CN108236965A - A kind of Hydrobon catalyst of modification and preparation method thereof - Google Patents
A kind of Hydrobon catalyst of modification and preparation method thereof Download PDFInfo
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- CN108236965A CN108236965A CN201611228561.2A CN201611228561A CN108236965A CN 108236965 A CN108236965 A CN 108236965A CN 201611228561 A CN201611228561 A CN 201611228561A CN 108236965 A CN108236965 A CN 108236965A
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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
- B01J29/60—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L, as exemplified by patent document US3216789
- B01J29/64—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L, as exemplified by patent document US3216789 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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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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- 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
- C10G2300/1048—Middle distillates
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
- C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
-
- 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
- C10G2300/1048—Middle distillates
- C10G2300/1059—Gasoil having a boiling range of about 330 - 427 °C
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Abstract
The invention discloses a kind of Hydrobon catalysts of modification and preparation method thereof, and L/Al is synthesized including (1)2O3Composite molecular screen carrier；(2) by the salting liquid of composite molecular screen carrier impregnation magnesium metal, magnesium-modified complex carrier is made in roasting；(3) by citric acid and magnesium-modified complex carrier mechanical mixture, double modified complex carriers are made in roasting；(4) salting liquid of metal molybdenum is added dropwise in double modified complex carriers, ultrasonic echography dispersion, then the salting liquid of metallic cobalt is added dropwise, ultrasonic echography dispersion, drying roasts to obtain modified Hydrobon catalyst；Wherein, on the basis of modified Hydrobon catalyst, metallic cobalt is in terms of CoO, and content is 0~5.0wt%, and metal molybdenum is with MoO3Meter, content are 15.0~20.0wt%, and for magnesium metal in terms of MgO, content is 0.5%~4.0wt%, and citric acid content is 0.5% 4.0wt%.Catalyst of the present invention has terraced distribution aperture, larger specific surface area and pore volume, suitable acidity, uses it for the hydrodesulfurization reaction of diesel oil, active up to more than 97.5%.
Description
Technical field
The present invention relates to a kind of Hydrobon catalysts and preparation method thereof more particularly to a kind of hydrodesulfurization of modification to urge
Agent and preparation method thereof.
Background technology
In recent years, haze weather shrouds each big city in the whole nation, and very big harm is caused to people's health and trip.It grinds
Study carefully discovery, motor-vehicle tail-gas is to cause one of main source of haze weather, and the sulfide in motor-vehicle tail-gas is main dirt
Contaminate one of object.For the emission problem of sulfide in motor-vehicle tail-gas, increasingly stringenter motor vehicle has been formulated in countries in the world
The fuel oil quality standard of exhaust emission standard and harshness.Wherein, the sulfur content in fuel oil must reach ultra low levels, and novel
The design and development of efficient hydrodesulfurization (HDS) catalyst is one of most effective means for realizing cleaning diesel production.At present,
Successfully have developed different types of catalyst both at home and abroad.
In diesel hydrogenation for removal sulphur field, AKZO companies are proposed STARS catalyst technologies：The technology is suitable for production sulphur and contains
Amount is less than 50 × 10-6Low-sulfur or super-low sulfur clean fuel, the main representative of commercial Application for KF-757 (Co-Mo) and
KF-848 (Ni-Mo) catalyst series.KF-848 (Ni-Mo) catalyst can produce sulfur nutrient under the conditions of mesolow and be less than
10x10-6Clean fuel.Then, the said firm is by controlling the generation of active cobalt molybdenum phase, so as to promote difficult sulfur-containing compound
Removing, develop KF-767 (Co-Mo) catalyst series, hydrodesulfurization volume activity is improved compared with KF-757 (Co-Mo)
30%-50%.In addition, the said firm also developed Nebula-1 and Nebula-20 catalyst.By Criterion catalyst technologies
Company's Ascent catalyst, employs improved support preparation method and dedicated dipping technique so that aluminium oxide surface area obtains
To optimization, active metal dispersion degree is improved, and I types and II types activated centre are mixed to get optimization, and representative catalyst is
DC-2531.These new technologies meet the needs of production ultra-low-sulphur diesel.Rope company of Top is proposed TK-558Brim (Co-
Mo) and TK-559Brim (Ni-Mo) catalyst, both new catalysts are used to add the edge active center of hydrogen and for straight
The corner angle activated centre for connecing desulfurization is obtained for optimization.
