CN110152723A - A kind of Hydrobon catalyst and its preparation method and application - Google Patents
A kind of Hydrobon catalyst and its preparation method and application Download PDFInfo
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- CN110152723A CN110152723A CN201810149392.6A CN201810149392A CN110152723A CN 110152723 A CN110152723 A CN 110152723A CN 201810149392 A CN201810149392 A CN 201810149392A CN 110152723 A CN110152723 A CN 110152723A
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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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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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
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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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
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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
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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- General Chemical & Material Sciences (AREA)
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Abstract
The present invention provides a kind of Hydrobon catalysts and its preparation method and application, wherein by the gross weight of catalyst for 100wt% in terms of, which includes the carrier of 50wt%-95wt% and the active metal component of 5wt%-50wt%；The carrier includes Sn (II) AlPO4- 5 molecular sieves and γ-Al2O3；The active metal component includes the oxide and/or sulfide of one or more of Co, Mo, Ni and W.Hydrobon catalyst provided by the invention, which uses, includes Sn (II) AlPO4- 5 molecular sieves and γ-Al2O3Carrier so that catalyst has suitable surface acidity, and there is biggish specific surface area, be capable of providing more activated centre；Effectively increase hydrodesulfurization, the denitrification reaction activity of catalyst.
Description
Technical field
The invention belongs to technical field of petrochemical industry, and in particular to a kind of Hydrobon catalyst and preparation method thereof and answer
With.
Background technique
Crude oil and from distillate obtained in crude oil contain sulphur, nitrogen, oxygen and metal impurities.The presence of these impurity
The stability of oil product is not only influenced, but also can also discharge SO in useX、NOXEqual pernicious gases pollute environment.In oil product
Secondary processing process in, the presence of sulphur, nitrogen, oxygen and metal impurities can make catalyst poisoning.Therefore, removing above-mentioned impurity is
Significant process in oil product processing.Distillate hydrogenation processing refers under certain temperature and pressure, feedstock oil and hydrogen and catalysis
Agent contact, the process of imurity-removal and aromatic hydrocarbons saturation.
As increasingly harsh environmental regulation releases one after another, people propose wanting of being increasingly stringenter to the quality of oil product
It asks, therefore the clean fuel for producing low pollution is concerned.Hydrotreating is one of important channel of Clean Fuel Production, is passed through
Hydrotreating, can make the impurity such as at least partly sulphur, nitrogen, the oxygen in oil product be converted into hydrogen sulfide, ammonia, water and remove；Simultaneously
It can make aromatic hydrocarbons, hydrocarbon fraction that hydrogen be added to be saturated, and then improve oil quality.
Catalyst activity improves, and hydrodesulfurization condition can be made more to mitigate, or under identical process conditions
Reach quality more preferably product or extend catalyst service life.So exploitation high-activity hydrofining catalyst is this
The target that field is constantly pursued.
Summary of the invention
To solve the above problems, the purpose of the present invention is to provide a kind of Hydrobon catalysts.
It is a further object of the present invention to provide a kind of preparation methods of above-mentioned Hydrobon catalyst.
It is a further object of the present invention to provide above-mentioned Hydrobon catalyst answering in gasoline, diesel oil hydrofining reaction
With.
It is a further object of the present invention to provide one kind to contain Sn (II) AlPO4- 5 molecular sieves and γ-Al2O3Carrier.
It is a further object of the present invention to provide a kind of Sn (II) AlPO4- 5 molecular sieves.
In order to achieve the above objectives, the present invention provides a kind of Hydrobon catalysts, wherein is with the gross weight of catalyst
100wt% meter, the catalyst includes the carrier of 35wt%-95wt% and the active metal component of 5wt%-50wt%；
The carrier includes Sn (II) AlPO4- 5 molecular sieves and γ-Al2O3；
The active metal component includes the oxide and/or sulfide of one or more of Co, Mo, Ni and W.
In above-mentioned Hydrobon catalyst, used in be a kind of composite carrier, include at least Sn (II)
AlPO4- 5 molecular sieves and γ-Al2O3Two kinds of components.It has been found that Sn (II) AlPO4The introducing of -5 molecular sieves has significant
The effect for improving support surface acidity, can improve the interaction of carrier and metal active constituent.
