CN109652122B - Deep hydrogenation denitrification method for inferior high-nitrogen heavy distillate oil - Google Patents

Deep hydrogenation denitrification method for inferior high-nitrogen heavy distillate oil Download PDF

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CN109652122B
CN109652122B CN201811650785.1A CN201811650785A CN109652122B CN 109652122 B CN109652122 B CN 109652122B CN 201811650785 A CN201811650785 A CN 201811650785A CN 109652122 B CN109652122 B CN 109652122B
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catalyst
carrier
hydrogenation
boehmite
temperature
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CN109652122A (en
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于海斌
肖寒
张景成
朱金剑
赵培江
张国辉
李晓静
张玉婷
宋国良
张尚强
潘月秋
陈永生
彭雪峰
李佳
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CNOOC Energy Technology and Services Ltd
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
CNOOC Zhoushan Petrochemical Co Ltd
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CNOOC Energy Technology and Services Ltd
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
CNOOC Zhoushan Petrochemical Co Ltd
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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
    • 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
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • 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
    • C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)

Abstract

The invention provides a method for deep hydrodenitrogenation of inferior high-nitrogen heavy distillate oil, which is characterized in that raw oil and hydrogen are mixed and enter a hydrogenation reactor together for hydrogenation reaction, and reaction products are cooled and separated to obtain a hydrogen-rich component and a low-nitrogen liquid product. The method deeply removes the nitride of the condensed ring aromatic hydrocarbon substituted nitrogen heterocycle by grading hydrogenation catalysts with different functions and utilizing the temperature gradient distribution characteristic of an adiabatic hydrogenation reactor to cooperatively play the role of the catalysts, thereby providing a low-nitrogen raw material for hydrocracking and catalyst cracking catalysts.

Description

Deep hydrogenation denitrification method for inferior high-nitrogen heavy distillate oil
Technical Field
The invention relates to the technical field of oil refining hydrogenation catalysts, in particular to a deep hydrogenation and denitrification method for inferior high-nitrogen heavy distillate oil.
Background
The hydrocracking technology is a comprehensive processing technology integrating heavy oil lightening and clean oil production, and the core of the hydrocracking technology is a hydrocracking catalyst. The hydrocracking catalyst has strict requirements on the nitrogen content in the raw material, particularly the basic nitrogen content, because the hydrocracking catalyst contains an acidic molecular sieve. Before the hydrocracking reaction, the raw material is pretreated, and subjected to hydrogenation impurity removal, hydrogenation denitrification and polycyclic aromatic hydrocarbon hydrogenation saturation. In recent years, with the increasing weight and deterioration of world raw oil, catalytic heavy diesel oil and coking distillate oil in hydrocracking raw materials show the characteristics of high impurities, high nitrogen content and high aromatic hydrocarbon content, and in addition, a small amount of medium-low temperature coal tar can be subjected to refining due to low price, so that deep hydrodenitrogenation is required to be performed on the poor distillate oil in order to provide a high-quality low-nitrogen raw material for a hydrocracking catalyst.
Chinese invention patent CN105524655A discloses a method for heavy oil hydrodenitrogenation, which comprises: under the condition of hydrotreatment, in the presence of hydrogen, sequentially contacting raw oil containing heavy oil with a hydrodemetallization catalyst, a hydrodesulfurization catalyst, a hydrogenation saturation catalyst and a hydrodenitrogenation catalyst to obtain hydrogenated product oil; wherein, after contacting with the hydrodesulfurization catalyst and before contacting with the hydrogenation saturation catalyst, the product obtained after contacting with the hydrodesulfurization catalyst is subjected to gas stripping to obtain a liquid phase material and a gas phase material containing hydrogen, wherein the contacting with the hydrodenitrogenation catalyst is carried out in the presence of a sulfur-containing material flow. The method can improve the heavy oil hydrogenation rate while obviously improving the heavy oil denitrification rate, improve the yield of liquid products in the heavy oil hydrogenation process and further save the production cost.
Chinese invention patent CN1448470 discloses a heavy oil fixed bed hydrodenitrogenation method, raw oil is contacted with a hydrodenitrogenation catalyst in the presence of hydrogen to react, the adopted hydrodenitrogenation catalyst is a catalyst with two pore diameters of large pore and small pore, the average pore diameter of the large pore denitrification catalyst is between 8nm and 25nm, the surface area is between 100m2/g and 270m2/g, and the pore volume is 0.30 to 0.75cm 3/g; the average pore diameter of the small-pore-diameter denitrification catalyst is between 4nm and 10nm, the surface area is between 150m2/g and 320m2/g, and the pore volume is between 0.30mL/g and 0.55 mL/g; wherein the loading amount of the large-aperture denitrification catalyst accounts for 3-30V percent of the whole denitrification catalyst. The invention is characterized in that: the resource utilization rate of the existing catalyst is improved, and the service life of the whole catalyst bed layer is prolonged; the diffusion effect of reactant flow in the catalyst bed layer is improved, so that the metal holding capacity of the catalyst is improved, the carbon deposition of the catalyst bed layer is slowed down, and the over-quick rise of the pressure drop of the catalyst bed layer and the generation of local hot spots are effectively delayed.