And at home, by the RS-1000 catalyst of Research Institute of Petro-Chemical Engineering's developmental research to inferior raw material and property
Very poor secondary processing gasoline and diesel raw material shows very high deep hydrodesulfurizationof activity, under suitable process conditions
The sulfur content of diesel oil can be dropped to below 50 μ g/g.Then, by selecting active metal ratio, auxiliary agent and organic complexing agent
The ultra-deep HDS catalyst RS-1100 of novel NiMo are prepared with optimization, in hydrogen partial pressure 6.4MPa, volume space velocity 2.0h-1It is anti-
Under the conditions of answering, the ultra-low-sulphur diesel that sulfur content is less than 10 μ g/g can be produced.By Sinopec, Fushun Petrochemical Research Institute grinds
The ultra-deep diesel hydrogenation for removal sulphur of FHUDS series for studying carefully exploitation has also obtained good application.Wherein, FHUDS-6 catalyst has
Good stability and hydrodesulfurization activity, in 352 DEG C of reaction temperature, hydrogen partial pressure 6.15MPa, air speed 2.53h-1, hydrogen oil volume
Under conditions of being 254.3, diesel oil sulfur content by 12200 μ g/g can be dropped to 250 μ g/g hereinafter, desulfurization degree is 98.02%,
The Cetane number of diesel product improves 5.7 units simultaneously.
As it can be seen that the performance of catalyst is still to produce the key of clear gusoline.And carrier pore passage structure, acidity and metal point
Scattered property affects its catalytic performance again, therefore, to improve catalyst hydrogenation performance it is necessary to start with from this several respect.Using difference
Element is modified catalyst or carrier, can be shown with the acidity and pore structure of regulating catalyst, the addition of a small amount of auxiliary agent
Write the catalytic performance for improving catalyst.It is that the metal-modified and complexing agent of catalyst and carrier is modified to study at present more.By
In pure silicon material without acid activated centre, it is impossible to directly apply to some acid catalyzed reactions.In order to solve this problem, in pure silicon
Loaded metal ion increases the acidic site and catalytic active center in framework of molecular sieve in material matrix.For example, by Al ions
Load to mesoporous SiO2In material, Si4+By Al3+Replaced, make to generate proton acid site with charge in framework of molecular sieve, so as to
Prepare the molecular sieve catalyst with acid centre.And before the content of institute's doped metal ion depends on metal ion used
Drive body and doping method.Element Zn is introduced into catalyst the hydrodesulfurization selection that can significantly increase catalyst as additive
Property, warm light has investigated the different types of aluminium oxide (γ-Al of ZnO modifications2O3With θ-Al2O3) hydrodesulfurization selectivity, hair
Now after two kinds of alumina supports load zinc oxide, the hydrodesulfurization activity of catalyst all significantly increases, and alkene saturation is lost
It varies less.Hou Yuandong respectively with Zn, Cu, Fe, Mn using step impregnation method (first impregnate Co, Mo, then impregnate modifying element) and
Co-impregnation (Co, Mo and modified metal single-steeping) is to Co-Mo/ γ-Al2O3Carry out chemical modification.Micro anti-evaluation result table
It is bright：The selectivity factor (S) of Cu modified catalysts is maximum in step impregnation modification method；The S of Zn modified catalysts in co-impregnation
It is maximum.Many studies have shown that modifying element is introduced in molecular sieve can also significantly improve its acid distribution.The system researches such as Pang
The influence that Zn, Cu and V transition metal are modified USY molecular sieve, pyridine infrared results show：By the L of modified USY molecular sieve
Acid amount is apparent to be increased, highly beneficial to FCC gasoline hygrogenating isomerization reaction.