In above-mentioned Hydrobon catalyst, for Sn (II) AlPO4- 5 molecular sieves and γ-Al2O3Dosage, this field
Technical staff can determine suitable proportion according to specific application environment.In a preferred embodiment, it is with the gross weight of carrier
100wt% meter, Sn (II) AlPO4The content of -5 molecular sieves is 5wt%-60wt%；Preferably 15wt%-45wt%.At this point, outstanding
It has good effect to the hydrofinishing of gasoline, diesel oil.
In above-mentioned Hydrobon catalyst, Sn (II) AlPO4- 5 molecular sieves and γ-Al2O3Hybrid mode have no it is special
It is required that being simply mixed for the two finished product；Carrier can also be prepared using following particular form: by Sn (II) AlPO4-5
Molecular sieve and preparation γ-Al2O3Predecessor mixing, then formed, roast the carrier is made.Using above-mentioned particular form
The carrier of preparation, acid distribution is more uniform, is also beneficial to consequent activities metal component and uniformly loads in the carrier, therefore,
Its catalytic activity is higher.Moreover, carrier prepared by this mode, also there is apparent increase in terms of mechanical strength.Therefore, comprehensive
Close the carrier that performance is substantially better than the preparation of finished product hybrid mode.Prepare γ-Al2O3Predecessor can be this field conventional object
Matter selects boehmite in a preferred embodiment.
In above-mentioned Hydrobon catalyst, when preparing carrier using above-mentioned particular form, the condition of roasting mainly considers
γ-Al2O3Formation.In a preferred embodiment, the temperature of roasting is 450-650 DEG C of roasting.In addition, molding can use
The usual manner of this field, for example, it is kneaded and formed.A period of time (for example, dry at 90-120 DEG C) can be first dried after molding,
Then it is roasted.
All γ-the Al of aluminium oxide are not required in above-mentioned Hydrobon catalyst, in carrier2O3, also allow that there are it
The aluminium oxide of its form.Certainly, in carrier can also the auxiliary agents such as the dispersing aid containing this field routine, adhesive, to improve
Its respective performances.In the present invention, particular determination is not also done to the forming shape of carrier, can be adjusted according to specific needs
Section.
In above-mentioned Hydrobon catalyst, Sn (II) AlPO4- 5 molecular sieves are a kind of AlPOs modified using divalent Sn4-
5 molecular sieves, that is, in AlPO4Sn (II) is introduced in -5 framework of molecular sieve.Under normal circumstances, in preparation AlPO4- 5 molecular sieves
In conventional method, divalent tin source is added in the feed and prepares gel, then common crystallization, can be prepared by Sn (II) AlPO4- 5 points
Son sieve.SnO is in Sn (II) AlPO4Content in -5 molecular sieves is with conventional ratio.In a preferred embodiment, described
Sn(II)AlPO4In -5 molecular sieves, in terms of SnO, content 0.1wt%-4.0wt%；Preferably 0.2wt%-2.0wt%.It surveys
Examination experiment shows catalyst made of the molecular sieve of the proportion, has better hydrogenation catalyst performance.
In above-mentioned Hydrobon catalyst, the active metal of supported on carriers can be one of Co, Mo, Ni and W
Or several combination.After these active metals are fired, generally exist in the form of the oxide, therefore, active metal component can
Think the oxide of respective metal.In addition, catalyst before use, will carry out presulfurization processing sometimes, partial oxide can turn
Become sulfide, therefore, active metal component may be the sulfide of respective metal, alternatively, simultaneously including oxide and sulphur
Compound.In a preferred embodiment, the oxide and/or sulfide that active metal component is Co and Mo (urge by Co/Mo bimetallic
Agent), the oxide and/or sulfide (Ni/W bimetallic catalyst) of Ni and W, Co and Mo and W oxide and/or sulfide
(Co/Mo/W trimetallic catalyst).Certainly, the combination of active metal component is not limited to above-mentioned three kinds, can of course
For other usual manners in this field.In another preferred embodiment, active metal component is selected from corresponding active metal
Oxide.By taking the catalyst of above-mentioned three kinds of forms as an example, active metal component is respectively CoO and MoO3Combination；NiO and MoO3
Combination；CoO,MoO3And MoO3Combination.
In above-mentioned Hydrobon catalyst, conventional ratio is can be used in the relative amount of active metal component and carrier.?
