CN106190232B - A kind of method of oil hydrofinishing production propylene cracking stock - Google Patents
A kind of method of oil hydrofinishing production propylene cracking stock 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
- 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
- C10G45/12—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 crystalline alumino-silicates, e.g. molecular sieves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
-
- 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
-
- 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
- C10G2400/02—Gasoline
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- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention provides a kind of method of oil hydrofinishing production propylene cracking stock, wherein, in 240~280 DEG C, 1.0~4.0MPa of hydrogen dividing potential drop, 1.0~4.0h of volume space velocity of reaction temperature‑1, hydrogen to oil volume ratio 100~500：Under 1 process conditions, catalysis processing oil, produces propylene cracking stock；Catalyst is using aluminium oxide, ZSM 5 and mesopore silicon oxide as complex carrier, using one kind in Zr, Ce, La metal, one kind in VI B races metal Mo, W metal and a kind of formed composition metal component in Fe, Cu, Ag as active component, reach the effect of deep desulfuration, denitrogenation, Olefin decrease, reach reformer feed requirement or propylene cracking stock requirement.
Description
Technical field
The present invention relates to a kind of method of oil hydrofinishing production propylene cracking stock, led especially suitable for petroleum refining
Hydrodesulfurization, hydrodenitrogeneration and the alkene saturation of inferior patrol cut in domain, produce the industrial chemicals of qualification.
Background technology
In petroleum refining industry, with the development of crude oil in poor quality and catalytic cracking technology and Delayed Coking Technology, cause
Increase the secondary operation oil such as the high catalytic gasoline of the impurity contents such as sulphur, nitrogen and coker gasoline ratio shared in gasoline total amount
Add.As oil Refining Technologies develop towards deep processing direction, the quality of catalytic gasoline and coker gasoline will be worse and worse.Therefore, such as
The quality what further improves the oil of secondary operation reaches the requirement of industrial chemicals, is important topic of concern.
Hydrobon catalyst is generally with aluminium oxide or the composite oxides such as aluminium oxide and silica, boron oxide, zirconium oxide
For carrier, using group vib W, Mo as active component element, using VIII group Co, Ni as adjuvant component element, their various combination,
Its catalytic performance respectively has feature, such as Co-Mo combinations with stronger desulphurizing activated；Ni-Mo combine and Ni-W combination have compared with
Strong denitrogenation and arene saturating activity.In order to further improve the performance of catalyst, be additionally added other addO-on therapies, as P, F, B,
Ti, Zr etc..
A kind of FCC gasoline low temperature hydrodesulfurisation technology is described in USP6042719.Patent used catalyst is difunctional
Catalyst, is supported on by ZSM-5 and Al with group vib metal Mo and group VIII metal Co2O3On the carrier of composition, ZSM-5/Al2O3
=80/20.Under lower temperature conditions, hydrodesulfurization rate is 80%~95%.
CN1004192 discloses one kind and prepares W-Mo-Ni-P/ γ-Al2O3The method of catalyst, the invention use are once common
Leaching method prepares catalyst, and when preparing maceration extract, the compound of W is ammonium tungstate, and the compound of Ni is nickelous carbonate, and the compound of P is
Orthophosphoric acid, the compound of Mo is molybdenum trioxide., will be certain when preparing co-impregnated solution since molybdenum trioxide water solubility is bad
At a temperature of (90 DEG C~120 DEG C) by molybdenum trioxide not soluble in water and orthophosphoric acid reaction to generate water-soluble phosphorus molybdenum miscellaneous more
Acid.In the co-impregnated solution of the patent, W, Mo, P are the anionic form presence with heteropoly acid.
A kind of Hydrobon catalyst and preparation method thereof disclosed in CN1194076, the catalyst belong to W-Mo-Ni-P/
γ-Al2O3Catalyst, the preparation of co-impregnated solution are to dissolve ammonium metatungstate, ammonium paramolybdate, nickel nitrate and orthophosphoric acid at room temperature to prepare
, the catalyst in the patent is prepared using a total immersion method.
CN100998952A discloses a kind of hydrogenation essence for coking gasoline hydrogenation refining production chemical industry and reformer feed
Catalyst processed and preparation method thereof, which is prepared using secondary co-impregnation, secondary drying, roasting, for coking vapour
Have the characteristics that alkene saturation low temperature active is good, coking speed is slow during oily hydrofinishing.
