CN106914260A - Oil hydrogenation catalyst for refining, its preparation method and application - Google Patents

Oil hydrogenation catalyst for refining, its preparation method and application Download PDF

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Publication number
CN106914260A
CN106914260A CN201510982941.4A CN201510982941A CN106914260A CN 106914260 A CN106914260 A CN 106914260A CN 201510982941 A CN201510982941 A CN 201510982941A CN 106914260 A CN106914260 A CN 106914260A
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catalyst
metal
molybdenum
hydrogenation catalyst
oil hydrogenation
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Inventor
侯远东
葛少辉
兰玲
赵秦峰
王鹏
朴佳锐
鲁旭
刘坤红
钟海军
王书芹
吕忠武
姜增琨
霍明辰
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China Petroleum and Natural Gas Co Ltd
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China Petroleum and Natural Gas Co Ltd
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Priority to CN201510982941.4A priority Critical patent/CN106914260A/en
Publication of CN106914260A publication Critical patent/CN106914260A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14Phosphorus; Compounds thereof
    • B01J27/186Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19Molybdenum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61Surface area
    • B01J35/615100-500 m2/g
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63Pore volume
    • B01J35/6350.5-1.0 ml/g
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G47/00Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12Inorganic carriers
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70Catalyst aspects
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02Gasoline

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

Abstract

The present invention relates to a kind of oil hydrogenation catalyst for refining, counted with catalyst weight as 100%, the catalyst is made up of the carrier of the reactive metal oxides of 10~35wt%, the promoter metal of 0.1~5wt%, the auxiliary agent of 1~5wt% and surplus;Wherein, one or two in the combination that active metal is constituted by molybdenum and selected from cobalt and nickel, promoter metal is one or more in iron, zinc and copper, and auxiliary agent is one or more in phosphorus, boron and silicon.The invention further relates to the preparation method and application of the catalyst.The active component yardstick of prepared catalyst is small, and good dispersion degree, catalyst activity is high, good stability, and the substantially all conversion of the sulfur-containing compound in gasoline can be retained the aromatic component in gasoline simultaneously, reduces the loss of octane number during gasoline hydrogenation.It is suitably applied the gasoline hydrogenation technique of producing country V standards and higher standard requirement.

Description

Oil hydrogenation catalyst for refining, its preparation method and application
Technical field
The present invention relates to a kind of for high-sulfur, the catalyst of rich aromatic type gasoline hydroprocessing technique and its preparation side Method, belongs to oil-refining chemical field.
Background technology
Catalytic cracking (FCC) is the core technology of modern refineries secondary operation, is that oil plant obtains economy A kind of important means of benefit, occupies very important status in petroleum refining industry.FCC techniques are by weight Matter oil lighting, purpose product includes gasoline, diesel oil and liquefied gas.In China's catalytic cracking unit status more Plus it is prominent, the main device of vehicle fuel is to provide, catalytically cracked gasoline accounts for China's motor petrol pond ratio and reaches 80%.
With increasingly stricter, the standard continuous improvement of motor petrol of environmental requirement, catalytic cracking production Gasoline also exposes many problems, and mainly sulphur and olefin(e) centent is high.According to statistics in motor petrol 90% with On sulphur and more than 98% alkene come from catalytically cracked gasoline.The sulfur content one of current catalytically cracked gasoline As in 100~700mg/kg, olefin(e) centent is 20~50%, arene content 10~20%.
Therefore, the key of production clean gasoline is the quality upgrading for solving the problems, such as FCC gasoline, particularly FCC The desulphurization problem of gasoline.It is more ripe to the treatment technology of cat naphtha in the prior art, typically adopt The characteristics of using selective hydrogenation technology, selective hydrodesulfurization technology is that operating condition relaxes, and yield of gasoline is high And hydrogen consumption is low.The main of current international most advanced level can be represented to be had:The Prime-G+ technologies of IFP and The SCANfining technologies of ExxonMobil, the catalyst with high selectivity as core, using conventional fixation Bed reactor, process is simple is easy to be reconstructed using existing apparatus;The CD Hydro/CD HDS of CDTech Technology is optimized the process conditions of process using unique catalytic distillation technology, improves selectivity And there is significant advantage at aspects such as operating condition, catalyst lifes.The domestic main RIPP with sinopec Based on the technology developed with FRIPP, such as:The RSDS selective hydrogenations of OCT-M, RIPP of FRIPP Desulfurization technology, RIDOS hydroisomerizings desulfurating and reducing olefinic hydrocarbon (octane value recovering) technology of RIPP, above-mentioned technology All exist when in face of high-sulfur, catalytic gasoline raw material inferior not high enough different degrees of desulfurization degree, poor selectivity, The problems such as loss of octane number is big.