In addition, many complexometric reagents are applied to have in the preparation of catalyst and to the raising of active constituent dispersion degree
There is apparent facilitation, such as aminotriacetic acid (NTA), citric acid (CA), ethylenediamine (EN) and disodium ethylene diamine tetraacetate
(EDTA) etc..These complexing agents can interact to form complex compound with metal ion Ni, Co and Mo.These networks in sulfidation
It closes object to decompose, releases Ni, Co and Mo atom, these atomic migrations to active phase MoS2Edge, therefore be formed high work
The II type NiMoS activity phases of property.In numerous complexometric reagents, citric acid has obtained widely should in the preparation of HDS catalyst
With.
Li et al. is prepared for four kinds of catalyst (NiW/Al2O3、NiW/C-Al2O3、C-NiW/Al2O3And C-NiW/C-Al2O3),
And the effect that citric acid plays in the preparation of NiW catalyst series is inquired into.The results show that the 4,6-DMDBT of four kinds of catalyst
HDS reaction rate constants sequence be：C-NiW/C-Al2O3>NiW/C-Al2O3>C-NiW/Al2O3>NiW/Al2O3.Author is also to lemon
The inherent effect of lemon acid is expounded：(1) catalyst of citric acid-modified can be carbonized partly in pre-vulcanization process, thus every
From with reduce WS2The length of layer；(2) citric acid can react to form hydrogen bond with the-OH of carrier surface, so as to weaken it is active mutually and
Al2O3Interaction between carrier.
Therefore, in order to meet increasingly stringent clear gusoline standard, how to prepare with appropriate acid, tied suitable for duct
The diesel hydrogenation for removal sulphur catalyst of structure and active metal and carrier intermolecular forces, makes this field research emphasis.
Invention content
It is existing to improve it is a primary object of the present invention to provide a kind of Hydrobon catalyst of modification and preparation method thereof
Have the hydrothermal stability of catalyst in technology, improve catalyst pore passage structure and acid and active metal and carrier it is mutual
Active force.
To achieve these goals, the present invention provides a kind of preparation method of the Hydrobon catalyst of modification, the party
Method includes the following steps：
(1) using nano microcrystalline self-assembly method, L/Al is synthesized2O3Composite molecular screen carrier；
(2) by L/Al2O3The salting liquid of composite molecular screen carrier impregnation magnesium metal, then roasting is made magnesium-modified compound
Carrier；
(3) by citric acid and magnesium-modified complex carrier mechanical mixture, double modified complex carriers are made in then roasting；And
(4) salting liquid of metal molybdenum is added dropwise in double modified complex carriers, stirs evenly, disperseed using ultrasonic echography
Then 10~40min is added dropwise the salting liquid of metallic cobalt, stirs evenly again, disperse 10~40min, drying using ultrasonic echography
Roast to obtain modified Hydrobon catalyst；
Wherein, on the basis of modified Hydrobon catalyst, for the metallic cobalt in terms of CoO, content is 0~5.0wt%,
The metal molybdenum is with MoO3Meter, content are 15.0~20.0wt%, the magnesium metal in terms of MgO, content for 0.5%~
4.0wt%, the citric acid content are 0.5%-4.0wt%.
The preparation method of the Hydrobon catalyst of modification of the present invention, wherein, the L/Al2O3Composite molecular screen
L-type molecular sieve and the mass ratio of aluminium oxide are preferably 4 in carrier:1~6:1.
The preparation method of the Hydrobon catalyst of modification of the present invention, wherein, the salting liquid of the magnesium metal is excellent
It is selected as magnesium acetate aqueous solution.
The preparation method of the Hydrobon catalyst of modification of the present invention, wherein, the salting liquid of the metal molybdenum is excellent
It is selected as ammonium molybdate aqueous solution.
The preparation method of the Hydrobon catalyst of modification of the present invention, wherein, the salting liquid of the metallic cobalt is excellent
It is selected as cobalt nitrate aqueous solution.
The preparation method of the Hydrobon catalyst of modification of the present invention, wherein it is preferred that the L/Al2O3It is multiple
The ammonium that composite molecular screen carrier is further included before the salting liquid of conjunction molecular sieve carrier impregnating metal magnesium exchanges, drying steps.