The Chinese invention patent CN106622270A discloses a hydrodenitrogenation catalyst, which contains an active metal component and a modified hydrogenation catalyst carrier, wherein the modified hydrogenation catalyst carrier comprises a carrier and a metal additive and an acid additive loaded on the carrier, the metal additive and the acid additive are distributed on the carrier in a layered manner, the metal additive is arranged on a first shell layer, the acid additive is arranged on a first nuclear layer, the metal additive is an IA group metal component and/or an IIA group metal component, and the acid additive is at least one component selected from F, P and B. The invention of Chinese invention patent CN106622269A relates to a hydrodenitrogenation catalyst, which contains active metal components and a modified hydrogenation catalyst carrier, and is characterized in that the modified hydrogenation catalyst carrier is prepared by the following method, and the method comprises the following steps: the carrier subjected to the hydrothermal treatment is repeatedly impregnated and dried in sequence, and the dried product obtained at the last time is calcined.
The invention discloses a hydrodenitrogenation catalyst for medium-low temperature coal tar and a preparation method thereof, which belong to Chinese patent CN 102773113A. The catalyst carrier is gamma-Al 2O3 and is loaded with Ni and W metal active components and P auxiliary agent; in the catalyst, the pores with the pore diameter of 5-10 nm account for 24-37%, the pores with the pore diameter of 10-20 nm account for 22-30%, the pore volume is 0.32-0.45 mL/g, and the specific surface area is 198.2-268.1 m 2/g. According to the catalyst, two carbon blacks, namely NEROX505 and FW200 are used as pore-enlarging agents, so that the distribution ratio of the pore diameters of the catalyst between 5nm and 10nm to 20nm is reasonably controlled, and the prepared catalyst is small in pore diameter and concentrated in distribution, so that the loading capacity of active metals and auxiliaries of the catalyst can be well improved. Chinese invention patent CN103386321A discloses a coal tar hydrodenitrogenation catalyst and a preparation method thereof, wherein the catalyst consists of an active component, an auxiliary agent and a carrier, and the active component consists of tungsten trioxide and nickel oxide; the carrier consists of active carbon, alumina and H beta molecular sieve. The catalyst is easy to vulcanize and has higher activity; the pore structure of the activated carbon is adjustable, which is beneficial to the conversion of colloid components and the removal of nitrogen impurities in the coal tar, thereby slowing down the carbon deposition of the catalyst. Compared with the conventional catalyst, the prepared catalyst has more excellent hydrodenitrogenation performance.
In the prior art, the hydrodenitrogenation activity is modulated only from a catalyst pore structure, a hydrogenation active center and an acid center. The nitrides difficult to remove in the poor distillate oil are aromatic rings substituted nitrogen heterocycles and are divided into non-basic nitrides and basic nitrides. The non-alkaline nitride has high adsorption difficulty in a hydrogenation catalyst, five-membered nitrogen heterocycle is required to be hydrogenated and saturated into a five-membered cyclohexane structure during reaction, the non-alkaline nitride is converted into an alkaline nitride, then C-N bond hydrogenolysis is carried out, and nitrogen heterocycle hydrogenation is used as a control step; the hydrogenation saturation activity of the basic nitride is higher than that of the non-basic nitride, but the hydrogenolysis activity of the C-N bond of the six-membered naphthenic structure is lower than that of the five-membered naphthenic structure, and the C-N hydrogenolysis reaction is a control step. The single type of hydrodenitrogenation catalyst is difficult to achieve the purpose of deep denitrification.
Disclosure of Invention
Aiming at the technical defects in the prior art and the hydrogenation reaction characteristics of non-alkaline nitrides and alkaline nitrides, the invention provides a method for deep hydrodenitrogenation of inferior high-nitrogen heavy distillate oil by preparing catalysts with high hydrogenation activity and high hydrogenolysis activity and grading different active hydrodenitrogenation catalysts according to the nitrogen type distribution of an oil product to achieve the aim of deep denitrification of inferior high-nitrogen distillate oil.