CN01127448.4 provides a kind of hydrogenation catalyst and preparation method thereof, the catalyst by metal active constituent and
Carrier is formed, and the metal component of catalyst is metal oxide MoO3, any two kinds or three kinds in CoO and NiO, metal is lived
Property component accounts for the 2%~35% of total catalyst weight, and carrier is by TiO2, modified zsm-5 zeolite and adhesive composition.Use this
The catalyst of invention, can reduce the content of sulphur and alkene in inferior patrol, and increase the octane number of gasoline.
CN0012315.0 discloses a kind of alumina support of large aperture titaniferous and silicon composite assistant and preparation method thereof.
The invention introduces silicon-containing compound and titanium-containing compound during aluminium hydroxide is prepared.This preparation process technique is simple, into
This is low.Simultaneous oxidation titanium and silica are uniform in aluminium oxide Dispersion on surface, and the invention titaniferous, the aluminium oxide of silicon have good
Peptization, eliminates routinely silicon-containing alumina pore size distribution disperse, the shortcomings that peptization is poor, the titaniferous silicon carrying alumina of the invention
Body, has big aperture, and average pore size is 10nm~15nm, while has stronger surface acid property, available for large aperture plus
Hydrogen handles the preparation of catalyst or hydrogenation conversion catalyst.
CN02116267.0 is related to a kind of gasoline hydrogenation catalyst and preparation method and its application in desulfurating and reducing olefinic hydrocarbon.
Based on the percentage by weight to catalyst, its component includes the catalyst of the invention：It is 20%~90% to include containing dosage
TiO2The carrier of component；A active components：Group VIII metal oxide content is 0.1%~8.0%；B activity component：Group vib gold
The content for belonging to oxide is 1%~13%；Surplus is binding agent.The catalyst of the invention adds after presulfurization what is relatively relaxed
Under hydrogen condition, processing sulfur-bearing, the FCC gasoline of alkene, show very high hydrodesulfurization activity and selectivity.Urged with tradition hydrogenation
Agent is compared, and under identical HDS level, the loss of octane number of gasoline is smaller, and the liquid receipts of product are higher.
CN102051206 discloses a kind of catalyst of producing ethylene cracking materials by hydrofining naphtha, the catalyst
It is group VIII metal at least one Fe, Co, Ni metal and group vib metal at least one Mo, W metal is active component, with phosphorus aluminium
Molecular sieve is AlPO4- 5 and Titanium Sieve Molecular Sieve be that ETS-10 is carrier, but the performance of the catalyst has still been short of, industry
Application level is lower.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of oil Hydrobon catalyst, are refined especially suitable for oil
The industrial chemicals of the hydrodesulfurization of inferior patrol cut, hydrodenitrogeneration and alkene saturation in field processed.
To solve the above problems, the technical solution adopted by the present invention is：
A kind of method of oil hydrofinishing production propylene cracking stock, in 240~280 DEG C of reaction temperature, hydrogen dividing potential drop 1.0
~4.0MPa, 1.0~4.0h of volume space velocity-1, hydrogen to oil volume ratio 100~500：Under 1 process conditions, catalysis processing oil is raw
Output propylene cracking stock；Catalyst is using aluminium oxide, ZSM-5 and mesopore silicon oxide as complex carrier, with Zr, Ce, La metal
In one kind, one kind in VI B races metal Mo, W metal and a kind of formed composition metal component in Fe, Cu, Ag be
Active component；Wherein, in terms of total catalyst weight 100%：ZSM-5 is 1~20wt%, and mesopore silicon oxide is 1~20 wt%, oxygen
Change aluminium is 20~80 wt%, and Zr, Ce or La metal are 1~10 wt%, and Mo, W metal are 10~20 wt%, and Fe, Cu or Ag are golden
Belong to for 5~15 wt%.
Wherein, the specific surface area of the catalyst is 260m2/ g~320m2/ g, pore volume are 0.25ml/g~0.30ml/g,
Wherein aperture accounts for the 50%~70% of total pore volume in the pore size distribution of 2nm~8nm, and aperture accounts for total hole in the pore size distribution of 10nm~16nm
20%~40% held.
The aluminium oxide is modified with alkali or alkaline earth metal salt, and wherein modified metal is relative to catalyst
Overall weight percent scope be 0.1~5%.
The ZSM-5 is modified with rare earth metal salt, wherein modified metal relative to catalyst gross weight
Percentage ranges are 0.1~5%.
The mesopore silicon oxide is modified with titanium, nickel, molybdenum or zirconium metallic salt, and wherein modified metal is relative to urging
The overall weight percent scope of agent is 0.1~5%.