CN102337153A discloses a kind of hydrotreating method of gasoline fraction oil, is related to catalytic gasoline The hydrotreating method of raw material, the enrichment of sulfide in petrol is realized by sulfur separation system, isolates high-sulfur The rich aromatic hydrocarbons extraction oil of content and the raffinate oil of high olefin content, then high-sulfur, rich aromatic component enter specific Hydrodesulfurization unit carries out hydrodesulfurization reaction, realizes the removing of sulfide, and the olefin component of high content enters Aromatisation device, produces high-octane aromatic hydrocarbons;Catalyst is hydroaromatization desulphurization catalyst.
Therefore, be high-sulfur, rich aromatic type gasoline component a kind of high desulfurization activity, inexpensive hydrofinishing are provided Catalyst, solves high-sulfur, the processing problem of inferior patrol, and product meets state V and higher standard requirement, Loss of octane number is reduced simultaneously, for enterprise's cost efficiency provides technical support.
The content of the invention
It is an object of the invention to provide a kind of oil hydrogenation catalyst for refining.
The present invention also aims to provide a kind of preparation method of oil hydrogenation catalyst for refining.
The present invention also aims to provide a kind of application of oil hydrogenation catalyst for refining.
To achieve the above object, the invention provides a kind of oil hydrogenation catalyst for refining, with catalyst weight It is 100% meter, the catalyst is by the reactive metal oxides of 10~35wt%, the auxiliary agent gold of 0.1~5wt% The carrier composition of category, the auxiliary agent of 1~5wt% and surplus;
Wherein, active metal is molybdenum and cobalt or for molybdenum and nickel or be molybdenum, cobalt and nickel, promoter metal It it is one or more in iron, zinc and copper, auxiliary agent is one or more in phosphorus, boron and silicon.
Wherein, the active metal is molybdenum and nickel, and molybdenum oxide:The weight ratio of nickel oxide is 2~8:1.
Wherein, the active metal is molybdenum and cobalt, and molybdenum oxide:The weight ratio of cobalt oxide is 2~8:1.
Wherein, the active metal be molybdenum, cobalt and nickel, and nickel oxide and cobalt oxide weight summation with oxidation The weight ratio of molybdenum is 1:2~8, wherein nickel oxide and cobalt oxide can be mixed with arbitrary proportion, preferred mass ratio It is 1:1.
Wherein, the carrier is inorganic porous oxide material.
Wherein, the carrier is Al2O3、SiO2, one or more in molecular sieve and activated carbon.
Wherein, the catalyst is cylindrical, spherical or cloverleaf pattern.
Wherein, the specific surface area of the catalyst is 150~280m2/ g, pore volume is 0.4~0.7cm2/g。
To achieve the above object, present invention also offers a kind of preparation method of oil hydrogenation catalyst for refining, Comprise the following steps:
Step one, first by boehmite, SiO2, one or more in molecular sieve and activated carbon with help Agent mixing is squeezed, is subsequently adding containing sour deionized water, through kneading, extrusion, then in atmosphere 80~150 DEG C Drying 6~8 hours, 400~700 DEG C are calcined 3~5 hours, and carrier is obtained;
Step 2, by active metallic compound and network containing one or more element in phosphorus, boron and silicon Mixture deionized water dissolving, is subsequently adding the dissolving of promoter metal compound and is made metal co-impregnated solution, by step Carrier obtained in one adds metal co-impregnated solution with saturation impregnation method, then 80~150 DEG C of drying in atmosphere 6~8 hours, 2~6h finished product catalyst is calcined at 200~500 DEG C.
To achieve the above object, present invention also offers a kind of preparation method of oil hydrogenation catalyst for refining, Comprise the following steps:
Step one, by the complexing agent containing one or more element in phosphorus, boron and silicon, promoter metal chemical combination Thing and boehmite, SiO2, one or more mixing in molecular sieve and activated carbon, be subsequently adding containing acid Deionized water, through kneading, extrusion, then in atmosphere 80~150 DEG C dry 6~8 hours, 400~700 DEG C roasting 3~5 hours, be obtained carrier;
Step 2, metal co-impregnated solution is made of deionized water dissolving by active metallic compound, then by step Carrier saturation impregnation method is added in metal co-impregnated solution obtained in one, then in atmosphere 80~150 DEG C Drying 6~8 hours, is calcined 2~6h finished product catalyst at 200~500 DEG C.
