CN109988612B - Flexible diesel hydro-upgrading process - Google Patents
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- 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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- Oil, Petroleum & Natural Gas (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a flexible diesel oil hydro-upgrading process. After being hydrofined, the diesel raw material enters a hydro-upgrading reactor, and the material passing through a first hydro-upgrading catalyst bed layer is divided into two parts; separating a strand of material to obtain liquid, pumping the liquid out of the modification reactor, mixing the liquid with hydrogen, and then entering a hydroisomerization pour point depression reactor to perform an isomerization pour point depression reaction; the other material continuously flows downwards through a second hydrogenation modification catalyst bed layer; the obtained hydrogenation modification reaction material and the hydrogenation isomerization pour point depression reaction material are respectively subjected to gas-liquid separation and fractionation to obtain diesel products with different specifications. The invention provides a hydro-upgrading process for simultaneously producing more than two diesel products with different specifications on one set of hydro-process device for the first time, which can fully utilize the heat carried by part of the upgrading material to realize the coupling operation of a hydro-upgrading reactor and a hydroisomerization pour point depressing reactor.
Description
Technical Field
The invention belongs to the field of petroleum refining, and particularly relates to a diesel hydro-upgrading process for flexibly producing high-quality diesel products.
Background
Increasingly strict environmental regulations require higher and higher quality diesel products, mainly with greater and greater limits on sulfur content, cetane number, density and polycyclic aromatic hydrocarbon content. The inferior diesel oil hydrogenation modification technology can greatly reduce the sulfur content and the aromatic hydrocarbon content of the diesel oil product, reduce the density and improve the cetane number. In addition, in winter, diesel products in cold regions have different limits and requirements on condensation points, and diesel products in China can be divided into specifications of 5#, 0#, -10#, -20#, -35# and-50 # according to the condensation points. The pour point of the diesel can be effectively reduced by the hydrogenation pour point depressing technology.
The diesel oil fraction hydrogenation upgrading technology, such as CN1156752A and CN1289832A, is a hydrogenation process technology using a hydrofining catalyst and a Y-type molecular sieve hydrogenation upgrading catalyst. Such techniques can increase the cetane number of diesel products by more than 10 units, but the pour point of the diesel does not change much.
Diesel oil fraction hydroisomerization pour point reducing technology, such as CN1718683A and CN1712499A, uses hydrofining catalyst and beta-zeolite-containing hydroisomerization pour point reducing catalyst, and adopts a one-stage series process to produce diesel oil product, but under the same hydro-upgrading condition, its cetane number is lower than that of hydro-upgraded diesel oil, and its technological condition is more strict than that of hydro-pour point diesel oil product.
In conclusion, the existing diesel oil hydro-upgrading technology can obtain higher diesel oil product yield, greatly improve the product quality such as cetane number, sulfur content, aromatic hydrocarbon content, density and the like, but the condensation point reduction amplitude is not large or reduced, and the requirement of low condensation point diesel oil cannot be met. The existing hydroisomerization pour point depressing technology can greatly lower the pour point of a diesel product, can meet the index requirement of low pour point diesel, but has lower yield when producing the low pour point diesel product. The diesel oil produced by the process technology is only one, and the product flexibility is poor.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a flexible diesel hydro-upgrading process, namely, a part of reaction liquid material flow is extracted from a gas-liquid separator arranged in the middle of a hydro-upgrading reactor, and the diesel raw oil is flexibly produced into high-quality hydro-upgraded diesel products and high-quality hydro-isomerized pour-point-reducing diesel products by a hydro-upgrading and hydro-isomerized pour-point-reducing combined method.