The invention relates to a method for deeply hydrodenitrifying inferior high-nitrogen heavy distillate oil, which comprises the steps of mixing the high-nitrogen heavy distillate oil with hydrogen, allowing the mixture to enter a hydrogenation reactor for reaction, cooling and separating reaction products to obtain a hydrogen-rich component and a low-nitrogen liquid product, wherein the hydrogenation reactor is provided with three reaction areas, a hydrogenation protection catalyst is filled in a first reaction area for removing impurities such as metal, colloid and the like, a type I hydrodenitrifying catalyst with high hydrogenation activity is filled in a second reaction area, and a type II hydrodenitrifying catalyst with high hydrogenolysis activity is filled in a third reaction area; the filling volume percentages of the three reaction zones are respectively 5-20 v%, 30-60 v% and 20-50 v% on the basis of the volume of the whole catalyst;
the hydrogenation protective agent consists of a metal component and a carrier, and the active components are NiO and MoO3The carrier is prepared by molding a macroporous alumina precursor; NiO and MoO in the hydrogenation protective agent3The total content is 6-20%, and the specific surface area is 100-240 m2A pore volume of 0.60 to 1.0 cm/g3The per gram, the average pore diameter is 12-20 nm, and the mechanical strength is not lower than 120N/cm;
the I-type hydrodenitrogenation catalyst consists of a carrier, active metals and a complexing agent, wherein the active metals are NiO and MoO3With WO3One or more of the metal components, wherein the total metal mass content is 24.0-36.0%; the complexing agent is one or more of dihydric alcohol, polyhydric alcohol, organic acid, organic amine and organic phosphorus, and the mass content of the complexing agent is 6-15%; the carrier is prepared from modified pseudo-boehmite and macroporous pseudo-boehmite, wherein the modified pseudo-boehmite and macroporous pseudo-boehmiteThe mass ratio of the diaspore to the diaspore is 0.5-1.0: 1.0; the preparation method of the I-type hydrodenitrogenation catalyst comprises the following steps:
1) uniformly mixing the modified pseudo-boehmite, the macroporous pseudo-boehmite and the extrusion aid in a certain ratio, adding inorganic and organic acid solutions, kneading into a plastic body, performing extrusion forming and shaping, and finally drying at 80-180 ℃ for 2-12 hours and roasting at 400-600 ℃ for 2-8 hours to obtain a carrier;
2) adding deionized water into an impregnation tank, sequentially adding a complexing agent, an active metal precursor and an auxiliary agent, uniformly stirring and heating until the complexing agent, the active metal precursor and the auxiliary agent are dissolved, and obtaining a stable impregnation solution after constant volume;
3) loading active metal onto a carrier by adopting isometric impregnation, placing the cultured catalyst under a vacuum condition for dehydration, wherein the vacuum degree is less than 20kPa, the dehydration temperature is 60-120 ℃, the dehydration time is 0.5-6.0 h, then placing the catalyst into a microwave activation furnace for activation, the activation temperature is 150-300 ℃, the activation time is 10-120 min, and obtaining the I-type hydrodenitrogenation catalyst after the activation is finished;
the II type hydrodenitrogenation catalyst consists of a carrier, active metal and an auxiliary agent, wherein the active metal is NiO or MoO3With WO3One or more of the above-mentioned compounds, the total metal mass content is 16.0-28.0%, the carrier is prepared from modified pseudo-boehmite and molecular sieve/amorphous silica-alumina composite material, the mass ratio of the modified pseudo-boehmite to the molecular sieve/amorphous silica-alumina composite material is 1.5-5.0: 1.0; the preparation method of the II-type hydrodenitrogenation catalyst comprises the following steps:
1) pulping the modified pseudo-boehmite and the molecular sieve/amorphous silica-alumina composite material according to a certain proportion, then carrying out filter pressing, adding a high-viscosity agent and an extrusion aid, uniformly mixing, kneading into a plastic body, carrying out extrusion forming and shaping, and finally drying at the temperature of 80-180 ℃ for 2-12 hours and roasting at the temperature of 400-600 ℃ for 2-8 hours to obtain a carrier;
2) adding deionized water into an impregnation tank, sequentially adding a complexing agent, an active metal precursor and an auxiliary agent, uniformly stirring and heating until the complexing agent, the active metal precursor and the auxiliary agent are dissolved, and obtaining a stable impregnation solution after constant volume;
3) loading active metal onto a carrier by adopting equal-volume impregnation, drying the cultured catalyst at the drying temperature of 80-150 ℃ for 2.0-8.0 h, then roasting and activating at the activating temperature of 350-550 ℃ for 0.5-4.0 h, and obtaining the II-type hydrodenitrogenation catalyst after activation.
According to the technical scheme of the invention, the high-nitrogen heavy distillate oil comprises one or more of coking heavy diesel oil, coking wax oil, catalytic cracking heavy diesel oil and medium-low temperature coal tar, wherein the total nitrogen content in the oil product is not less than 3000 mu g/g, and the basic nitrogen content is not less than 800 mu g/g.