To achieve the above object, present invention also offers a kind of method that oil hydrogenation is refined, used catalyst It is above-mentioned oil hydrogenation catalyst for refining.
The refined method of the oil hydrogenation, using fixed bed reactors, reaction pressure be 1.5~3.0MPa, Temperature is 210~300 DEG C, air speed is 1.5~5.0h-1, hydrogen-oil ratio is 150~450:1.
Catalyst of the invention is particularly suited for C6~C12, rich aromatic hydrocarbons midbarrel of the boiling range at 120~200 DEG C Oil.
Heretofore described active metallic compound can be the soluble metallic salt or oxide of diversified forms, Such as molybdenum compound has ammonium molybdate, molybdenum trioxide, and nickel salt includes ortho phosphorous acid nickel, can also include other shapes The nickel salt of formula, such as nickel nitrate, basic nickel carbonate, nickel acetate;Cobalt salt includes ortho phosphorous acid cobalt, can be with Cobalt salt including other forms, such as cobalt nitrate, basic cobaltous carbonate, cobalt acetate.
Heretofore described promoter metal compound can be the soluble metallic salt or oxide of diversified forms, Such as zinc nitrate, zinc acetate and zinc oxide.
Complexing agent used is material commonly used in the art in the present invention, can be phosphoric acid, citric acid etc..
The acid containing in sour deionized water used is material commonly used in the art in the present invention, can for nitric acid, Acetic acid, phosphoric acid etc., the consumption of acid is the 2~6% of carrier quality.
Extrusion aid used is material commonly used in the art, such as sesbania powder in the present invention.
The beneficial effects of the invention are as follows:
Catalyst of the invention is based on the stable carrier of high-ratio surface, by introduce in active metal it is a kind of or Liang Zhong B races metal, improves decentralization of the active metal on carrier, and then improve adding for catalyst Hydrogen is desulphurizing activated, makes that the active component yardstick of catalyst is small, and good dispersion degree, catalyst activity is high, stabilization Property good advantage, aromatic hydrocarbons group in gasoline can be retained while conversion that sulfur-containing compound in gasoline is substantially all Point, reduce the loss of octane number during gasoline hydrogenation.
Specific embodiment
In order to be further detailed to the present invention, spy enumerates following examples, but the present invention and not only limits In embodiment.
The invention provides a kind of oil hydrogenation catalyst for refining, counted with catalyst weight as 100%, it is described Catalyst is by the oxide of active metal of 10~35wt%, the promoter metal of 0.1~5wt%, 1~5wt% The carrier composition of auxiliary agent and surplus;
Wherein, active metal is molybdenum and cobalt or for molybdenum and nickel or be molybdenum, cobalt and nickel, promoter metal It it is one or more in iron, zinc and copper, auxiliary agent is one or more in phosphorus, boron and silicon.
Wherein, molybdenum oxide:Cobalt oxide:The weight ratio of nickel oxide is 2~8:1.
Wherein, molybdenum oxide:Cobalt oxide:The weight ratio of nickel oxide is 2~8:1.
Wherein, the active metal be molybdenum, cobalt and nickel, and nickel oxide and cobalt oxide weight summation with oxidation The weight ratio of molybdenum is 1:2~8, wherein nickel oxide and cobalt oxide can be mixed with arbitrary proportion, preferred mass ratio It is 1:1.
Wherein, the carrier is inorganic porous oxide material.
Wherein, the carrier is Al2O3、SiO2, one or more in molecular sieve and activated carbon.
Wherein, the catalyst is cylindrical, spherical or cloverleaf pattern.
Wherein, the specific surface area of the catalyst is 150~280m2/ g, pore volume is 0.4~0.7cm2/g。
To achieve the above object, present invention also offers a kind of preparation method of oil hydrogenation catalyst for refining, Comprise the following steps:
Step one, first by boehmite, SiO2, one or more in molecular sieve and activated carbon with help Agent mixing is squeezed, is subsequently adding containing sour deionized water, through kneading, extrusion, then in atmosphere 80~150 DEG C Drying 6~8 hours, 400~700 DEG C are calcined 3~5 hours, and carrier is obtained;
Step 2, by active metallic compound and network containing one or more element in phosphorus, boron and silicon Mixture deionized water dissolving, is subsequently adding the dissolving of promoter metal compound and is made metal co-impregnated solution, by step Carrier obtained in one adds metal co-impregnated solution with saturation impregnation method, then 80~150 DEG C of drying in atmosphere 6~8 hours, 2~6h finished product catalyst is calcined at 200~500 DEG C.