The flexible diesel hydro-upgrading process comprises the following steps:
a. firstly, passing diesel raw oil through a hydrofining catalyst bed under the hydrofining condition to obtain a hydrofining material flow;
b. b, passing the hydrofined material flow obtained in the step a through a first hydro-upgrading catalyst bed under hydro-upgrading conditions to obtain a first hydro-upgrading material flow, dividing the part of the reaction material flow into two parts, separating one part of the reaction material flow into a gas-liquid separator to obtain a liquid material flow, and pumping out the liquid material flow from the hydrogenation reactor;
c. b, continuously allowing the rest part of the first hydro-upgrading material flow in the step b to pass through a second hydro-upgrading catalyst bed under the hydro-upgrading condition, and separating and fractionating the hydro-upgrading material flow to obtain hydro-upgrading high-pressure hydrogen-rich gas, a hydro-upgrading gas product, a hydro-upgrading naphtha product and a hydro-upgrading diesel product;
d. and c, mixing the first hydro-upgrading liquid material flow obtained in the step b with hydrogen, passing the mixture through a hydro-isomerization pour point depressing catalyst bed layer of a hydro-isomerization pour point depressing reactor under the hydro-isomerization pour point depressing condition, and separating and fractionating the hydro-isomerization pour point depressing material flow to obtain hydro-isomerization pour point depressing high-pressure hydrogen-rich gas, hydro-isomerization pour point depressing naphtha and hydro-isomerization pour point depressing diesel oil products.
The hydro-upgrading process according to the invention may further comprise step e: and d, mixing the hydro-upgrading high-pressure hydrogen-rich gas obtained in the step c with the hydro-isomerization pour point depressing high-pressure hydrogen-rich gas obtained in the step d for recycling.
In the invention, the hydrofining catalyst bed, the first hydro-upgrading catalyst bed and the second hydro-upgrading catalyst bed can be arranged in one hydrogenation reactor, for example, three catalyst beds can be arranged in one hydro-upgrading reactor in sequence; or the hydrofining catalyst bed layer is arranged in a single hydrogenation reactor, and the first hydro-upgrading catalyst bed layer and the second hydro-upgrading catalyst bed layer are arranged in one hydro-upgrading reactor; or the hydrorefining catalyst bed layer and the first hydroupgrading catalyst bed layer are arranged in one hydroupgrading reactor, and the second hydroupgrading catalyst bed layer is arranged in the other hydroupgrading reactor.
S, N, O and other impurities in the raw diesel oil are effectively removed through a hydrofining catalyst, aromatic hydrocarbon is subjected to hydrogenation saturation to a certain extent, partial ring opening reaction of annular hydrocarbon occurs when hydrofining material flow continuously passes through a hydrofining catalyst bed layer, a component with a low cetane number is changed into a component with a high cetane number, and part of hydrofining material flow is continuously subjected to hydrogenation modification, so that the cetane number of the diesel oil is improved to the maximum extent, and a diesel oil product with a relatively high condensation point and a high cetane number is obtained; and mixing a part of the extracted first hydro-upgrading liquid material flow with hydrogen, and then passing through a hydroisomerization pour point reducing catalyst to reduce the pour point of diesel oil, thereby obtaining a diesel oil product with cetane number meeting the requirement and low pour point.
Compared with the prior art, the flexible diesel hydro-upgrading process has the advantages that:
1. in the invention, the hydro-upgrading reactor comprises at least two hydro-upgrading catalyst beds. A part of the modified liquid material is extracted by the gas-liquid separator arranged in the middle of the bed layer of the hydro-upgrading reactor, so that the effective distribution of the hydro-upgrading material strand can be realized, and the obtained material is subjected to different hydrogenation processes, thereby flexibly producing target diesel products with different specifications. At the same time, it is technically easy to extract the reactant stream in the middle of the reactor bed. In the prior art, a set of hydrogenation devices can only obtain diesel products with one specification; if diesel oil products with different specifications are required, more than two sets of hydrogenation devices are required. Therefore, the invention provides a hydro-conversion process for simultaneously producing more than two diesel oil products with different specifications on one set of hydrogenation process device.
2. According to the invention, the gas-liquid separator is arranged in the middle of the catalyst bed layer of the hydrogenation modification reactor, the first hydrogenation modification liquid flow of the diesel raw material subjected to hydrofining and hydrogenation modification is extracted out of the reactor through the gas-liquid separator and is sent into the independently arranged hydrogenation isomerization pour point depressing reactor for hydrogenation isomerization pour point depressing reaction, so that the pour point of the hydrogenation modified material is further reduced, and therefore, the method disclosed by the invention can be used for flexibly producing diesel products with different pour points and different cetane numbers.
3. In the invention, the diesel oil product obtained after hydrogenation modification has high cetane number; the diesel oil product obtained after partial hydro-upgrading and hydro-isomerism pour point depression has low pour point and relatively high cetane number; can respectively meet the requirements of producing high-quality diesel products with different specifications.
