CN109988638B - Hydrogenation process for flexibly producing low-condensation-point diesel oil - Google Patents
Hydrogenation process for flexibly producing low-condensation-point diesel oil Download PDFInfo
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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
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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Abstract
The invention discloses a hydrogenation process for flexibly producing low-condensation-point diesel oil. After the diesel raw material is hydrorefined, firstly passing through a hydroupgrading catalyst bed layer, and dividing the hydroupgrading material into two strands; separating a strand of material by a gas-liquid separator to obtain liquid, pumping the liquid out of the reactor, mixing the liquid with hydrogen, and entering a hydrogenation pour point depression reactor for pour point depression reaction; the other material is a mixture of gas in the reactor and liquid left after extraction, and the mixture continuously flows downwards through the hydroisomerization pour point depression catalyst bed; and respectively carrying out gas-liquid separation and fractionation on the obtained hydroisomerization pour point depression reaction material and the hydrogenation pour point depression reaction material to obtain diesel products with different specifications. The invention provides a hydrogenation coupling process for simultaneously producing more than two diesel oil products with different specifications on one set of hydrogenation process device for the first time, which can fully utilize the heat carried by partial heterogeneous pour point depressing materials to realize the coupling operation of a hydrogenation modification pour point depressing reactor and a hydrogenation pour point depressing reactor.
Description
Technical Field
The invention belongs to the field of petroleum refining, and particularly relates to a hydrogenation process for flexibly producing a low-condensation-point diesel product.
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.
Diesel oil fraction hydrogenation pour point depression technology, such as CN102051232A and CN1257107A, uses hydrofining catalyst and hydrogenation pour point depression catalyst, adopts a series flow to produce low pour point diesel oil product, but the yield of the diesel oil product is lower. CN102453531A, CN103805258A, CN103805254A and the like all use hydrofining catalysts and hydrodewaxing catalysts alternately, the condensation point of the obtained diesel oil product is low, but the yield of the diesel oil is low, and only one diesel oil product can be produced.
By adopting the hydrogenation technology CN105087063A, after diesel fraction is subjected to hydroisomerization and pour point depression, the diesel fraction is directly subjected to hydrogenation and pour point depression by utilizing reaction heat to produce a low-pour-point diesel product, but the process can only produce a diesel product with a pour point specification.
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 existing hydrogenation pour point depressing technology can greatly lower the pour point of a diesel product and can meet the index requirement of low-pour-point diesel, but the diesel yield is lower and is usually less than 90m%, the quality improvement range of the diesel product is not large, and the cetane number of the diesel product is reduced particularly when normal paraffin with high cetane number is cracked into gas or naphtha fraction. The product is single when the coupling hydrogenation technology is adopted. 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 hydrogenation process for flexibly producing low-freezing-point diesel, namely, a part of reaction liquid material flow is extracted from a gas-liquid separator arranged in the middle of a hydrogenation modification pour point depressing reactor, and the diesel raw oil is subjected to hydrogenation modification, hydrogenation isomerization pour point depressing and hydrogenation pour point depressing coupling methods to flexibly produce hydrogenation isomerization pour point depressing diesel products and hydrogenation pour point depressing diesel products with different freezing points.
The hydrogenation process for flexibly producing the low-condensation-point diesel oil comprises the following steps of:
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 hydro-upgrading catalyst bed under the hydro-upgrading condition to obtain a hydro-upgrading material flow, dividing the part of the reactant material flow into two parts, separating one part of the reactant material flow through a gas-liquid separator to obtain a hydro-upgrading liquid material flow, and pumping the hydro-upgrading liquid material flow out of the hydrogenation reactor;
c. b, allowing the residual hydrogenation modified material flow in the step b to pass through a hydrogenation isomerization pour point depressing catalyst bed layer under the hydrogenation isomerization pour point depressing condition, and separating and fractionating the hydrogenation isomerization pour point depressing material flow to obtain hydrogenation isomerization pour point depressing high-pressure hydrogen-rich gas, hydrogenation isomerization pour point depressing gas products, hydrogenation isomerization pour point depressing naphtha products and hydrogenation isomerization pour point depressing diesel products;
d. and b, mixing the hydrogenated modified liquid material flow obtained in the step b with circulating hydrogen, passing through a hydrogenation pour point depression catalyst bed under a hydrogenation pour point depression condition, and separating and fractionating the hydrogenated pour point depression material flow to obtain hydrogenation pour point depression high-pressure hydrogen-rich gas, hydrogenation pour point depression naphtha and hydrogenation pour point depression diesel products.