To achieve the above object, present invention also offers a kind of preparation method of oil hydrogenation catalyst for refining, Comprise the following steps:
Step one, by the complexing agent containing one or more element in phosphorus, boron and silicon, promoter metal chemical combination Thing and boehmite, SiO2, one or more mixing in molecular sieve and activated carbon, be subsequently adding containing acid Deionized water, through kneading, extrusion, then in atmosphere 80~150 DEG C dry 6~8 hours, 400~700 DEG C roasting 3~5 hours, be obtained carrier;
Step 2, metal co-impregnated solution is made of deionized water dissolving by active metallic compound, then by step Carrier saturation impregnation method is added in metal co-impregnated solution obtained in one, then in atmosphere 80~150 DEG C Drying 6~8 hours, is calcined 2~6h finished product catalyst at 200~500 DEG C.
To achieve the above object, present invention also offers a kind of method that oil hydrogenation is refined, used catalyst It is above-mentioned oil hydrogenation catalyst for refining.
The refined method of the oil hydrogenation, using fixed bed reactors, reaction pressure be 1.5~3.0MPa, Temperature is 210~300 DEG C, air speed is 1.5~5.0h-1, hydrogen-oil ratio is 150~450:1.
Catalyst of the invention is particularly suited for C6~C12, rich aromatic hydrocarbons midbarrel of the boiling range at 120~200 DEG C Oil.
Heretofore described active metallic compound can be the soluble metallic salt or oxide of diversified forms, Such as molybdenum compound has ammonium molybdate, molybdenum trioxide, and nickel salt includes ortho phosphorous acid nickel, can also include other shapes The nickel salt of formula, such as nickel nitrate, basic nickel carbonate, nickel acetate;Cobalt salt includes ortho phosphorous acid cobalt, can be with Cobalt salt including other forms, such as cobalt nitrate, basic cobaltous carbonate, cobalt acetate.
Heretofore described promoter metal compound can be the soluble metallic salt or oxide of diversified forms, Such as zinc nitrate, zinc acetate and zinc oxide.
Complexing agent used is material commonly used in the art in the present invention, can be phosphoric acid, citric acid etc..
The acid containing in sour deionized water used is material commonly used in the art in the present invention, can for nitric acid, Acetic acid, phosphoric acid etc., the consumption of acid is the 2~6% of carrier quality.
Extrusion aid used is material commonly used in the art, such as sesbania powder in the present invention.
Embodiment 1
Aluminum oxide 500g powders are taken, sesbania powder 16g mixing is added, is then added to contain industrial nitric acid 21g 450ml water in, through kneading, extruded moulding, dry 8h at 120 DEG C, then through 500 DEG C of roasting 4h, Catalyst carrier is obtained.Settled solution is configured with ammonium molybdate and nickel nitrate, phosphoric acid is added dropwise, on above-mentioned carrier NiO, 15% MoO of load 3%3P with 1%2O5, then dried 10 hours at 120 DEG C, 450 DEG C of calcination process, the time is 3h, obtains catalyst.
Embodiment 2
The carrier of embodiment 2 is prepared according to the same method of embodiment 1, configures clear with ammonium molybdate and cobalt nitrate Clear solution, is added dropwise phosphoric acid, the CoO in above-mentioned supported on carriers 3%, 15% MoO3P with 1%2O5, Dried 10 hours at 120 DEG C, 450 DEG C of calcination process, the time is 3h, obtains catalyst.
Embodiment 3
The carrier of embodiment 3 is prepared according to the same method of embodiment 1, with molybdenum trioxide and cobalt nitrate, alkali Formula nickelous carbonate, phosphoric acid configuration settled solution, in above-mentioned supported on carriers totally 3% CoO, NiO and 15% MoO3Active component and 1% P2O5, dried 10 hours at 120 DEG C, 450 DEG C of calcination process, Time is 3h, obtains catalyst.
Embodiment 4
The carrier of embodiment 4 is prepared according to the same method of embodiment 1, with molybdenum trioxide, basic nickel carbonate Settled solution is configured with phosphoric acid, in the MoO of the NiO and 18% of above-mentioned supported on carriers 3%3Active component And 1.5% P2O5, while adding promoter metal Zn elements, weigh a certain amount of zinc nitrate and be added to and match somebody with somebody In the NiMo solution put, then on carrier, ZnO content accounts for catalyst weight 3% to stain, 120 Dried 10 hours at DEG C, 500 DEG C of calcination process, the time is 3h, obtains catalyst.