4. In the invention, the impurities such as S, N in the raw oil are converted into H after hydrofining and partial hydro-upgrading2S and NH3By gas-liquid separationMost of H after separation in the separator2S and NH3Present in the gas phase, and H in the liquid phase2S and NH3The content of the catalyst is less, so that the inhibiting effect on the molecular sieve of the hydroisomerization pour point depressing catalyst is reduced, the reaction activity of the hydroisomerization pour point depressing catalyst is improved, namely the reaction temperature required when the same pour point depressing effect is achieved is reduced, the liquid obtained in the middle of a modified catalyst bed layer of a hydro-modification reactor has very high temperature and pressure, although the temperature of the liquid mixed with the circulating hydrogen is slightly reduced, the liquid can still directly enter the newly-arranged hydroisomerization pour point depressing reactor for reaction and achieve the pour point depressing effect, and therefore the heat carried by the partially-modified material is fully utilized, and the coupling operation of the hydroisomerization pour point depressing reactor and the hydro-modification reactor is achieved.
Drawings
Fig. 1 is a schematic flow chart of the principle of the present invention. The method is described by taking an example of arranging a hydrofining reactor, a hydro-upgrading reactor and a hydro-isomerization pour point depressing reactor.
Wherein: 1-raw oil, 2-hydrofining reactor, 3-hydrofining material flow, 4-hydroupgrading reactor, 5-hydroisomerized pour point depressing raw material flow, 6-hydroupgrading material flow, 7-hydroisomerized pour point depressing reactor, 8-hydroupgrading high-pressure separator, 9-hydroisomerized pour point depressing high-pressure separator, 10-hydroupgrading fractionating tower, 11-hydroisomerized pour point depressing fractionating tower, 12-hydroupgrading gas product, 13-hydroupgrading naphtha product, 14-hydroupgrading diesel product, 15-hydroisomerized pour point depressing gas product, 16-hydroisomerized pour point depressing naphtha product, 7-hydroisomerized pour point depressing diesel product, 18-hydroupgrading high-pressure separator gas product, 19-hydroisomerized pour point depressing high-pressure separator gas product, 20-make up hydrogen. 21-hydrogenation upgrading recycle hydrogen, 22-hydrogenation isomerization condensation point reduction recycle hydrogen and 23-gas-liquid separator.
Detailed Description
The initial boiling point of the diesel raw material in the step a is 100-260 ℃, and the final boiling point is 300-450 ℃. The diesel raw oil can be one of straight-run diesel oil, coking diesel oil, catalytic diesel oil, hydrotreated diesel oil and the like obtained by petroleum processing, one of coal tar, coal direct liquefaction oil, coal indirect liquefaction oil, shale oil and the like obtained from coal, and can also be mixed oil of a plurality of the coal tar, the coal direct liquefaction oil, the coal indirect liquefaction oil and the shale oil.
The hydrofining catalyst in the step a is a conventional diesel hydrofining catalyst. Generally, metals in a VIB group and/or a VIII group are used as active components, alumina or silicon-containing alumina is used as a carrier, the metals in the VIB group are generally Mo and/or W, and the metals in the VIII group are generally Co and/or Ni. Based on the weight of the catalyst, the content of the VIB group metal is 10-35 wt% calculated by oxide, the content of the VIII group metal is 3-15 wt% calculated by oxide, and the properties are as follows: the specific surface area is 100 to 650m2The pore volume is 0.15 to 0.6 mL/g. The main catalysts comprise hydrofining catalysts such as FH-5, FH-98, 3936 and 3996, FHUDS series and the like developed by the petrochemical research institute, and can also be similar catalysts with functions developed by foreign catalyst companies, such as HC-K, HC-P of UOP company, TK-555 and TK-565 of Topsoe company, KF-847 and KF-848 of Akzo company and the like. The operation conditions can adopt the conventional operation conditions, generally the reaction pressure is 3.0MPa to 15.0MPa, the reaction temperature is 300 ℃ to 430 ℃, and the liquid hourly volume space velocity is 0.2h-1～6.0h-1The volume ratio of the hydrogen to the oil is 100: 1-2000: 1.