The preparation method of the Hydrobon catalyst of modification of the present invention, wherein, step (2) calcination temperature is excellent
It is selected as 450~750 DEG C.
The preparation method of the Hydrobon catalyst of modification of the present invention, wherein, step (3) calcination temperature is excellent
It is selected as 450~750 DEG C.
The preparation method of the Hydrobon catalyst of modification of the present invention, wherein, step (4) calcination temperature is excellent
It is selected as 450~750 DEG C.
The present invention also provides catalyst prepared by the preparation method of the Hydrobon catalyst of above-mentioned modification.
Beneficial effects of the present invention：
1st, different from other micro porous molecular sieves, there is L molecular sieves special LTL topological structures, acid strong, acid amount to be easy to adjust
The features such as section and pore-size distribution are uniform, it is compound with conventional aluminium oxide, and prepared complex carrier has trapezoidal pore-size distribution,
Suitable acidity, the specific surface area and pore volume of bigger, this is conducive to diffusion of the reactant molecule in carrier duct, suitable
The acid interaction force for improving active metal and carrier again, more than feature are conducive to the hydrodesulfurization reaction of diesel oil.
2nd, the addition of Mg does not destroy the crystal form and structure of catalyst, and Mg2+Instead of Al2O3In spinel structure
Tetrahedron Al3+, this is conducive to the surface distribution of active component；The addition of Mg also makes active metal Mo be more easy in sulfidation
Vulcanization has higher reactivity.The addition of citric acid can promote the dispersion of metal, the aggregation of inhibitory activity component, increase
The specific surface area of catalyst.Citric acid can form complex compound with active metal Co, Mo, increase the number of easy reduction activation species
Amount；And interaction of the modulation between metal and carrier, enhance the active force between active metal and molecular sieve, and then
Promote the dispersion of active metal, be conducive to diesel hydrogenation for removal sulphur reaction.
3rd, by double modified catalyst, there is terraced distribution aperture, larger specific surface area and pore volume, suitable
Acidity uses it for the hydrodesulfurization reaction of diesel oil, active up to more than 97.5%.
Specific embodiment
It elaborates below to the embodiment of the present invention：The present embodiment is carried out lower based on the technical solution of the present invention
Implement, give detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
Embodiment 1
By molar ratio K2O：Al2O3：SiO2：H2O is 0.5：0.15:1:20 weigh potassium hydroxide, distilled water and sial
Microballoon (silica alumina ratio Al2O3：SiO2It is 0.15:1) it, by the potassium hydroxide weighed, distilled water, pours into beaker and stirs
To being completely dissolved, extraordinary silicon and aluminum source-silicon aluminium microsphere is slowly added in lye under stirring, and make silicon aluminium microsphere completely molten
Solution.It is 4 according still further to L molecular sieves and quality of alumina ratio:1 adds in aluminium oxide, continues to stir 30min, by what is stirred evenly
Coagulant liquid pours into crystallizing kettle, and L/Al is made after filtering roasting in crystallization2O3Complex carrier.
Magnesium acetate is added in deionized water, the modified solution for being configured to 0.1mol/L is for use.By the L/Al of preparation2O3
Complex carrier carries out ammonium exchange, does not roast the prepared magnesium acetate solution of direct impregnation after dry, is then roasted in Muffle furnace again
3h is burnt, calcination temperature is 550 DEG C, and the complex carrier of Mg modifications is made.0.4g citric acids are weighed again, are added to the compound of Mg modifications
It in carrier, stirs evenly, ultrasonic disperse 20min is carried out using ultrasonic wave, then again in Muffle kiln roasting 3h, calcination temperature is
550 DEG C, obtain double modified complex carriers, water absorption rate 66%.
Ammonium Molybdate Tetrahydrate is weighed, deionized water is added in and is made into a concentration of 0.9mol/L solution, according to the suction of complex carrier
Water rate is stirred in drop to the complex carrier of double modifications, reaches saturated water adsorptive value, stirring is up to uniform, using ultrasonic wave
Ultrasonic disperse 20min is carried out, cobalt nitrate is then weighed, is configured to 0.1mol/L solution, urging to load Mo is then slowly added dropwise
In agent, addition is identical with ammonium molybdate solution, stirs evenly.Ultrasonic disperse about 20min, then carries out in 110 DEG C of baking ovens
Dry about 4h, and roast 4h under the conditions of 550 DEG C, you can obtain CoMo loaded catalysts.Tabletting is carried out to catalyst, and
The catalyst granules that size is screened as 40-60 mesh is for use, is denoted as catalyst A.Wherein Mg contents be 0.5wt%, citric acid content
For 4wt%.