The reaction condition is preferably：260 DEG C, hydrogen dividing potential drop 2.5MPa, volume space velocity 2.0h of temperature-1, hydrogen to oil volume ratio
300：1.
The shape of the catalyst can be sheet, spherical, cylindrical bars or clover, bunge bedstraw herb.
The shape clover of the catalyst or bunge bedstraw herb, a diameter of 0.6mm~1.6mm of catalyst.
The preparation method of the catalyst includes the following steps：
（1）The preparation of complex carrier：Aluminium oxide, ZSM-5 and mesoporous oxidation are weighed respectively by each component content in catalyst
Silicon is mixed, and adds a certain amount of dust technology, sesbania powder, is then stirred 1-3h, then extruded moulding under room temperature again, is finally existed
80-110 DEG C is dried overnight, and 6-10h is roasted at 450-650 DEG C up to complex carrier；
（2）The load of active component：The method for taking step impregnation is loaded, first by Zr, Ce or La metal in catalyst
Content prepares its precursor solution, then by step（1）Complex carrier be added in above-mentioned solution, and be stirred continuously lower leaching
Stain 12-24h, finally centrifuges out solids, is dried overnight at 80-110 DEG C, and 6-10h is roasted at 350-550 DEG C up to loading
The catalyst of Zr, Ce or La metal；Further, above-mentioned same dipping method is taken by Mo, W metal and Fe, Cu or Ag gold
Belong to load on a catalyst.
The present invention technique effect be：（1）Catalyst of the present invention takes three component of aluminium oxide, ZSM-5 and mesopore silicon oxide
Complex carrier, on the one hand obtain the surface nature carrier material very excellent such as than surface and pore-size distribution, be activearm
The load divided provides abundant site, on the other hand, after three kinds of materials are for composite, acts synergistically between each other, pole
The big hydrofinishing performance for improving catalyst, reaches the effect of deep desulfuration, denitrogenation, Olefin decrease in the process of oil.
(2) catalyst of the present invention first with one kind in Zr, Ce, La metal, VI B races metal Mo, W metal it is a kind of with
And a kind of formed composition metal component in Fe, Cu, Ag is active component, the activity of catalyst is greatly improved, three kinds
Metal ingredient mutually acts synergistically, and has been greatly facilitated the lifting of catalyst stability and selectivity.
Embodiment
Technical scheme is further elaborated with reference to embodiment：
Embodiment 1
Take 150g boehmites, 50gZSM-5 and the mesoporous SiO of 30g2With 15g sesbania powders, it is uniformly mixed, is added dropwise by 10g
The mixed solution of nitric acid and 230g deionized waters composition, then stirs 2h, then kneading, three leaves of the extrusion into 1.1mm again under room temperature
Careless shape, 110 DEG C are dried overnight, and then roast 8h at 550 DEG C, carrier is made.Again with zirconium nitrate maceration extract dipping 18h, 100 DEG C dry
Dry overnight, 450 DEG C of roasting 6h, further take same method to impregnate ammonium molybdate and ferric nitrate, catalyst A are made.
Embodiment 2
Take 200g boehmites, 60gZSM-5 and the mesoporous SiO of 20g2With 15g sesbania powders, it is uniformly mixed, is added dropwise by 20g
The mixed solution of nitric acid and 260g deionized waters composition, then stirs 3h, then kneading, four leaves of the extrusion into 0.8mm again under room temperature
Careless shape, 100 DEG C are dried overnight, and then roast 6h at 550 DEG C, carrier is made.Again with lanthanum nitrate maceration extract dipping 16h, 110 DEG C dry
Dry overnight, 350 DEG C of roasting 8h, further take same method to impregnate ammonium metatungstate and copper nitrate, catalyst B are made.
Embodiment 3
Take 180g boehmites, 40gZSM-5 and the mesoporous SiO of 30g2With 25g sesbania powders, it is uniformly mixed, is added dropwise by 20g
The mixed solution of nitric acid and 240g deionized waters composition, then stirs 3h, then kneading, four leaves of the extrusion into 1.2mm again under room temperature
Careless shape, 100 DEG C are dried overnight, and then roast 6h at 600 DEG C, carrier is made.Again with cerous nitrate maceration extract dipping 20h, 90 DEG C dry
Dry overnight, 450 DEG C of roasting 8h, further take same method to impregnate ammonium metatungstate and silver nitrate, catalyst C are made.