Embodiment 5
The carrier of embodiment 5 is prepared according to the same method of embodiment 1, with molybdenum trioxide, basic cobaltous carbonate Settled solution is configured with phosphoric acid, in the MoO of the CoO and 20% of above-mentioned supported on carriers 4%3Active component And 2.0% P2O5, while adding promoter metal Cu elements, weigh a certain amount of copper nitrate and be added to and match somebody with somebody In the CoMo solution put, then impregnated on carrier, CuO contents account for catalyst weight 3%, Dried 10 hours at 120 DEG C, 500 DEG C of calcination process, the time is 3h, obtains catalyst.
Embodiment 6
Aluminum oxide 475g powders are taken, zinc oxide 17g, sesbania powder 16g mixing is added, is then added to contain Have in the 450ml water of industrial nitric acid 21g, through kneading, extruded moulding, 8h is dried at 120 DEG C, then Through 500 DEG C of roasting 4h, catalyst carrier is obtained.Settled solution is configured with ammonium molybdate and nickel nitrate, phosphorus is added dropwise Acid, in the MoO of the NiO and 15% of above-mentioned supported on carriers 3%3, 1% P2O5, then 120 Dried 10 hours at DEG C, 450 DEG C of calcination process, the time is 3h, obtains catalyst.
Embodiment 7
This example introduces the activity rating process of catalyst.
It is raw material to use rich arenes catalytic gasoline, and feedstock property is shown in Table 1.
The micro anti-evaluation experiment of the same terms is carried out to catalyst in embodiment and comparative example, is taken within every 24 hours Sample analysis product sulphur, nitrogen content, research octane number (RON), analysis result are averaged and are shown in Table 2.Catalyst is filled Fill out as follows with appreciation condition:
Evaluation device is 100ml fixed bed reactors, and reactor interlude can realize thermostatic control, Evaluate catalyst and take length between 2-5mm, be seated in control of the reactor interlude beneficial to reaction temperature, Upper-lower section φ 2, the filling of the inert ceramic balls of φ 3, N2Airtight qualified rear temperature programming vulcanization, 150 DEG C of dryings 2h, then with the speed elevated temperature cure of 20 DEG C/h, 280 DEG C of constant temperature 6h, vulcanization terminates rear swap-in feedstock oil. Appreciation condition:Reaction pressure 2.0MPa, 240 DEG C of reaction temperature, raw material volume air speed 2.0h-1, hydrogen-oil ratio 200:1.
The catalyst activity of table 1 evaluates raw material oil nature
Comparative example
Comparative catalyst is from the CoMo/Al in patent CN101134909A2O3Selective hydrodesulfurization is urged Agent A, catalyst uses proprietary metal impregnation technology, can be used for gasoline hydrodesulfurizationmethod treatment, can reduce Total sulfur and mercaptans content in FCC gasoline cut, without a large amount of loss gasoline, moreover it is possible to minimize octane number Decline.
The catalyst activity of embodiment 1-6 and comparative example is investigated with the appreciation condition of embodiment 7, is as a result shown Using the catalyst of the inventive method preparation, hydrodesulfurization performance is more excellent compared with the catalyst in comparative example It is different, catalyst desulfurizing performance is improve after addition promoter metal, and product loss of octane number is effectively reduced, It is particularly well-suited to the hydrotreating production high standard gasoline component of high-sulfur, rich aromatic type gasoline cut.
Concrete outcome is shown in Table 2.
The embodiment 1-6 of table 2 is constituted and micro anti-evaluation result with the catalyst preparation of comparative example 1
Catalyst prepared by embodiment 4 carries out desulphurizing activated and long period study on the stability, and vulcanization terminates Afterwards, catalyst evaluation test in 1000 hours is carried out.
Every 96 hours sampling analysis products sulphur, nitrogen content, analysis result statistics are shown in Table 3.From table 3 Hydrogenation catalyst of the present invention is in reaction pressure 2.0MPa, 240 DEG C of reaction temperature, raw material volume air speed 2.0h-1、 Hydrogen-oil ratio 200:1, during condition, still keep good Hydrogenation, Hydrogenation stabilization, so originally Invention is there is provided the refined method for preparing catalyst of a kind of high activity, high stability poor quality gasoline hydrogenation.