Embodiment 2
By molar ratio K2O：Al2O3：SiO2：H2O is 0.5：0.15:1:20 weigh potassium hydroxide, distilled water and sial
Microballoon (silica alumina ratio Al2O3：SiO2It is 0.15:1) it, by the potassium hydroxide weighed, distilled water, pours into beaker and stirs
To being completely dissolved, extraordinary silicon and aluminum source-silicon aluminium microsphere is slowly added in lye under stirring, and make silicon aluminium microsphere completely molten
Solution.It is 6 according still further to L molecular sieves and quality of alumina ratio:1 adds in aluminium oxide, continues to stir 30min, by what is stirred evenly
Coagulant liquid pours into crystallizing kettle, and L/Al is made after filtering roasting in crystallization2O3Complex carrier.
Magnesium acetate is added in deionized water, the modified solution for being configured to 0.2mol/L is for use.By the L/Al of preparation2O3
Complex carrier carries out ammonium exchange, does not roast the prepared magnesium acetate solution of direct impregnation after dry, is then roasted in Muffle furnace again
3h is burnt, calcination temperature is 550 DEG C, and the complex carrier of Mg modifications is made.0.2g citric acids are weighed again, are added to the compound of Mg modifications
It in carrier, stirs evenly, ultrasonic disperse 20min is carried out using ultrasonic wave, then again in Muffle kiln roasting 3h, calcination temperature is
550 DEG C, obtain double modified complex carriers, water absorption rate 66%.
Ammonium Molybdate Tetrahydrate is weighed, deionized water is added in and is made into a concentration of 1.0mol/L solution, according to the suction of complex carrier
Water rate is stirred in drop to the complex carrier of double modifications, reaches saturated water adsorptive value, stirring is up to uniform, using ultrasonic wave
Ultrasonic disperse 20min is carried out, cobalt nitrate is then weighed, is configured to 0.2mol/L solution, urging to load Mo is then slowly added dropwise
In agent, addition is identical with ammonium molybdate solution, stirs evenly.Ultrasonic disperse about 20min, then carries out in 110 DEG C of baking ovens
Dry about 4h, and roast 4h under the conditions of 550 DEG C, you can obtain CoMo loaded catalysts.Tabletting is carried out to catalyst, and
The catalyst granules that size is screened as 40-60 mesh is for use, is denoted as catalyst B.Wherein Mg contents be 1.0wt%, citric acid content
For 2.0wt%.
Embodiment 3
By molar ratio K2O：Al2O3：SiO2：H2O is 0.5：0.15:1:20 weigh potassium hydroxide, distilled water and sial
Microballoon (silica alumina ratio Al2O3：SiO2It is 0.15:1) it, by the potassium hydroxide weighed, distilled water, pours into beaker and stirs
To being completely dissolved, extraordinary silicon and aluminum source-silicon aluminium microsphere is slowly added in lye under stirring, and make silicon aluminium microsphere completely molten
Solution.It is 5 according still further to L molecular sieves and quality of alumina ratio:1 adds in aluminium oxide, continues to stir 30min, by what is stirred evenly
Coagulant liquid pours into crystallizing kettle, and L/Al is made after filtering roasting in crystallization2O3Complex carrier.