The hydrogenation process according to the invention may further comprise step e: and d, mixing the hydroisomerization pour point depressing high-pressure hydrogen-rich gas obtained in the step c with the hydrogenation pour point depressing high-pressure hydrogen-rich gas obtained in the step d for recycling.
S, N, O and other impurities in the raw oil of the diesel oil are effectively removed by a hydrofining catalyst, aromatic hydrocarbon is subjected to hydrogenation saturation to a certain extent, the ring-shaped hydrocarbon is subjected to partial ring opening reaction when a 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, one part of the hydrofining material flow is continuously subjected to hydroisomerization pour point depressing, the cetane number of the diesel oil is improved to the maximum extent, the branched chain alkane with a high pour point is changed into a branched chain alkane component with a low pour point, and a diesel oil product with a relatively high pour point and a high cetane number is obtained; and (3) reducing the condensation point of diesel after a part of the extracted hydro-upgrading material flow passes through a hydro-dewaxing catalyst to obtain a diesel product with a slightly lower cetane number and a very low condensation point.
Compared with the prior art, the hydrogenation process for flexibly producing the low-condensation-point diesel oil has the advantages that:
1. in the invention, the hydro-upgrading pour point depressing reaction part comprises at least one hydro-upgrading catalyst bed layer and at least one hydroisomerization pour point depressing catalyst bed layer. The effective distribution of the hydrogenation modified material strand can be realized by arranging the gas-liquid separator between two types of catalyst beds of the hydrogenation modified pour point depressing reactor and extracting a part of the modified liquid material out of the reactor, and the obtained material is subjected to different hydrogenation processes, so that the target diesel oil products with different pour points can be flexibly produced. 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 producing more than two diesel oil products with different specifications on one set of hydrogenation process device for the first time.
2. According to the invention, the hydro-upgrading material flow extracting device is arranged between the hydro-upgrading catalyst bed and the hydroisomerization pour point depressing catalyst bed of the hydro-upgrading pour point depressing reactor, the liquid material flow of the diesel raw material after hydro-refining and hydro-upgrading is extracted out of the reactor and is respectively sent into the hydro-upgrading pour point depressing reactors which are independently arranged for hydro-upgrading pour point depressing reaction, so that the pour point of the hydro-upgraded 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 and hydroisomerization pour point depression has high cetane number and slightly higher pour point; the diesel oil product obtained after hydrogenation modification and hydrogenation pour point depression has low pour point and relatively low cetane number; can respectively meet the requirements of producing high-quality diesel products with different specifications.
4. In the invention, impurities such as S, N in the raw oil are converted into H after hydrofining and hydro-upgrading2S and NH3Most of H is separated by a gas-liquid 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 hydrogenation pour point depressing catalyst is reduced, the reaction activity of the hydrogenation pour point depressing catalyst is improved, namely the reaction temperature required when the same pour point depressing effect is achieved is reduced, the liquid extracted from the hydrogenation modified pour point depressing reactor has 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 hydrogenation pour point depressing reactor for reaction and achieve the pour point depressing effect, and therefore the heat carried by the partial modified material is fully utilized, and the coupling operation of the hydrogenation pour point depressing reactor and the hydrogenation modified pour point depressing reactor is achieved.
Drawings
Fig. 1 is a schematic flow chart of the principle of the present invention. Wherein, a hydrofining reactor, a hydrogenation modification and isomerization pour point depressing reactor and a hydrogenation pour point depressing reactor are arranged.