According to the technical scheme of the invention, the hydrogenation reaction conditions are as follows: hydrogen partial pressure of 6.0-14.0 MPa, hydrogen-oil volume ratio of 400-1500 Nm3/m3The volume airspeed is 0.2-4.0 h-1The temperature of the first reaction zone is 200-360 ℃, the temperature of the second reaction zone is 280-400 ℃, and the temperature of the third reaction zone is 320-430 DEG C
According to the technical scheme of the invention, the specific surface area of the type I hydrodenitrogenation catalyst is 140-260 m2Per g, pore volume of 0.35-0.55 cm3The content of the pore diameter in the range of 6-12 nm is more than or equal to 80 percent.
According to the technical scheme of the invention, the specific surface area of the II-type hydrodenitrogenation catalyst is 180-340 m2A pore volume of 0.35-0.60 cm/g3The total acid amount is 0.3-0.8 mmol/g, and the content of the medium-strength B acid accounts for 40-70% of the total acid amount.
According to the technical scheme of the invention, the modified pseudo-boehmite is a pseudo-boehmite material modified by one or more of boron, phosphorus, silicon, titanium and zirconium elements; the macroporous pseudo-boehmite is synthesized by a hydrothermal crystal transformation method, and the specific surface area is 280-400 m2A pore volume of 1.0-1.6 cm3The content of the pore diameter in the range of 10-16 nm is more than or equal to 70 percent; the molecular sieve/amorphous silica-alumina composite material is a composite material synthesized by taking a dodecahedron Y, Beta or SAPO-5 molecular sieve as a core and wrapping the molecular sieve with amorphous silica-alumina.
The invention relates to a deep hydrodenitrogenation method for inferior high-nitrogen heavy distillate oil, which aims at the hydrogenation reaction characteristics of non-alkaline nitrides and achieves the purpose of deep denitrification of the inferior high-nitrogen distillate oil by grading different active hydrodenitrogenation catalysts according to the nitrogen type distribution of an oil product.
Detailed Description
The process of the present invention is further illustrated below with reference to specific examples.
Example 1
This example provides a density of 896kg/m3The hydrodenitrogenation method of the mixed raw material of the coking heavy diesel oil and the catalytic cracking heavy diesel oil (raw oil 1, distillation range temperature 200-400 ℃) with the total nitrogen content of 3820 mu g/g and the basic nitrogen content of 1330 mu g/g.
The proportions of the constituents of the catalyst in example 1, based on the total mass of the catalyst, are as follows:
hydrogenation protection catalyst (C-11): NiO: 2.0 wt%, MoO3：8.0wt％，P2O5: 0.8 wt% and the balance Al2O3；
Type I hydrodenitrogenation catalyst (C-12): NiO: 4.0 wt%, MoO3：18.0wt％，WO3：6.0wt％，P2O5: 2.5 wt%, complexing agent content 8.0 wt%, silicon and phosphorus modified alumina (SiO in it)2Content 2.0 wt%, P2O5Content 4.0 wt.%) 35.0 wt.% and Al as component2O3：
Type II hydrodenitrogenation catalyst (C-13): : NiO: 4.8 wt%, MoO3：18.0wt％，P2O5: 1.2 wt%, SAPO-5/amorphous silica-alumina composite: 30.0 wt%, and the balance of silicon-modified alumina (wherein SiO)2Content 4.0 wt%).
Preparation of catalyst C-12:
269.0g of silicon-phosphorus modified pseudo-boehmite (Zhonghai oil Tianjin chemical research design institute Co., Ltd., dry basis content of 75%) and 284.0g of macroporous pseudo-boehmite (Zhonghai oil Tianjin chemical research design institute Co., Ltd., dry basis content of 70%) are mixed with 12.0g of extrusion aid uniformly, 505.0g of acid solution prepared from nitric acid, citric acid and water is added, then the mixture is kneaded into a plastic body, the plastic body is extruded and shaped, and finally the plastic body is dried at 120 ℃ for 4h and roasted at 500 ℃ for 4h to obtain a clover-shaped carrier ZC-12 with the diameter of 1.5 mm;
adding deionized water into the impregnation tank, preparing NiO and MO by adopting basic nickel carbonate, molybdenum trioxide, ammonium metatungstate, phosphoric acid, ethylene diamine tetraacetic acid and glycerol to prepare the catalyst according to the stoichiometric ratio3、WO3And P2O5Uniformly spraying the impregnation liquid on a C-12 catalyst carrier by adopting an isometric impregnation method, placing the cultured catalyst under a vacuum condition for dehydration, wherein the vacuum degree is 10kPa, the dehydration temperature is 100 ℃, the dehydration time is 4.0h, then placing the catalyst in a microwave activation furnace for activation, the activation temperature is 180 ℃, the activation time is 30min, and obtaining the catalyst C-12 after the activation is finished.
