CN111100699A - Hydrocracking method for high-nitrogen high-dry-point raw oil - Google Patents
Hydrocracking method for high-nitrogen high-dry-point raw oil Download PDFInfo
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
Abstract
The invention discloses a hydrocracking method of high-nitrogen high-dry-point 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, and the lower part of each hydrofining catalyst bed is filled with a 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. The method can effectively treat the high-nitrogen high-dry-point raw oil, and has the advantages of simple process, easy operation and the like.
Description
Technical Field
The invention relates to a hydrocracking method of high-nitrogen high-dry-point raw oil, in particular to a hydrocracking method of high-nitrogen high-dry-point 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 high-nitrogen high-dry-point raw oil cannot be processed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the hydrocracking method for the high-nitrogen high-dry-point raw oil, which can effectively treat the high-nitrogen high-dry-point raw oil and has the advantages of simple process, easy operation and the like.
The invention relates to a hydrocracking method of high-nitrogen high-dry-point 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 hydrofining catalyst A is an unfired hydrofining catalyst, supports an organic compound while supporting an active metal, and the hydrofining catalyst B is a calcined catalyst;
(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 granularity of the hydrofining catalyst A is higher than that of the hydrofining catalyst B, and the granularity of the hydrofining catalyst A is 1.3-3 times that of the hydrofining catalyst B. The hydrofining catalysts A and B can be in the shape of a strip or a ball, for example, a strip catalyst is selected, the granularity of the catalyst A is 5-10 mm, for example, a ball catalyst is selected, the granularity of the catalyst A is 3-6 mm,
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 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, silica, titanium oxide and the like, and the carrier can contain other auxiliary agents such as P, Si, B, Ti, Zr and the like; the active component in the catalyst is one or more of W, Mo, Ni and Co, the active component is in an oxidation state, and the content of the active component is generally 15-45% by weight of oxide. The oxidation state 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 catalyst A is subjected to high-temperature roasting after the carrier is formed, roasting is carried out for 0.5-20 hours at the temperature of 300-750 ℃, and then an active metal component and an organic auxiliary agent are impregnated, wherein the organic compound comprises but is not limited to at least one of sulfoxide, the hydrorefining catalyst is obtained without roasting after drying, the drying temperature is 70-290 ℃, and the drying time is 0.5-20 hours; the commercially available catalysts comprise FF-46 and FF-56 which are developed by the research and development institute of petrochemical engineering (FRIPP), and can also be prepared by the method of CN101491766A and the like; the catalyst A can not be dried at high temperature in the start-up process, and the temperature of a catalyst bed layer can not be higher than 160 ℃ before start-up oil is introduced. The catalyst B is roasted at high temperature after the carrier is molded, the catalyst B is roasted at the temperature of 300-750 ℃ for 0.5-20 hours, then an active metal component and an organic auxiliary agent are impregnated, and the hydrogenation refining catalyst is obtained by roasting, wherein the roasting temperature is 300-750 ℃, the roasting time is 0.5-20 hours, the commercially available catalysts comprise hydrogenation catalysts such as 3926, 3936, CH-20, FF-14, FF-18, FF-24, FF-26, FF-36, FH-98, FH-UDS, FZC-41 and the like developed by the research and development institute of petrochemical industry (FRIPP), hydrogenation catalysts such as HR-416, HR-448 and the like of IFP company, hydrogenation catalysts such as ICR174, ICR178, ICR 179 and the like of CLG company, hydrogenation catalysts such as HC-P, HC-K UF-210/220, TK-525, TK-555, TK-557 and the like of Topsor company, KF-752, KF-840, KF-848, KF-901, KF-907 and the like hydrogenation catalysts available from AKZO corporation.
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 method of the present invention, 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 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, more than ten theoretical models are proposed in turn aiming at the structure of the active phase of the hydrotreating catalyst, wherein the Co-Mo-S model proposed by Tops ø e and the like is the model which has the most influence at present, the Co-Mo-S active phase is divided into a single-layer (called I type Co-Mo-S) and a multi-layer (called II type Co-Mo-S), the I type Co-Mo-S is connected with a carrier through a Mo-O-Al bond and is a low-sulfur coordinated Co-Mo-S active phase, and the interaction of Mo and Al is strong, so that MoS is influenced2The edge, corner Co electronic states, result in low intrinsic (intrinsic) activity per active center. The type II Co-Mo-S has lower interaction with the carrier, so the type II Co-Mo-S is easier to completely vulcanize and is in a stacked MoS2The structure, a highly sulfur coordinated Co-Mo-S active phase, is usually stacked (laminated) together from larger sheets, not attached to a support, and the intrinsic activity of each active center of the type II active phase is high. Pure Al2O3By Mo-O-Al connection, MoS2The single-layer dispersion is good, the single-layer dispersion is an I-type active phase, and the P, B, Si auxiliary agent is added, so that Mo-O-Al connection can be weakened, and a mixed active phase of the I type and the II type can be generated. The II type active phase catalyst has better hydrogenation activity, and is particularly characterized in that the effects of hydrodenitrogenation and aromatic hydrocarbon saturation are better at a lower flat reaction temperature; however, since the catalyst is not calcined at high temperature during the preparation process, the high temperature stability is poor, so that when processing heavy and poor raw materials, a higher reaction temperature is required, which also makes the catalystThe catalytic activity of the catalyst in the high-temperature reaction zone of the reactor cannot be effectively exerted. The invention fills II type active phase hydrogenation catalyst at the upper part (namely low temperature reaction zone) of each catalyst bed layer, and fills common I type active phase hydrogenation catalyst at the lower part (namely high temperature reaction zone), thereby fully playing the characteristic of good low temperature activity of the II type active phase hydrogenation catalyst, improving the hydrogenation saturation effect, generating larger reaction heat, promoting the activity of the common I type active phase hydrogenation catalyst to play, better improving the aromatic hydrocarbon saturation and denitrification depth of the hydrogenation refining reaction, and improving the product quality.