Magnesium acetate is added in deionized water, the modified solution for being configured to 0.4mol/L is for use.By the L/Al of preparation2O3
Complex carrier carries out ammonium exchange, does not roast the prepared magnesium acetate solution of direct impregnation after dry, is then roasted in Muffle furnace again
3h is burnt, calcination temperature is 550 DEG C, and the complex carrier of Mg modifications is made.0.1g citric acids are weighed again, are added to the compound of Mg modifications
It in carrier, stirs evenly, ultrasonic disperse 20min is carried out using ultrasonic wave, then again in Muffle kiln roasting 3h, calcination temperature is
550 DEG C, obtain double modified complex carriers, water absorption rate 66%.
Ammonium Molybdate Tetrahydrate is weighed, deionized water is added in and is made into a concentration of 1.1mol/L solution, according to the suction of complex carrier
Water rate is stirred in drop to the complex carrier of double modifications, reaches saturated water adsorptive value, stirring is up to uniform, using ultrasonic wave
Ultrasonic disperse 20min is carried out, cobalt nitrate is then weighed, is configured to 0.3mol/L solution, urging to load Mo is then slowly added dropwise
In agent, addition is identical with ammonium molybdate solution, stirs evenly.Ultrasonic disperse about 20min, then carries out in 110 DEG C of baking ovens
Dry about 4h, and roast 4h under the conditions of 550 DEG C, you can obtain CoMo loaded catalysts.Tabletting is carried out to catalyst, and
The catalyst granules that size is screened as 40-60 mesh is for use, is denoted as catalyst C.Wherein Mg contents be 2.0wt%, citric acid content
For 1.0wt%.
Embodiment 4
By molar ratio K2O：Al2O3：SiO2：H2O is 0.5：0.15:1:20 weigh potassium hydroxide, distilled water and sial
Microballoon (silica alumina ratio Al2O3：SiO2It is 0.15:1) it, by the potassium hydroxide weighed, distilled water, pours into beaker and stirs
To being completely dissolved, extraordinary silicon and aluminum source-silicon aluminium microsphere is slowly added in lye under stirring, and make silicon aluminium microsphere completely molten
Solution.It is 4 according still further to L molecular sieves and quality of alumina ratio:1~6:1 adds in aluminium oxide, continues to stir 30min, will stir evenly
Coagulant liquid pour into crystallizing kettle, L/Al is made after filtering roasting in crystallization2O3Complex carrier.
Magnesium acetate is added in deionized water, the modified solution for being configured to 0.8mol/L is for use.By the L/Al of preparation2O3
Complex carrier carries out ammonium exchange, does not roast the prepared magnesium acetate solution of direct impregnation after dry, is then roasted in Muffle furnace again
3h is burnt, calcination temperature is 550 DEG C, and the complex carrier of Mg modifications is made.0.05g citric acids are weighed again, are added to answering for Mg modifications
It closes in carrier, stirs evenly, ultrasonic disperse 20min is carried out using ultrasonic wave, then again in Muffle kiln roasting 3h, calcination temperature
It is 550 DEG C, obtains double modified complex carriers, water absorption rate 66%.
Ammonium Molybdate Tetrahydrate is weighed, deionized water is added in and is made into a concentration of 1.2mol/L solution, according to the suction of complex carrier
Water rate is stirred in drop to the complex carrier of double modifications, reaches saturated water adsorptive value, stirring is up to uniform, using ultrasonic wave
Ultrasonic disperse 20min is carried out, cobalt nitrate is then weighed, is configured to 0.4mol/L solution, urging to load Mo is then slowly added dropwise
In agent, addition is identical with ammonium molybdate solution, stirs evenly.Ultrasonic disperse about 20min, then carries out in 110 DEG C of baking ovens
Dry about 4h, and roast 4h under the conditions of 550 DEG C, you can obtain CoMo loaded catalysts.Tabletting is carried out to catalyst, and
The catalyst granules that size is screened as 40-60 mesh is for use, is denoted as catalyst D.Wherein Mg contents be 4.0wt%, citric acid content
For 0.5wt%.
The evaluation of catalyst carries out on high pressure fixed-bed micro-reactor.Concrete operation step and experiment condition are such as
Under：
1. the filling of catalyst：Reactor inside diameter is 20mm, and in reactor flat-temperature zone, lower edge loads silica wool, then adds in
Certain thickness quartz sand, will be in catalyst 2g (about 2.5ml) the merging reactors of 40-60 mesh.Then side is covered on a catalyst
Cover certain thickness quartz sand and silica wool and ceramic ring.