Preparation of catalyst C-13:
336.0g of silicon modified pseudo-boehmite (72 percent of dry basis content, available from Zhonghai oil Tianjin chemical research design institute Co., Ltd.) and 186.0g of SAPO-5/amorphous silica-alumina composite material (85 percent of dry basis content, available from Zhonghai oil Tianjin chemical research design institute Co., Ltd.) are pulped, filter-pressed until the dry basis content reaches 32 wt%, put into a kneading machine, added with a high-viscosity agent and an extrusion aid to be uniformly mixed, kneaded into a plastic body, extruded and shaped, and finally dried at 150 ℃ for 3h and roasted at 550 ℃ for 3h to obtain a clover-shaped carrier ZC-13 with the diameter of 1.5 mm;
adding deionized water into a dipping tank, preparing NiO and MO by adopting basic nickel carbonate, molybdenum trioxide, phosphoric acid and citric acid to prepare the catalyst according to the stoichiometric ratio3And P2O5Loading active metal on the carrier by adopting equal-volume impregnation, drying the cultured catalyst at the drying temperature of 120 ℃ for 4.0h, then roasting and activating at the activation temperature of 480 ℃ for 3.0h, and obtaining the catalyst C-13 after the activation is finished.
According to the catalyst filling scheme in the reactor, the filling volume ratio of the catalyst C-11 in the first reaction zone is 8 percent, the filling volume ratio of the catalyst C-12 in the second reaction zone is 55 percent, and the filling volume ratio of the catalyst C-13 in the third reaction zone is 37 percent based on the volume of the whole catalyst.
The hydrodenitrogenation reaction conditions are as follows: hydrogen partial pressure 8.0MPa, hydrogen-oil volume ratio 600Nm3/m3And the volume space velocity is 1.5h-1The temperature of the first reaction zone was 320 ℃, the temperature of the second reaction zone was 345 ℃ and the temperature of the third reaction zone was 370 ℃. The hydrodenitrogenation reaction results are shown in table 1.
Example 2
This example provides a density of 928kg/m3The hydrodenitrogenation method of the coker gas oil (with the distillation range temperature of 350-500 ℃) with the total nitrogen content of 6580 mu g/g and the basic nitrogen content of 2160 mu g/g.
The proportions of the constituents of the catalyst in example 2, based on the total mass of the catalyst, are as follows:
hydrogenation protection catalyst (C-21): NiO: 2.5 wt%, MoO3：10.0wt％，P2O5:1.0 wt%, the balance being Al2O3；
Type I hydrodenitrogenation catalyst (C-22): NiO: 4.5 wt%, MoO3：14.0wt％，WO3：12.0wt％，P2O5: 3.0 wt%, complexing agent content 9.0 wt%, silicon-zirconium modified alumina (SiO in it)2Content of 2.0 wt%, ZrO2Content 6.0 wt.%) 28.0 wt.% and Al as component2O3：
Type II hydrodenitrogenation catalyst (C-23): : NiO: 6.0 wt%, MoO3：12.0wt％，WO3：6.0wt％，P2O5: 1.5 wt%, Beta/amorphous silica-alumina composite: 25.0 wt%, and the balance of silicon-modified alumina (wherein SiO)2Content 2.0 wt%);
preparation of catalyst C-22:
uniformly mixing 234.0g of silicon-zirconium modified pseudo-boehmite (Zhonghai oil Tianjin chemical research design institute Co., Ltd., dry basis content of 72%) and 322.0g of macroporous pseudo-boehmite (Zhonghai oil Tianjin chemical research design institute Co., Ltd., dry basis content of 72%) with 9.0g of extrusion aid, adding 520.0g of acid solution prepared from nitric acid, acetic acid and water, kneading into a plastic body, performing extrusion forming and shaping, and finally drying at 120 ℃ for 4h and roasting at 550 ℃ for 3h to obtain a butterfly-shaped carrier ZC-22 with the diameter of 1.5 mm;
adding deionized water into a dipping tank, preparing NiO and MO by adopting basic nickel carbonate, molybdenum trioxide, ammonium metatungstate, phosphoric acid, nitrilotriacetic acid and triethanolamine according to the stoichiometric ratio of the catalyst3、WO3And P2O5Uniformly spraying the impregnation liquid on a C-22 catalyst carrier by adopting an isometric impregnation method, placing the cultured catalyst under a vacuum condition for dehydration with the vacuum degree of 15kPa, the dehydration temperature of 150 ℃ and the dehydration time of 1.5h, then placing the catalyst in a microwave activation furnace for activation with the activation temperature of 220 ℃ and the activation time of 60min, and obtaining the catalyst C-22 after the activation is finished.