The hydro-upgrading catalyst in the steps B and c is a conventional diesel hydro-upgrading catalyst, generally, metals in a VIB group and/or a VIII group are used as active components, the metals in the VIB group are generally Mo and/or W, and the metals in the VIII group are generally Co and/or Ni. The catalyst carrier contains one or more of alumina, siliceous alumina and molecular sieve, preferably containing molecular sieve; the molecular sieve can be a Y-type molecular sieve. Based on the weight of the catalyst, the content of the VIB group metal is 10-35 wt% calculated by oxide, the content of the VIII group metal is 3-15 wt% calculated by oxide, the content of the molecular sieve is 5-40 wt%, and the content of the alumina is 10-80 wt%; its specific surface area is 100m2/g～650m2The pore volume is 0.15mL/g to 0.50 mL/g. The main catalysts comprise 3963, FC-18, FC-32 catalysts and the like which are developed by the petrochemical research institute. For the hydro-upgrading catalyst, a certain hydrogenation activity and a certain cracking activity are required to be ensuredThe hydrogenation saturation of olefins and aromatics in diesel oil fractions requires ring-opening reaction of saturated aromatics. The operating conditions for the hydro-upgrading can be conventional and are generally: the reaction pressure is 3.0MPa to 15.0MPa, the reaction temperature is 300 ℃ to 430 ℃, and the liquid hourly volume space velocity is 0.3h-1～15.0h-1The volume ratio of the hydrogen to the oil is 100: 1-2000: 1.
And in the step b, the gas-liquid separator is a device arranged between the beds of the hydro-upgrading reactor or at the inlet of the catalyst bed. The gas-liquid separator at least comprises a reactant inlet, a liquid phase conduit and a gas phase conduit, wherein the liquid phase conduit pumps the separated liquid phase out of the hydro-upgrading reactor, and the gas phase conduit introduces the separated gas phase into the lower hydro-upgrading catalyst bed layer.
According to a preferred embodiment of the present invention, the catalyst used in the first hydrogenation upgrading catalyst bed is hydrogenation catalyst a, and the catalyst used in the second hydrogenation upgrading catalyst bed is hydrogenation catalyst B. The content percentage x of the molecular sieve in the hydrogenation catalyst A1Less than the percentage content x of the molecular sieve in the hydrogenation catalyst B2Preferably x1Ratio x21-6 percentage points lower, more preferably x1Ratio x22-5 percentage points lower. According to the preferred embodiment, the hydro-upgrading reaction can achieve a better ring-opening effect, thereby contributing to further improvement in the cetane number of the resulting product. The reason is that after the raw oil passes through the first hydrogenation modified catalyst bed layer, a part of polycyclic aromatic hydrocarbon is subjected to hydrofining saturation and a ring at the outermost layer is subjected to ring opening reaction after hydrogenation modified reaction, so that the volume of the hydrocarbon molecules subjected to ring opening is increased, the steric hindrance is increased, and the difficulty of continuing the modification reaction is correspondingly increased, therefore, the content of the molecular sieve in the second hydrogenation modified catalyst (namely, the catalyst B) is properly increased to improve the reaction activity of the catalyst, the subsequent ring opening reaction of the second ring can be better completed, and the cetane number of the obtained diesel oil can be increased.
And c, allowing a part of the hydro-upgrading reactant flow in the step b to enter a gas-liquid separator through an inlet of the gas-liquid separator, wherein the extracted part of the liquid phase material flow accounts for 5-95 wt% of the raw oil in terms of liquid phase, and preferably 10-80 wt%.
The separation described in step c typically comprises separating two parts for a hydro-upgrading high pressure separator and a low pressure separator. Wherein the high-pressure separator separates to obtain hydro-upgrading high-pressure hydrogen-rich gas and liquid, and the liquid separated by the high-pressure separator enters the low-pressure separator. The low pressure separator separates the high pressure liquid product to yield a hydrocarbon-rich gas and a low pressure liquid product. Separating the hydrocarbon-rich gas to obtain the required hydrogenation modified gas product.
The fractionation described in step c is carried out in a hydro-upgrading fractionator system. And fractionating the low-pressure liquid product in a fractionating tower to obtain a hydrogenation modified naphtha product and a hydrogenation modified diesel product.