Drawings
FIG. 1 is a schematic diagram of a principle flow of the process of the present invention.
Mixing the high-nitrogen high-dry-point 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
TABLE 2 Main physicochemical Properties of the hydrorefining and hydrocracking catalysts
Table 3 example process conditions and test results
Comparative example 1
The hydrofining reactor is completely filled with hydrofining catalyst A by adopting the prior art.
Comparative example 2
The hydrofining reactor is completely filled with a hydrofining catalyst B by adopting the prior art.
Table 4 examples process conditions and test results
The embodiment shows that the high-nitrogen high-dry-point 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.
Claims (10)
1. A hydrocracking method for high-nitrogen high-dry-point raw oil is characterized by comprising the following steps: the method 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 hydrofining catalyst A is an unfired hydrofining catalyst, supports an organic compound while supporting an active metal, and the hydrofining catalyst B is a calcined catalyst;
(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.
2. The method of claim 1, wherein: the initial boiling point of the high-nitrogen high-dry-point raw oil is 220-450 ℃; the final distillation point is 500-650 ℃, and the nitrogen content is not lower than 1500 ug/g.
3. The method of claim 1, wherein: the initial boiling point of the high-nitrogen high-dry-point raw oil is 330-390 ℃; the final distillation point is 550-600 ℃.
4. The method of claim 1, wherein: the particle size of the hydrofining catalyst A is higher than that of the hydrofining catalyst B.
5. The method of claim 4, wherein: the granularity of the hydrofining catalyst A is 1.3-3 times that of the hydrofining catalyst B, the hydrofining catalyst A and the hydrofining catalyst B are in the shape of a strip or a ball, the granularity of the hydrofining catalyst A is 5-10 mm when the strip catalyst is selected, and the granularity of the hydrofining catalyst A is 3-6 mm when the ball catalyst is selected.
6. The method of claim 1, wherein: the hydrofinishing reactor operating conditions include: the reaction pressure is 5.0-35.0 MPa; the average reaction temperature is 200-480 ℃; the volume space velocity is 0.1-15.0 h-1(ii) a The volume ratio of hydrogen to oil is 100: 1-2500: 1.
7. the method of claim 6, wherein: the hydrofinishing reactor operating conditions include: the reaction pressure is 6.0-19.0 MPa; the average reaction temperature is 270-450 ℃; the volume airspeed is 0.2-3.0 h-1(ii) a The volume ratio of hydrogen to oil is 400: 1-2000: 1.
8. the method of claim 1, wherein: the inlet temperature of each bed layer of the hydrocracking pretreatment reactor is TnIs represented by, and n is ≧ 2, wherein Tn≥Tn-1，Tn-Tn-1≤20℃。
9. The method of claim 1, wherein: the filling volume of the hydrofining catalyst A in the first hydrofining catalyst bed layer accounts for 1-80 v% of that of the first hydrofining catalyst bed layer; and 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.
10. The method of claim 9, wherein: the filling volume of the hydrofining catalyst A in the first hydrofining catalyst bed layer accounts for 10-50 v% of the first hydrofining catalyst bed layer; the hydrofining catalyst B filled in the second hydrofining catalyst bed layer is 10-50% higher than the hydrofining catalyst B filled in the first hydrofining catalyst bed layer.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090065396A1 (en) * | 2007-09-07 | 2009-03-12 | Peter Kokayeff | Hydrodesulfurization Process |
| CN103059935B (en) * | 2011-10-20 | 2014-12-31 | 中国石油化工股份有限公司 | Fixed bed hydrotreating method of heavy oil |
| CN104560156A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrocracking method |
| CN104611055A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Two-stage hydrotreating method of high dry point raw material |
| CN104611016A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Poor-quality raw material hydrocracking method |
| US20150247098A1 (en) * | 2012-09-21 | 2015-09-03 | China Petroleum & Chemical Corporation | Reformate hydrotreatment method |
| CN108070404A (en) * | 2016-11-17 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of method for hydrogen cracking |
-
2018
- 2018-10-29 CN CN201811264084.4A patent/CN111100699A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090065396A1 (en) * | 2007-09-07 | 2009-03-12 | Peter Kokayeff | Hydrodesulfurization Process |
| CN103059935B (en) * | 2011-10-20 | 2014-12-31 | 中国石油化工股份有限公司 | Fixed bed hydrotreating method of heavy oil |
| US20150247098A1 (en) * | 2012-09-21 | 2015-09-03 | China Petroleum & Chemical Corporation | Reformate hydrotreatment method |
| CN104560156A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrocracking method |
| CN104611055A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Two-stage hydrotreating method of high dry point raw material |
| CN104611016A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Poor-quality raw material hydrocracking method |
| CN108070404A (en) * | 2016-11-17 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of method for hydrogen cracking |
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