Wherein: 1-raw oil, 2-hydrofining reactor, 3-hydrofining material flow, 4-hydrogenation modified pour point depression reactor, 5-hydrogenation pour point depression raw material flow, 6-hydrogenation isomerization pour point depression material flow, 7-hydrogenation pour point depression reactor, 8-hydrogenation isomerization pour point depression high-pressure separator, 9-hydrogenation pour point depression high-pressure separator, 10-hydrogenation isomerization pour point depression fractionating tower, 11-hydrogenation pour point depression fractionating tower, 12-hydrogenation isomerization pour point depression gas product, 13-hydrogenation isomerization pour point depression naphtha product, 14-hydrogenation isomerization pour point depression diesel oil product, 15-hydrogenation pour point depression gas product, 16-hydrogenation pour point depression naphtha product, 7-hydrogenation pour point depression diesel oil product, 18-hydrogenation isomerization pour point depression high-pressure separator gas product, 19-hydrogenation pour point depression high-pressure separator gas product, 20-make up hydrogen, 21-hydro-upgrading pour point depressing recycle hydrogen, 22-hydro-depressing 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, 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. 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 step B is a conventional diesel hydro-upgrading catalyst, and generally takes VIB group and/or VIII group metals as active groupsIn general, the group VIB metal is Mo and/or W, and the group VIII metal is Co and/or Ni. The catalyst carrier contains one or more of alumina, silicon-containing alumina and molecular sieve, preferably molecular sieve, which may be 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%; the 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 hydrogenation modification catalyst, certain hydrogenation activity and certain cracking activity are required, and both hydrogenation saturation of olefin and aromatic hydrocarbon in diesel oil fraction and ring-opening reaction of saturated aromatic hydrocarbon are required. 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.
The hydroisomerization pour point depressing catalyst in the step c 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 contains one or more of alumina, siliceous alumina and molecular sieve, preferably contains 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, FC-20 and the like 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 straight-chain paraffin production are requiredAnd (4) isomerization reaction. 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 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.
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 mass ratio of the extracted part of the liquid phase material flow to the raw oil is 5-95 wt%, and preferably 10-80 wt%.
The separation described in step c generally comprises a hydroisomerization pour point depression high pressure separator and a low pressure separator. Wherein the high-pressure separator separates to obtain the hydroisomerization pour point depression 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.
The fractionation described in step c is carried out in a hydroisomerized pour point depressant fractionation column system. And fractionating the low-pressure liquid product in a fractionating tower to obtain a hydroisomerization pour point depressing naphtha product and a hydroisomerization pour point depressing diesel product.
The hydrogenation pour point depression catalyst in the step d is a conventional hydrogenation pour point depression 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 ZSM-5, ZSM-11, ZSM-22 or ZSM-35 type molecular sieve, and preferably is ZSM-5 molecular sieve. Based on the weight of the catalyst, the total metal content is 1wt percent to 20wt percent calculated by oxide,the content of the molecular sieve is 40wt% -85 wt%, and the content of the adhesive is 10wt% -40 wt%. The binder is conventional in the art, and alumina is preferred in the present invention. The main catalysts comprise 3881 and FDW-1 catalysts which are developed by the petrochemical research institute. The hydrodewaxing conditions may be conventional, and are generally: the reaction pressure is 3.0MPa to 15.0MPa, the reaction temperature is 300 ℃ to 440 ℃, and the liquid hourly volume space velocity is 0.3h-1～12.0h-1The volume ratio of the hydrogen to the oil is 100: 1-1500: 1.
The separation in step d is carried out in a hydrodewaxing high pressure separator and a low pressure separator. The hydrogenation pour point depression high-pressure separator separates to obtain hydrogenation pour point depression 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 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 hydrodewaxing naphtha product and a hydrodewaxing diesel product.
The hydroisomerization pour point depressing gas product and the hydrogenation 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 hydroisomerized pour point depressing naphtha product and the hydroisomerized pour point depressing naphtha product in the step c and the step d can be used as the 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.
In the invention, the hydrofining catalyst bed, the hydrogenation modified catalyst bed and the hydroisomerization pour point depression catalyst bed can be arranged in one hydrogenation reactor, for example, three catalyst beds can be arranged in one hydrogenation reactor in sequence; or the hydrofining catalyst bed layer is arranged in a single hydrogenation reactor, and the hydro-upgrading catalyst bed layer and the hydroisomerization pour point depression catalyst bed layer are arranged in one hydrogenation reactor; or the hydrofining catalyst bed layer and the hydro-upgrading catalyst bed layer are arranged in one hydrogenation reactor, and the hydroisomerization pour point depression catalyst bed layer is arranged in the other hydrogenation reactor. The hydrogenation pour point depression catalyst bed layer is arranged in a single hydrogenation reactor.
