|
100
|
0
|
Catalyst B
|
20
|
0
|
100
|
Second bed filling ratio%
|
|
|
|
Catalyst A
|
70
|
100
|
100
|
Catalyst B
|
30
|
0
|
0
|
Reaction pressure/MPa
|
16.0
|
16.0
|
16.0
|
Average reaction temperature/. degree.C
|
380
|
380
|
380
|
Volume space velocity/h-1 |
1.0
|
1.0
|
1.0
|
Volume ratio of hydrogen to oil
|
800
|
800
|
800
|
Refined oil containing nitrogen/ug.g-1 |
5.6
|
33
|
24
|
Cracking reactor
|
|
|
|
Average reaction temperature/. degree.C
|
375
|
388
|
384
|
Volume space velocity/h-1 |
1.5
|
1.5
|
1.5
|
Conversion rate%
|
75
|
71
|
73 |
The embodiment shows that the high-dry-point and high-nitrogen raw oil can effectively reduce the nitrogen content of refined oil and improve the cracking performance of the cracking catalyst by the hydrotreating method of the technology.