The hydroisomerization pour point depressing catalyst in the step d is a conventional diesel hydroisomerization pour point depressing catalyst, generally, metals in a VIB group and/or a VIII group are used as active components, the metals in the VIB group are generally Mo and/or W, and the metals in the VIII group are generally Co and/or Ni. The carrier of the catalyst comprises one or more of alumina, siliceous alumina and molecular sieve, preferably containing molecular sieve; the molecular sieve can be a beta type molecular sieve, a Sapo type molecular sieve and the like. Based on the weight of the catalyst, the content of the VIB group metal is 10-35 wt% calculated by oxide, the content of the VIII group metal is 3-15 wt% calculated by oxide, the content of the molecular sieve is 5-40 wt%, and the content of the alumina is 10-80 wt%; the specific surface area is 100m2/g～650m2The pore volume is 0.15mL/g to 0.50 mL/g. The main catalysts comprise FC-14 and FC-20 catalysts developed by the petrochemical research institute. For the hydrogenation modification catalyst, certain hydrogenation activity and certain cracking activity are required, and both the hydrogenation saturation of olefin and aromatic hydrocarbon in diesel oil fraction and the isomerization reaction of straight-chain paraffin are required. The hydroisomerization pour point depression may be carried out under conventional operating conditions, typically: the reaction pressure is 3.0MPa to 15.0MPa, the reaction temperature is 200 ℃ to 430 ℃, and the liquid hourly volume space velocity is 0.3h-1～15.0h-1The volume ratio of the hydrogen to the oil is 100: 1-1500: 1.
The separation described in step d is carried out in a hydroisomerization pour point depression high pressure separator and a low pressure separator. Wherein the hydroisomerization pour point depressing high-pressure separator separates to obtain hydroisomerization pour point depressing high-pressure hydrogen-rich gas and liquid, and the liquid separated by the high-pressure separator enters the low-pressure separator. The low pressure separator separates the high pressure liquid product to yield a hydrocarbon-rich gas and a low pressure liquid product. Separating the hydrocarbon-rich gas to obtain the required hydroisomerization pour point depression gas product.
And d, fractionating in the step d to obtain a fractionating tower system, and fractionating the low-pressure liquid product in the fractionating tower to obtain a hydroisomerization pour point depression naphtha product and a hydroisomerization pour point depression diesel product.
The hydro-upgrading gas product and the hydro-isomerization pour point depressing gas product in the step c and the step d can be used as products independently or can be mixed into a mixed gas product.
The hydro-upgrading naphtha product and the hydroisomerization pour point depressing naphtha product in the step c and the step d can be used as products independently or can be mixed into a mixed naphtha product.
And e, mixing the high-pressure hydrogen-rich gas in the step e, and then directly using the mixed gas as recycle hydrogen, or recycling the mixed gas after hydrogen sulfide is removed by a recycle hydrogen desulfurization system.
With reference to fig. 1, the method of the present invention is as follows: raw oil 1 and recycle hydrogen 21 are mixed and enter a hydrofining reactor 2, a hydrofining material flow 3 enters a hydro-upgrading reactor 4, a reactant flow passing through a first hydro-upgrading catalyst bed layer is pumped out of a hydroisomerization pour point depressing raw material flow 5 through a gas-liquid separator 23, the material flow after the hydrogenation pour point depressing raw material flow 5 is pumped out continues to enter a subsequent hydro-upgrading catalyst bed layer, a hydro-upgrading product flow 6 enters a hydro-upgrading high-pressure separator 8 for gas-liquid separation, the liquid obtained by separation enters a fractionating tower 10 for fractionation to obtain a hydro-upgrading gas product 12, a hydro-upgrading naphtha product 13 and a hydro-upgrading diesel product 14, the hydroisomerization pour point depressing raw material flow 5 and the recycle hydrogen 22 enter a hydroisomerization pour point depressing reactor 7, and the product flow passing through the hydro-isomerization pour point depressing catalyst bed layer enters a hydroisomerization pour point depressing high-pressure separator 9 for gas-liquid separation, the separated liquid enters a fractionating tower 11 to be fractionated to obtain a hydroisomerized pour point depressing gas product 15, a hydroisomerized pour point depressing naphtha product 16 and a hydroisomerized pour point depressing diesel oil product 17, the hydroisomerized modified gas product 12 and the hydroisomerized pour point depressing gas product 15 can be used as products independently or mixed to obtain a mixed gas product, the hydroisomerized modified naphtha product 13 and the hydroisomerized pour point depressing naphtha product 16 can be used as products independently or mixed to obtain a mixed naphtha product, and the gas 18 separated by the hydroisomerized pour point depressing high-pressure separator 8 and the gas 19 separated by the hydroisomerized pour point depressing high-pressure separator 9 are mixed and then mixed with a recycle hydrogen compressor and then mixed with a make-up hydrogen 20 to obtain the recycle hydrogen.