The catalyst long period Activity evaluation of table 3
Certainly, the present invention can also have other various embodiments, without departing substantially from spirit of the invention and its essence In the case of, those of ordinary skill in the art can make various corresponding changes and change according to the present invention Shape, but these corresponding changes and deformation should all belong to the protection domain of the claims in the present invention.

Claims (12)

1. a kind of oil hydrogenation catalyst for refining, it is characterised in that counted with catalyst weight as 100%, The catalyst by 10~35wt% reactive metal oxides, the promoter metal of 0.1~5wt%, 1~5wt% Auxiliary agent and surplus carrier composition;
Wherein, active metal is molybdenum and cobalt or for molybdenum and nickel or be molybdenum, cobalt and nickel, promoter metal It it is one or more in iron, zinc and copper, auxiliary agent is one or more in phosphorus, boron and silicon.
2. oil hydrogenation catalyst for refining according to claim 1, it is characterised in that the activity Metal is molybdenum and nickel, and molybdenum oxide:The weight ratio of nickel oxide is 2~8:1.
3. oil hydrogenation catalyst for refining according to claim 1, it is characterised in that the activity Metal is molybdenum and cobalt, and molybdenum oxide:The weight ratio of cobalt oxide is 2~8:1.
4. oil hydrogenation catalyst for refining according to claim 1, it is characterised in that the activity Metal is molybdenum, cobalt and nickel, and the weight summation of nickel oxide and cobalt oxide and the weight ratio of molybdenum oxide are 1:2~8.
5. oil hydrogenation catalyst for refining according to claim 1, it is characterised in that the carrier It is inorganic porous oxide material.
6. oil hydrogenation catalyst for refining according to claim 1, it is characterised in that the carrier It is Al2O3、SiO2, one or more in molecular sieve and activated carbon.
7. oil hydrogenation catalyst for refining according to claim 1, it is characterised in that the catalysis Agent is cylindrical, spherical or cloverleaf pattern.
8. oil hydrogenation catalyst for refining according to claim 1, it is characterised in that the catalysis The specific surface area of agent is 150~280m2/ g, pore volume is 0.4~0.7cm2/g。
9. the preparation method of the oil hydrogenation catalyst for refining described in any one of claim 1~8, its feature It is to comprise the following steps:
Step one, first by boehmite, SiO2, one or more in molecular sieve and activated carbon with help Agent mixing is squeezed, is subsequently adding containing sour deionized water, through kneading, extrusion, then in atmosphere 80~150 DEG C Drying 6~8 hours, 400~700 DEG C are calcined 3~5 hours, and carrier is obtained;
Step 2, by active metallic compound and network containing one or more element in phosphorus, boron and silicon Mixture deionized water dissolving, is subsequently adding the dissolving of promoter metal compound and is made metal co-impregnated solution, by step Carrier obtained in one adds metal co-impregnated solution with saturation impregnation method, then 80~150 DEG C of drying in atmosphere 6~8 hours, 2~6h finished product catalyst is calcined at 200~500 DEG C.
10. the preparation method of the oil hydrogenation catalyst for refining described in any one of claim 1~8, it is special Levy and be, comprise the following steps:
Step one, by the complexing agent containing one or more element in phosphorus, boron and silicon, promoter metal chemical combination Thing and boehmite, SiO2, one or more mixing in molecular sieve and activated carbon, be subsequently adding containing acid Deionized water, through kneading, extrusion, then in atmosphere 80~150 DEG C dry 6~8 hours, 400~700 DEG C roasting 3~5 hours, be obtained carrier;
Step 2, metal co-impregnated solution is made of deionized water dissolving by active metallic compound, then by step Carrier saturation impregnation method is added in metal co-impregnated solution obtained in one, then in atmosphere 80~150 DEG C Drying 6~8 hours, is calcined 2~6h finished product catalyst at 200~500 DEG C.
The refined method of 11. a kind of oil hydrogenations, it is characterised in that used catalyst is claim 1~8 Oil hydrogenation catalyst for refining described in any one.
The refined method of 12. oil hydrogenations according to claim 11, it is characterised in that the method Using fixed bed reactors, reaction pressure is 1.5~3.0MPa, temperature is 210~300 DEG C, air speed is 1.5~5.0h-1, hydrogen-oil ratio is 150~450:1.
CN201510982941.4A 2015-12-24 2015-12-24 Oil hydrogenation catalyst for refining, its preparation method and application Pending CN106914260A (en)

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Application publication date: 20170704