Preparation of catalyst C-23:
pulping 380.0g of silicon-modified pseudo-boehmite (70% of dry basis content, available from Zhonghai oil Tianjin chemical research design institute Co., Ltd.) and 158.0g of Beta/amorphous silica-alumina composite material (85% of dry basis content, available from Zhonghai oil Tianjin chemical research design institute Co., Ltd.), press-filtering until the dry basis content reaches 35 wt%, putting into a kneader, adding a high-viscosity agent and an extrusion aid, uniformly mixing, kneading into a plastic body, carrying out extrusion forming and shaping, and finally drying at 120 ℃ for 3h and roasting at 550 ℃ for 3h to obtain a butterfly-shaped carrier ZC-23 with the diameter of 1.5 mm;
adding deionized water into a dipping tank, preparing NiO and MO by adopting basic nickel carbonate, molybdenum trioxide, ammonium metatungstate, phosphoric acid and nitrilotriacetic acid according to the stoichiometric ratio of the catalyst3、WO3And P2O5Loading active metal on the carrier by adopting equal-volume impregnation, drying the cultured catalyst at the drying temperature of 150 ℃ for 3.0h, then roasting and activating at the activation temperature of 520 ℃ for 2.0h, and obtaining the catalyst C-23 after the activation is finished.
According to the catalyst filling scheme in the reactor, the filling volume ratio of the catalyst C-21 in the first reaction zone is 10 percent, the filling volume ratio of the catalyst C-22 in the second reaction zone is 45 percent, and the filling volume ratio of the catalyst C-23 in the third reaction zone is 45 percent based on the volume of the whole catalyst.
The hydrodenitrogenation reaction conditions are as follows:hydrogen partial pressure 11.5MPa, hydrogen-oil volume ratio 800Nm3/m3And the volume space velocity is 1.0h-1The temperature of the first reaction zone was 325 ℃, the temperature of the second reaction zone was 355 ℃ and the temperature of the third reaction zone was 380 ℃. The hydrodenitrogenation reaction results are shown in table 1.
Example 3
This example provides a density of 992kg/m3The hydrodenitrogenation method of medium and low temperature coal tar (with the distillation range temperature of 205-400 ℃) with total nitrogen content of 8620 mu g/g and alkaline nitrogen content of 4280 mu g/g.
The proportions of the constituents of the catalyst in example 3, based on the total mass of the catalyst, are as follows:
hydrogenation protection catalyst (C-31): NiO: 3.6 wt%, MoO3：12.0wt％，P2O5: 1.2 wt%, the balance being Al2O3；
Type I hydrodenitrogenation catalyst (C-32): NiO: 6.0 wt%, MoO3：6.0wt％，WO3：20.0wt％，P2O5: 3.5 wt%, complexing agent content 8.0 wt%, boron modified alumina (wherein B)2O3Content of 2.0 wt%) 30.0 wt%, and its component is Al2O3：
Type II hydrodenitrogenation catalyst (C-33): NiO: 6.0 wt%, MoO3：12.0wt％，WO3：6.0wt％，P2O5: 1.5 wt%, Y/amorphous silica-alumina composite: 35.0 wt%, the balance being phosphorus-modified alumina (wherein P2O5Content 2.5 wt%);
preparation of catalyst C-32:
uniformly mixing 258.0g of boron modified pseudo-boehmite (Zhonghai oil Tianjin chemical research design institute Co., Ltd., dry basis content of 72%) and 306.0g of macroporous pseudo-boehmite (Zhonghai oil Tianjin chemical research design institute Co., Ltd., dry basis content of 70%) with 12.0g of extrusion aid, adding 510.0g of acid solution prepared from nitric acid, tartaric acid and water, kneading into a plastic body, extruding, molding and shaping, drying at 180 ℃ for 3h, and roasting at 580 ℃ for 4h to obtain a five-tooth spherical carrier ZC-32 with the diameter of 2.5 mm;
adding deionized water into an impregnation tank, preparing NiO and MO by adopting basic nickel carbonate, molybdenum trioxide, ammonium metatungstate, phosphoric acid, citric acid and amino trimethylene phosphonic acid to prepare the catalyst according to the stoichiometric ratio3、WO3And P2O5Uniformly spraying the impregnation liquid on a C-32 catalyst carrier by adopting an isometric impregnation method, placing the cultured catalyst under a vacuum condition for dehydration, wherein the vacuum degree is 5kPa, the dehydration temperature is 80 ℃, the dehydration time is 3.0h, then placing the catalyst in a microwave activation furnace for activation, the activation temperature is 250 ℃, the activation time is 45min, and obtaining the catalyst C-32 after the activation is finished.