The embodiments and effects of the present invention are described below by way of examples.
Examples 1 to 4
The protective agents FZC-100, FZC-105 and FZC106 are hydrogenation protective agents developed and produced by the smooth petrochemical research institute of the China petrochemical industry, Inc.; the catalyst FHUDS-5 is a hydrofining catalyst developed and produced by the smoothing petrochemical research institute of China petrochemical industry Limited company; the catalyst 3963 is a hydro-upgrading catalyst developed and produced by the research institute of the smooth petrochemical industry of the limited petrochemical company in China, and contains a Y-type molecular sieve; the content of the Y-type molecular sieve in the 3963B catalyst is 4 percent (number) higher than that of the Y-type molecular sieve in the 3963 catalyst, and the rest is unchanged; the catalyst FC-20 is a hydrogenation pour point depression catalyst developed and produced by China petrochemical company Limited, compliant petrochemical research institute, and contains a beta-type molecular sieve.
TABLE 1 Main Properties of Diesel feed stock
Table 2 examples process conditions and test results
Table 2 example process conditions and test results
It can be seen from the examples that the flexible diesel hydro-upgrading process of the present invention can achieve the purpose of producing diesel with different properties by extracting a part of reactant flow from the hydro-upgrading reactor and using hydro-upgrading catalyst and hydroisomerization pour point depressing catalyst, and the production mode is flexible.
Claims (17)
1. A flexible diesel hydro-upgrading process comprises the following steps:
a. firstly, passing diesel raw oil through a hydrofining catalyst bed under the hydrofining condition to obtain a hydrofining material flow;
b. b, passing the hydrofined material flow obtained in the step a through a first hydro-upgrading catalyst bed under hydro-upgrading conditions to obtain a first hydro-upgrading material flow, dividing the part of the reaction material flow into two parts, separating one part of the reaction material flow into a gas-liquid separator to obtain a liquid material flow, and pumping out the liquid material flow from the hydrogenation reactor;
c. b, continuously allowing the rest part of the first hydro-upgrading material flow in the step b to pass through a second hydro-upgrading catalyst bed under the hydro-upgrading condition, and separating and fractionating the hydro-upgrading material flow to obtain hydro-upgrading high-pressure hydrogen-rich gas, a hydro-upgrading gas product, a hydro-upgrading naphtha product and a hydro-upgrading diesel product;
d. and c, mixing the first hydro-upgrading liquid material flow obtained in the step b with hydrogen, passing the mixture through a hydro-isomerization pour point depressing catalyst bed layer of a hydro-isomerization pour point depressing reactor under the hydro-isomerization pour point depressing condition, and separating and fractionating the hydro-isomerization pour point depressing material flow to obtain hydro-isomerization pour point depressing high-pressure hydrogen-rich gas, hydro-isomerization pour point depressing naphtha and hydro-isomerization pour point depressing diesel oil products.
2. The hydro-upgrading process of claim 1, further comprising step e: and d, mixing the hydro-upgrading high-pressure hydrogen-rich gas obtained in the step c with the hydro-pour point depressing high-pressure hydrogen-rich gas obtained in the step d for recycling.
3. The hydro-upgrading process of claim 1, wherein the diesel feedstock has a first boiling point of 100 to 260 ℃ and an end point of 300 to 450 ℃.
4. The hydro-upgrading process according to claim 3, wherein the diesel feedstock is selected from one or more of the group consisting of straight-run diesel, coker diesel, catalytic diesel, hydrotreated diesel, coal tar, direct coal liquefaction oil, indirect coal liquefaction oil, and shale oil.
5. The hydro-upgrading process according to claim 1, wherein the hydrofining catalyst in step a takes VIB group and/or VIII group metals as active components, and takes alumina or siliceous alumina as a carrier; based on the weight of the catalyst, the content of the VIB group metal is 10-35 wt% calculated by oxide, and the content of the VIII group metal is 3-15 wt% calculated by oxide; the properties are as follows: the specific surface area is 100 to 650m2The pore volume is 0.15 to 0.6 mL/g.