Embodiment 4
Take 280g boehmites, 70gZSM-5 and the mesoporous SiO of 50g2With 45g sesbania powders, it is uniformly mixed, is added dropwise by 30g
The mixed solution of nitric acid and 300g deionized waters composition, then stirs 3h, then kneading, four leaves of the extrusion into 0.9mm again under room temperature
Careless shape, 100 DEG C are dried overnight, and then roast 10h at 550 DEG C, carrier is made.Again with zirconium nitrate maceration extract dipping 20h, 90 DEG C dry
Dry overnight, 450 DEG C of roasting 8h, further take same method to impregnate metamolybdic acid ammonium and copper nitrate, catalyst D are made.
Embodiment 5
Take 160g boehmites, 10gZSM-5 and the mesoporous SiO of 20g2With 20g sesbania powders, it is uniformly mixed, is added dropwise by 10g
The mixed solution of nitric acid and 200g deionized waters composition, then stirs 2h, then kneading, three leaves of the extrusion into 1.20mm again under room temperature
Careless shape, 100 DEG C are dried overnight, and then roast 7h at 450 DEG C, carrier is made.Again with lanthanum nitrate maceration extract dipping 16h, 90 DEG C dry
Dry overnight, 550 DEG C of roasting 6h, further take same method to impregnate ammonium metatungstate and ferric nitrate, catalyst E are made.
Embodiment 6
Take 250g boehmites, 30gZSM-5 and the mesoporous SiO of 30g2With 35g sesbania powders, it is uniformly mixed, is added dropwise by 30g
The mixed solution of nitric acid and 230g deionized waters composition, then stirs 2h, then kneading, four leaves of the extrusion into 0.6mm again under room temperature
Careless shape, 100 DEG C are dried overnight, and then roast 6h at 500 DEG C, carrier is made.Again with cerous nitrate maceration extract dipping 15h, 100 DEG C dry
Dry overnight, 450 DEG C of roasting 8h, further take same method to impregnate metamolybdic acid ammonium and silver nitrate, catalyst F are made.
Comparative example 1
200g boehmites, 20g phosphate aluminium molecular sieve AlPO4-5,10g titanium silicon molecular sieve ETS-4-10 and 10g sesbania powders are taken,
It is uniformly mixed, is added dropwise the mixed solution kneading being made of 15g nitric acid, 10g citric acids and 200g deionized waters, extrusion is into 1.5mm
Cloverleaf pattern, 110 DEG C of dry 2h, then 550 DEG C roast 4h, carrier is made.Prepared again with nickel nitrate and ammonium metatungstate
Maceration extract impregnates, 120 DEG C of dry 4h, and 550 DEG C of roasting 4h, are made catalyst G.
Comparative example 2
Take the boehmite, 20g phosphate aluminium molecular sieve AlPO4-5,10g titanium silicon molecular sieve ETS-4-10 and 10g sesbanias of 200g
Powder, is uniformly mixed, the mixed solution being made of 15g nitric acid, 10g citric acids, 20g Ludox and 200g deionized waters is added dropwise and mixes
Pinch, into the cloverleaf pattern of 1.5mm, 110 DEG C of dry 2h, then roast 4h at 550 DEG C, carrier is made extrusion.Prepared with ammonium fluoride
Into maceration extract dipping is obtained, 120 DEG C of dry 4h, 350 DEG C roast 4h, then are impregnated with the maceration extract that nickel nitrate and ammonium metatungstate are prepared,
120 DEG C of dry 4h, 550 DEG C of roasting 4h, are made catalyst H.
Embodiment 7
This example introduces the micro anti-evaluation result of above-mentioned catalyst.
The catalytic amount that micro anti-evaluation uses is 1.5g, respectively by the xylene solution containing thiophene (in terms of sulphur 1000 μ g/g)
With the xylene solution containing pyridine (counting 500 μ g/g using nitrogen) as evaluation raw material, hydrodesulfurization and hydrodenitrogeneration performance comparison are carried out
Experiment, reaction condition are shown in Table 1.
The micro- anti-hydrogenation appreciation condition of table 1
| Appreciation condition | Reaction temperature | Hydrogen dividing potential drop | Volume space velocity | Hydrogen to oil volume ratio |
| Desulphurization control parameter | 255 | 2.0 | 2.5 | 200：1 |
| Denitrogenation control parameter | 255 | 2.0 | 2.5 | 200：1 |
The micro- reaction evaluating result of table 2
| Catalyst | The extrusion rate wt% of sulphur | The extrusion rate wt% of nitrogen |
| A | 99.7 | 80.6 |
| B | 98.7 | 82.1 |
| C | 99.3 | 84.8 |
| D | 99.2 | 86.3 |
| E | 98.5 | 88.6 |
| F | 99.1 | 82.6 |
| G | 96.7 | 71.6 |
| H | 95.4 | 67.2 |
The hydrodesulfurization of the catalyst of embodiment 1-6 prepared by the present invention and hydrodenitrogeneration performance are bright as can be seen from Table 2
The aobvious catalyst being better than in comparative example 1-2 using different carriers and active ingredient.