With reference to fig. 1, the method of the present invention is as follows: raw oil 1 is firstly mixed with recycle hydrogen and enters a hydrofining reactor 2, a hydrofining material flow 3 enters a hydrofining pour point depressing reactor 4, a reaction material flow passing through a first hydrofining catalyst bed layer is pumped out a hydrofining pour point depressing liquid material flow 5 through a gas-liquid separator 23, the material flow after the hydrofining pour point depressing material flow 5 is pumped out continues to enter a subsequent hydroisomerizing pour point depressing catalyst bed layer, a hydroisomerizing pour point depressing generated material flow 6 enters a hydroisomerizing pour point depressing high-pressure separator 8 for gas-liquid separation, the separated liquid enters a fractionating tower 10 for fractionation to obtain a hydroisomerizing pour point depressing gas product 12, a hydroisomerizing pour point depressing naphtha product 13 and a hydroisomerizing pour point depressing diesel oil product 14, the hydroisomerizing pour point depressing liquid material flow 5 and the recycle hydrogen 22 are mixed and then enter a hydrofining pour point depressing reactor 7, and the generated material flow passing through the hydrofining pour point depressing catalyst bed layer, the separated liquid enters a fractionating tower 11 to be fractionated to obtain a hydrogenation pour point depression gas product 15, a hydrogenation pour point depression naphtha product 16 and a hydrogenation pour point depression diesel product 17, the hydrogenation isomerization pour point depression gas product 12 and the hydrogenation pour point depression gas product 15 can be independently used as products or can be mixed to obtain a mixed gas product, the hydrogenation isomerization pour point depression naphtha product 13 and the hydrogenation pour point depression naphtha product 16 can be independently used as products or can be mixed to obtain a mixed naphtha product, and the gas 18 separated by the hydrogenation isomerization pour point depression high-pressure separator 8 and the gas 19 separated by the hydrogenation pour point depression high-pressure separator 9 are mixed and then are mixed with a supplementary hydrogen 20 through a recycle hydrogen compressor to obtain recycle hydrogen.
The embodiments and effects of the present invention are described below by way of examples.
Examples 1 to 3
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 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; the catalyst 3881 is a hydrogenation pour point depressing catalyst which is developed and produced by China petrochemical company Limited and comforts petrochemical research institute and contains ZSM-5 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 hydroisomerization pour point depressing process of the present invention can achieve the purpose of producing diesel oil with different properties by extracting a part of the reactant flow from the hydroisomerization pour point depressing reactor and using the hydroisomerization pour point depressing catalyst and the hydroisomerization pour point depressing catalyst, and the production mode is flexible.
Claims (15)
1. A hydrogenation process for flexibly producing low-condensation-point diesel oil 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 hydro-upgrading catalyst bed under the hydro-upgrading condition to obtain a hydro-upgrading material flow, dividing the part of the reactant material flow into two parts, separating one part of the reactant material flow through a gas-liquid separator to obtain a hydro-upgrading liquid material flow, and pumping out the hydro-upgrading liquid material flow from a hydrogenation reactor;
c. b, allowing the residual hydrogenation modified material flow in the step b to pass through a hydrogenation isomerization pour point depressing catalyst bed layer under the hydrogenation isomerization pour point depressing condition, and separating and fractionating the hydrogenation isomerization pour point depressing material flow to obtain hydrogenation isomerization pour point depressing high-pressure hydrogen-rich gas, hydrogenation isomerization pour point depressing gas products, hydrogenation isomerization pour point depressing naphtha products and hydrogenation isomerization pour point depressing diesel products;
d. and b, mixing the hydrogenated modified liquid material flow obtained in the step b with circulating hydrogen, passing through a hydrogenation pour point depression catalyst bed under a hydrogenation pour point depression condition, and separating and fractionating the hydrogenated pour point depression material flow to obtain hydrogenation pour point depression high-pressure hydrogen-rich gas, hydrogenation pour point depression naphtha and hydrogenation pour point depression diesel products.
2. The hydrogenation process of claim 1, further comprising step e: and d, mixing the hydroisomerization pour point depressing high-pressure hydrogen-rich gas obtained in the step c with the hydrogenation pour point depressing high-pressure hydrogen-rich gas obtained in the step d for recycling.
3. The hydrogenation process according to claim 1, wherein the initial boiling point of the diesel feedstock is 100 to 260 ℃ and the final boiling point is 300 to 450 ℃.