Preparation of catalyst C-33:
pulping 315.0g of silicon-modified pseudo-boehmite (Zhonghai oil Tianjin chemical research design institute Co., Ltd., dry basis content of 70%) and 203.0g Y/amorphous silica-alumina composite material (Zhonghai oil Tianjin chemical research design institute Co., Ltd., dry basis content of 85%), filter-pressing until the dry basis content is 35 wt%, putting into a kneader, adding a high-viscosity agent and an extrusion aid, uniformly mixing, kneading into a plastic body, carrying out extrusion forming and shaping, and finally drying at 120 ℃ for 6h and roasting at 520 ℃ for 4h to obtain a clover-shaped carrier ZC-33;
adding deionized water into an impregnation tank, preparing NiO and MO by adopting basic nickel carbonate, molybdenum trioxide, ammonium metatungstate, phosphoric acid and ethylenediamine tetraacetic acid to prepare the catalyst according to the stoichiometric ratio3、WO3And P2O5Loading active metal on the carrier by adopting equal-volume impregnation, drying the cultured catalyst at the drying temperature of 120 ℃ for 6.0h, then roasting and activating at the activation temperature of 450 ℃ for 4.0h, and obtaining the catalyst C-33 after the activation is finished.
According to the catalyst filling scheme in the reactor, the filling volume ratio of the catalyst C-31 in the first reaction zone is 15 percent, the filling volume ratio of the catalyst C-32 in the second reaction zone is 35 percent, and the filling volume ratio of the catalyst C-33 in the third reaction zone is 50 percent based on the volume of the whole catalyst.
The hydrodenitrogenation reaction conditions are as follows: hydrogen partial pressure 14.0MPa, hydrogen-oil volume ratio 1200Nm3/m3Volume space velocity of 0.75h-1The temperature of the first reaction zone was 340 deg.C, the temperature of the second reaction zone was 365 deg.C, and the temperature of the third reaction zone was 390 deg.C. The hydrodenitrogenation reaction results are shown in table 1.
Comparative example 1
According to the catalyst filling scheme in the reactor, the filling volume ratio of the catalyst C-21 in the first reaction zone is 10 percent, and the filling volume ratio of the catalyst C-22 in the second reaction zone and the third reaction zone is 90 percent.
The hydrodenitrogenation reaction conditions are as follows: hydrogen partial pressure 11.5MPa, hydrogen-oil volume ratio 800Nm3/m3And the volume space velocity is 1.0h-1The temperature of the first reaction zone was 325 ℃, the temperature of the second reaction zone was 355 ℃ and the temperature of the third reaction zone was 380 ℃. The hydrodenitrogenation reaction results are shown in table 1.
Comparative example-2
According to the catalyst filling scheme in the reactor, the filling volume ratio of the catalyst C-21 in the first reaction zone is 10 percent, and the filling volume ratio of the catalyst C-23 in the second reaction zone and the third reaction zone is 90 percent.
The hydrodenitrogenation reaction conditions are as follows: hydrogen partial pressure 11.5MPa, hydrogen-oil volume ratio 800Nm3/m3And the volume space velocity is 1.0h-1The temperature of the first reaction zone was 325 ℃, the temperature of the second reaction zone was 355 ℃ and the temperature of the third reaction zone was 380 ℃. The hydrodenitrogenation reaction results are shown in table 1.
TABLE 1 results of hydrodenitrogenation reaction in examples and comparative examples
Figure BDA0001932938570000101

Claims (6)

1. A method for deep hydrogenation denitrification of inferior high-nitrogen heavy distillate oil is characterized by comprising the following steps:
mixing high-nitrogen heavy distillate oil and hydrogen, jointly entering a hydrogenation reactor for hydrogenation reaction, cooling and separating reaction products to obtain a hydrogen-rich component and a low-nitrogen liquid product, wherein the hydrogenation reactor is provided with three reaction zones, a hydrogenation protection catalyst is filled in a first reaction zone for removing metal and colloid impurities, a type I hydrodenitrogenation catalyst with high hydrogenation activity is filled in a second reaction zone, and a type II hydrodenitrogenation catalyst with high hydrogenolysis activity is filled in a third reaction zone; based on the volume of the whole catalyst, the filling volume percentages of the three reaction zones are respectively 5-20 v%, 30-60 v% and 20-50 v%; wherein, the total nitrogen content in the high-nitrogen heavy fraction oil is not less than 3000 mu g/g, and the basic nitrogen content is not less than 800 mu g/g;
the hydrogenation protection catalyst consists of a metal active component and a carrier, wherein the metal active component is NiO and MoO3The carrier is prepared by molding a macroporous alumina precursor; NiO and MoO in the hydrogenation protection catalyst3The total content is 6-20%, and the specific surface area is 100-240 m2A pore volume of 0.60 to 1.0 cm/g3The per gram, the average pore diameter is 12-20 nm, and the mechanical strength is not lower than 120N/cm;