Finally it should be noted that：The foregoing is only a preferred embodiment of the present invention, is not intended to limit the invention,
Although the present invention is described in detail with reference to the foregoing embodiments, for those skilled in the art, it still may be used
To modify to the technical solution described in foregoing embodiments, or equivalent substitution is carried out to which part technical characteristic.
Within the spirit and principles of the invention, any modification, equivalent replacement, improvement and so on, should be included in the present invention's
Within protection domain.
Claims (8)
- A kind of 1. method of oil hydrofinishing production propylene cracking stock, it is characterised in that：In 240~280 DEG C of reaction temperature, 1.0~4.0MPa of hydrogen dividing potential drop, 1.0~4.0h of volume space velocity-1, hydrogen to oil volume ratio 100~500：Under 1 process conditions, catalysis adds Work oil, produces propylene cracking stock；Catalyst be using aluminium oxide, ZSM-5 and mesopore silicon oxide as complex carrier, with Zr, One kind in Ce, La metal, one kind in VI B races metal Mo, W metal and a kind of formed compound gold in Fe, Cu, Ag Category component is active component；Wherein, in terms of total catalyst weight 100%：ZSM-5 is 1~20wt%, mesopore silicon oxide for 1~ 20wt%, aluminium oxide are 20~80wt%, and Zr, Ce or La metal are 1~10wt%, and Mo, W metal are 10~20wt%, Fe, Cu Or Ag metals are 5~15wt%；The specific surface area of the catalyst is 260m2/ g~320m2/ g, pore volume for 0.25ml/g~ 0.30ml/g, wherein aperture account for the 50%~70% of total pore volume in the pore size distribution of 2nm~8nm, and aperture is in the hole of 10nm~16nm Distribution accounts for the 20%~40% of total pore volume.
- 2. according to the method described in claim 1, it is characterized in that：The aluminium oxide be with alkali or alkaline earth metal salt into Row modification, wherein modified metal is 0.1~5% relative to the overall weight percent scope of catalyst.
- 3. according to the method described in claim 1, it is characterized in that：ZSM-5 is modified with rare earth metal salt, wherein Modified metal is 0.1~5% relative to the overall weight percent scope of catalyst.
- 4. according to the method described in claim 1, it is characterized in that：The mesopore silicon oxide is to use titanium, nickel, molybdenum or zirconium metal salt What class was modified, wherein modified metal is 0.1~5% relative to the overall weight percent scope of catalyst.
- 5. according to the method described in claim 1, it is characterized in that：The reaction condition is：260 DEG C of temperature, hydrogen dividing potential drop 2.5MPa, volume space velocity 2.0h-1, hydrogen to oil volume ratio 300：1.
- 6. according to the method described in claim 1, it is characterized in that：The shape of the catalyst be sheet, spherical, cylindrical bars or Clover, bunge bedstraw herb.
- 7. according to the method described in claim 6, it is characterized in that：The shape clover of the catalyst or bunge bedstraw herb, catalysis A diameter of 0.6mm~1.6mm of agent.
- 8. according to the method described in claim 7, it is characterized in that：The preparation method of the catalyst includes the following steps：(1) preparation of complex carrier：By each component content in catalyst weigh respectively aluminium oxide, ZSM-5 and mesopore silicon oxide into Row mixing, and a certain amount of dust technology, sesbania powder are added, 1-3h, then extruded moulding are then stirred at normal temperatures, finally in 80- 110 DEG C are dried overnight, and 6-10h is roasted at 450-650 DEG C up to complex carrier；(2) load of active component：The method for taking step impregnation is loaded, first by the content of Zr, Ce or La metal in catalyst Its precursor solution is prepared, then the complex carrier of step (1) is added in above-mentioned solution, and is being stirred continuously lower dipping 12-24h, finally centrifuges out solids, is dried overnight at 80-110 DEG C, and 6-10h is roasted at 350-550 DEG C up to loading The catalyst of Zr, Ce or La metal；Further, above-mentioned same dipping method is taken by Mo, W metal and Fe, Cu or Ag gold Belong to load on a catalyst.
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