4. The hydrogenation process according to claim 3, wherein the diesel feedstock is at least one selected from the group consisting of straight-run diesel, coker diesel, catalytic diesel, hydrotreated diesel, coal tar, coal direct liquefaction oil, coal indirect liquefaction oil, and shale oil.
5. The hydrogenation 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; group VIB metal content based on weight of catalyst10-35 wt% calculated by oxide, and 3-15 wt% calculated by oxide for group VIII metal; 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 hydrogenation process of claim 1, wherein the hydrofinishing 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 hydrogenation process of claim 1, wherein the hydro-upgrading catalyst of step B comprises a group VIB and/or group VIII metal as an active component, and the catalyst carrier 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.
8. The hydrogenation process of claim 1, wherein the hydro-upgrading conditions are: the reaction pressure is 3.0-15.0 MPa, and the reaction temperature is 300 ℃4The liquid hourly space velocity is 0.3h at 30 DEG C-1～15.0h-1The volume ratio of the hydrogen to the oil is 100: 1-2000: 1.
9. The hydrogenation process according to claim 1, wherein the mass ratio of the liquid phase material flow extracted in the step b to the raw material oil is 5-95 wt%.
10. The hydrogenation process according to claim 9, wherein the mass ratio of the liquid phase material flow extracted in the step b to the raw material oil is 10-80 wt%.
11. The hydrogenation process according to claim 1,the hydroisomerization pour point depressing catalyst takes VIB group and/or VIII group metal as an active component, and a catalyst carrier contains 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.
12. The hydrogenation process of claim 1, wherein said hydroisomerization pour point depression conditions are: the reaction pressure is 3.0MPa to 15.0MPa, the reaction temperature is 300 ℃ to 430 ℃, and the liquid hourly space velocity is 0.3h-1～15.0h-1The volume ratio of the hydrogen to the oil is 100: 1-2000: 1.
13. The hydrogenation process according to claim 1, wherein the hydrogenation pour point depressing catalyst is a catalyst containing metals of VIB group and/or VIII group as active components, the catalyst carrier contains alumina and a molecular sieve, the molecular sieve is a ZSM-5, ZSM-11, ZSM-22 or ZSM-35 type molecular sieve, and based on the weight of the catalyst, the total metal content is 1wt% -20 wt% calculated by oxide, the molecular sieve content is 40wt% -85 wt%, and the alumina content is 10wt% -40 wt%.
14. The hydrogenation process of claim 1, wherein the hydrodewaxing conditions are: the reaction pressure is 3.0MPa to 15.0MPa, the reaction temperature is 300 ℃ to 440 ℃, and the liquid hourly space velocity is 0.3h-1～12.0h-1The volume ratio of the hydrogen to the oil is 100: 1-1500: 1.
15. The hydrogenation process according to claim 1, wherein the hydrofinishing catalyst bed, the hydro-upgrading catalyst bed and the hydroisomerization pour point depression catalyst bed are arranged in a reactor; or the hydrofining catalyst bed layer is arranged in a single hydrofining reactor, and the hydro-upgrading catalyst bed layer and the hydroisomerization pour point depression catalyst bed layer are arranged in one hydrogenation reactor; or the hydrofining catalyst bed layer, the hydro-upgrading catalyst and the hydroisomerization pour point depression catalyst bed layer are respectively arranged in the three hydrogenation reactors.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1289831A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Process for preparing high-quality low-coagulation diesel oil with high hexadecane value |
| CN101724457A (en) * | 2008-10-29 | 2010-06-09 | 中国石油化工股份有限公司 | Hydrogenation combined method for diesel oil |
| CN102942958A (en) * | 2012-11-12 | 2013-02-27 | 大连理工大学 | Long chain paraffin hydrogenation heterogeneous condensation freezing point depressing method and catalyst thereof |
| CN103773455A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Animal and vegetable oil-catalytic diesel oil combined hydrogenation method |
| 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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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1289831A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Process for preparing high-quality low-coagulation diesel oil with high hexadecane value |
| CN101724457A (en) * | 2008-10-29 | 2010-06-09 | 中国石油化工股份有限公司 | Hydrogenation combined method for diesel oil |
| CN103773455A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Animal and vegetable oil-catalytic diesel oil combined hydrogenation method |
| 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 |
| CN102942958A (en) * | 2012-11-12 | 2013-02-27 | 大连理工大学 | Long chain paraffin hydrogenation heterogeneous condensation freezing point depressing method and catalyst thereof |
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