the I-type hydrodenitrogenation catalyst consists of a carrier, active metal, an auxiliary agent and a complexing agent, wherein the active metal is NiO or MoO3With WO3One or more of the above, wherein the total active metal mass content is 24.0-36.0%; the complexing agent is one or more of dihydric alcohol, polyhydric alcohol, organic acid, organic amine and organic phosphorus, and the mass content of the complexing agent is 6-15%; the auxiliary agent is P element;
the carrier is prepared from modified pseudo-boehmite and macroporous pseudo-boehmite, wherein the mass ratio of the modified pseudo-boehmite to the macroporous pseudo-boehmite is 0.5-1.0: 1.0; the preparation method of the I-type hydrodenitrogenation catalyst comprises the following steps:
1) uniformly mixing the modified pseudo-boehmite, the macroporous pseudo-boehmite and the extrusion aid, adding inorganic and organic acid solutions, kneading into a plastic body, performing extrusion forming and shaping, and finally drying at the temperature of 80-180 ℃ for 2-12 hours and roasting at the temperature of 400-600 ℃ for 2-8 hours to obtain a carrier;
2) adding deionized water into an impregnation tank, sequentially adding a complexing agent, an active metal precursor and an auxiliary agent, uniformly stirring and heating until the complexing agent, the active metal precursor and the auxiliary agent are dissolved, and obtaining a stable impregnation solution after constant volume;
3) loading active metal onto a carrier by adopting equal-volume impregnation, and dehydrating the cultured catalyst under a vacuum condition, wherein the vacuum degree is less than 20kPa, and the dehydration temperature is 60-120 DEG CoC, dehydrating for 0.5-6.0 h, and then placing the mixture in a microwave activation furnace for activation at the activation temperature of 150-300 DEG CoC, activating for 10-120 min to obtain the I-type hydrodenitrogenation catalyst after activation is finished;
the II type hydrodenitrogenation catalyst consists of a carrier, active metal and an auxiliary agent, wherein the active metal is NiO or MoO3With WO3One or more of the above components, wherein the total active metal mass content is 16.0-28.0%, the carrier is prepared from modified pseudo-boehmite and a molecular sieve/amorphous silica-alumina composite material, and the mass ratio of the modified pseudo-boehmite to the molecular sieve/amorphous silica-alumina composite material is 1.5-5.0: 1.0; the preparation method of the II-type hydrodenitrogenation catalyst comprises the following steps:
1) pulping the modified pseudo-boehmite and the molecular sieve/amorphous silica-alumina composite material, then carrying out filter pressing, adding a high-viscosity agent and an extrusion promoter, uniformly mixing, kneading into a plastic body, carrying out extrusion forming and shaping, and finally drying at 80-180 ℃ for 2-12 h and roasting at 400-600 ℃ for 2-8 h to obtain a carrier;
2) adding deionized water into an impregnation tank, sequentially adding a complexing agent, an active metal precursor and an auxiliary agent, uniformly stirring and heating until the complexing agent, the active metal precursor and the auxiliary agent are dissolved, and obtaining a stable impregnation solution after constant volume;
3) loading active metal onto a carrier by adopting equal-volume impregnation, and drying the cultured catalyst at the drying temperature of 80-150 DEG CoC, drying for 2.0-8.0 hours, and then roasting and activating at the activation temperature of 350-550oAnd C, activating for 0.5-4.0 h, and obtaining the II-type hydrodenitrogenation catalyst after activation is finished.
2. The method of claim 1, wherein the high-nitrogen heavy fraction oil comprises one or more of coked heavy diesel oil, coked wax oil, catalytic cracking heavy diesel oil and medium-low temperature coal tar.
3. The method of claim 1, wherein the hydrogenation reaction conditions are: the reaction hydrogen partial pressure is 6.0-14.0 MPa, and the volume ratio of hydrogen to oil is 400-1500 Nm3/ m3The volume airspeed is 0.2-4.0 h-1The temperature of the first reaction zone is 200-360 ℃, the temperature of the second reaction zone is 280-400 ℃, and the temperature of the third reaction zone is 320-430 ℃.
4. The method of claim 1, wherein the type I hydrodenitrogenation catalyst has a specific surface area of 140 to 260m2Per g, pore volume of 0.35-0.55 cm3The content of the pore diameter in the range of 6-12 nm is more than or equal to 80 percent.
5. The method of claim 1, wherein the type II hydrodenitrogenation catalyst has a specific surface area of 180 to 340m2A pore volume of 0.35-0.60 cm/g3The total acid amount is 0.3-0.8 mmol/g, and the content of the medium-strength B acid accounts for 40-70% of the total acid amount.
6. The method according to claim 1, wherein the modified pseudoboehmite is a pseudoboehmite material modified by one or more of boron, phosphorus, silicon, titanium and zirconium elements; the macroporous pseudo-boehmite is synthesized by a hydrothermal crystal transformation method, and the specific surface area is 280-400 m2A pore volume of 1.0-1.6 cm3The content of the pore diameter in the range of 10-16 nm is more than or equal to 70 percent; the molecular sieve/amorphous silica-alumina composite material is a composite material synthesized by using a twelve-membered ring Y, Beta or SAPO-5 molecular sieve as a core and wrapping the molecular sieve with amorphous silica-alumina.
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