6. The hydro-upgrading process of claim 1, wherein the operating conditions of step a are: the reaction pressure is 3.0MPa to 15.0MPa, the reaction temperature is 300 ℃ to 430 ℃, and the liquid hourly volume space velocity is 0.2h-1～6.0h-1The volume ratio of hydrogen to oil is 100: 1-2000: 1.
7. The hydro-upgrading process of claim 1, wherein the hydro-upgrading catalyst comprises a group VIB and/or group VIII metal as an active component, and the catalyst support comprises one or more of alumina, siliceous alumina and a molecular sieve.
8. The hydro-upgrading process of claim 7, wherein the support for the catalyst comprises alumina and a molecular sieve; based on the weight of the catalyst, the content of the VIB group metal is 10-35 wt% calculated by oxide, and the content of the VIII group metal is calculated by oxide3 to 15 weight percent, 5 to 40 weight percent of molecular sieve and 10 to 80 weight percent of alumina; the specific surface area is 100m2/g～650m2The pore volume is 0.15mL/g to 0.50 mL/g.
9. The hydro-upgrading process of claim 8, wherein the catalyst used in the first hydro-upgrading catalyst bed is hydrogenation catalyst A, the catalyst used in the second hydro-upgrading catalyst bed is hydrogenation catalyst B, and the content percentage x of the molecular sieve in the hydrogenation catalyst A is1Less than the percentage content x of the molecular sieve in the hydrogenation catalyst B2。
10. The hydro-upgrading process of claim 9, wherein x is1Ratio x21-6 percentage points lower.
11. The hydro-upgrading process of claim 1, wherein the hydro-upgrading conditions are: the reaction pressure is 3.0MPa to 15.0MPa, the reaction temperature is 300 ℃ to 430 ℃, and the liquid hourly volume space velocity is 0.3h-1～15.0h-1The volume ratio of the hydrogen to the oil is 100: 1-2000: 1.
12. The hydro-upgrading process according to claim 1, wherein the hydroisomerization pour point depressing catalyst takes a group VIB and/or group VIII metal as an active component, and the catalyst carrier contains one or more of alumina, siliceous alumina and a molecular sieve.
13. The hydro-upgrading process of claim 12, wherein the catalyst support comprises alumina and a molecular sieve; based on the weight of the catalyst, the content of the VIB group metal is 10-35 wt% calculated by oxide, the content of the VIII group metal is 3-15 wt% calculated by oxide, the content of the molecular sieve is 5-40 wt%, and the content of the alumina is 10-80 wt%; the specific surface area is 100m2/g～650m2The pore volume is 0.15mL/g to 0.50 mL/g.
14. The hydro-upgrading process of claim 1, wherein the hydroisomerization pour point depressant operating conditions are: the reaction pressure is 3.0MPa to 15.0MPa, the reaction temperature is 200 ℃ to 430 ℃, and the liquid hourly volume space velocity is 0.3h-1～15.0h-1The volume ratio of the hydrogen to the oil is 100: 1-1500: 1.
15. The hydro-upgrading process according to claim 1, wherein the partial stream extracted in the step b accounts for 5 to 95wt% of the raw material oil in terms of liquid phase.
16. The hydro-upgrading process according to claim 1, wherein the partial stream extracted in the step b accounts for 10 to 80wt% of the raw material oil in terms of liquid phase.
17. The hydro-upgrading process of claim 1, wherein the bed of hydrofinishing catalyst, the first bed of hydro-upgrading catalyst and the second bed of hydro-upgrading catalyst are disposed within one hydrogenation reactor; or the hydrofining catalyst bed layer is arranged in a single hydrogenation reactor, and the first hydro-upgrading catalyst bed layer and the second hydro-upgrading catalyst bed layer are arranged in one hydro-upgrading reactor; or the hydrorefining catalyst bed layer and the first hydroupgrading catalyst bed layer are arranged in one hydroupgrading reactor, and the second hydroupgrading catalyst bed layer is arranged in the other hydroupgrading reactor.
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| CN103805270A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Production method of low-condensation point diesel oil |
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| CN103805270A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Production method of low-condensation point diesel oil |
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