2. reaction evaluating：Presulfurization is carried out to catalyst, curing temperature is 350 DEG C, sulfide stress 3.0MPa, during vulcanization
Between for 4h, presulfurization flow quantity is 5ml/h.Black petrochemical industry FCC diesel oil is used as raw material, the catalyst series of preparation are carried out to add hydrogen
Refined performance evaluation, reaction temperature are 350 DEG C, reaction pressure 5.0MPa, volume space velocity 1.0h-1, hydrogen-oil ratio H2/oil(V/V)
=600.The quantitative analysis of element sulphur measures sulfur content using chemiluminescence constant sulphur appliance in reactant and product.
3. the reactivity of catalyst is calculated according to hydrodesulfurization rate：
HDS%=(Sf-Sp)/Sf× 100%
In formula：SfRepresent sulfur content in raw material, SpRepresent the sulfur content in product.The reactivity of each embodiment catalyst
Data are shown in Table 1.
Table 1：The hydrodesulfurization activity of different catalysts
By double modified catalyst, there is terraced distribution aperture, larger specific surface area and pore volume, suitable acid
Property, the hydrodesulfurization reaction of diesel oil is used it for, it is active up to more than 97.5%.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (10)
1. a kind of preparation method of the Hydrobon catalyst of modification, which is characterized in that this method comprises the following steps：
(1) using nano microcrystalline self-assembly method, L/Al is synthesized2O3Composite molecular screen carrier；
(2) by L/Al2O3Magnesium-modified complex carrier is made in the salting liquid of composite molecular screen carrier impregnation magnesium metal, then roasting；
(3) by citric acid and magnesium-modified complex carrier mechanical mixture, double modified complex carriers are made in then roasting；And
(4) salting liquid of metal molybdenum is added dropwise in double modified complex carriers, stirred evenly, using ultrasonic echography dispersion 10~
Then 40min is added dropwise the salting liquid of metallic cobalt, stirs evenly again, disperse 10~40min, drying roasting using ultrasonic echography
Obtain modified Hydrobon catalyst；
Wherein, on the basis of modified Hydrobon catalyst, for the metallic cobalt in terms of CoO, content is 0~5.0wt%, described
Metal molybdenum is with MoO3Meter, content be 15.0~20.0wt%, the magnesium metal in terms of MgO, content be 0.5%~4.0wt%, institute
Citric acid content is stated as 0.5%~4.0wt%.
2. the preparation method of the Hydrobon catalyst of modification according to claim 1, which is characterized in that the L/Al2O3
L-type molecular sieve and the mass ratio of aluminium oxide are 4 in composite molecular screen carrier:1~6:1.
3. the preparation method of the Hydrobon catalyst of modification according to claim 1, which is characterized in that the magnesium metal
Salting liquid be magnesium acetate aqueous solution.
4. the preparation method of the Hydrobon catalyst of modification according to claim 1, which is characterized in that the metal molybdenum
Salting liquid be ammonium molybdate aqueous solution.
5. the preparation method of the Hydrobon catalyst of modification according to claim 1, which is characterized in that the metallic cobalt
Salting liquid be cobalt nitrate aqueous solution.
6. the preparation method of the Hydrobon catalyst of modification according to claim 1, which is characterized in that the L/Al2O3
The ammonium that composite molecular screen carrier is further included before the salting liquid of composite molecular screen carrier impregnation magnesium metal exchanges, drying steps.
7. the preparation method of the Hydrobon catalyst of modification according to claim 1, which is characterized in that the step
(2) calcination temperature is 450~750 DEG C.
8. the preparation method of the Hydrobon catalyst of modification according to claim 1, which is characterized in that the step
(3) calcination temperature is 450~750 DEG C.
9. the preparation method of the Hydrobon catalyst of modification according to claim 1, which is characterized in that the step
(4) calcination temperature is 450~750 DEG C.
10. catalyst prepared by the preparation method for the Hydrobon catalyst that claim 1-9 any one of them is modified.
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