In one preferred embodiment, by the gross weight of catalyst for 100wt% in terms of, the catalyst includes the load of 60wt%-80wt%
The active metal component of body and 20wt%-40wt%.
In above-mentioned Hydrobon catalyst, in a preferred embodiment, active metal component includes NiO and WO3；Two
The content of person is respectively the 2wt%-13wt% and 8wt%-37wt% of overall catalyst weight.
In above-mentioned Hydrobon catalyst, when to supported on carriers active metal, the routine side of this field can be used
Formula.In a preferred embodiment provided by the invention, loaded using infusion process；For example, can be with containing one in Ni and W
Kind or two kinds of metal salt solution impregnated carrier.When it is implemented, equi-volume impregnating can be used.
Hydrobon catalyst provided by the invention, which uses, includes Sn (II) AlPO4- 5 molecular sieves and γ-Al2O3Load
Body so that catalyst has suitable surface acidity, and has biggish specific surface area, is capable of providing in more activity
The heart.Hydrodesulfurization, the denitrification reaction activity of catalyst can be effectively improved.
The present invention also provides a kind of preparation methods of above-mentioned Hydrobon catalyst, wherein this method includes following step
It is rapid:
By Sn (II) AlPO4- 5 molecular sieves and preparation γ-Al2O3Predecessor mixing, then formed, roast obtained load
Body；
Impregnate the carrier with containing one or more of soluble metal salt solution in Co, Mo, Ni and W, then through drying,
The Hydrobon catalyst is made in roasting.
Scheme provided by the invention, by Sn (II) AlPO4- 5 molecular sieves, which are introduced into alumina support, to be effectively improved
The interaction of carrier and metal active constituent improves the activity of catalyst.It is catalyzed compared to traditional gasoline, diesel oil hydrogenation
Agent, preparation process provided by the invention can add in carrier preparation process under the premise of not changing existing production technology substantially
Enter corresponding Sn (II) AlPO4- 5 molecular sieves carry out the structure and acidity of modulation carrier so that catalyst have higher desulfurization,
The hydrogenation reaction activity of denitrogenation.
The present invention also provides a kind of application of above-mentioned Hydrobon catalyst in gasoline, diesel oil hydrofining reaction.
Above-mentioned Hydrobon catalyst is using the active metal (Co, Mo, Ni and W) in gasoline, diesel oil hydrofining catalyst, activity gold
The oxide of category can get higher hydrogenation activity after vulcanizing.The supported active metals Co/Mo group especially on complex carrier
It closes, the bimetallic catalyst that Ni/W is combined, Co/Mo/W combination is prepared, it is very good to have in terms of the hydrofinishing to diesel oil
Effect, for improve hydrogenated diesel oil quality have positive effect.
The present invention also provides one kind to contain Sn (II) AlPO4- 5 molecular sieves and γ-Al2O3Carrier, wherein with described
The gross weight of carrier is 100wt% meter, Sn (II) AlPO4The weight of -5 molecular sieves accounts for 5wt%-60wt%；The carrier is
It is prepared by the following method: by Sn (II) AlPO4- 5 molecular sieves and preparation γ-Al2O3Predecessor mixing, after roasting be made
The carrier.The carrier prepared using above-mentioned particular form, performance are substantially better than Sn (II) AlPO directly4- 5 molecular sieves and
γ-Al2O3The carrier of hybrid mode preparation.Prepare γ-Al2O3Predecessor can be this field conventional substances, one preferably
In embodiment, boehmite is selected.
Contain Sn (II) AlPO above-mentioned4- 5 molecular sieves and γ-Al2O3Carrier in, the condition of roasting mainly considers γ-
Al2O3Formation.In a preferred embodiment, the condition of roasting are as follows: roast 2-8h at 450-650 DEG C.In addition, molding can be with
Using the usual manner of this field, for example, it is kneaded and formed.A period of time can be first dried after molding (for example, doing at 90-120 DEG C
It is dry), then roasted.
Contain Sn (II) AlPO above-mentioned4- 5 molecular sieves and γ-Al2O3Carrier in, it is complete that aluminium oxide is not required in carrier
Portion is γ-Al2O3, also allow that there are the aluminium oxide of other forms.Certainly, the dispersion of this field routine can also be contained in carrier
The auxiliary agents such as auxiliary agent, adhesive, to improve its respective performances.In the present invention, particular determination is not also done to the forming shape of carrier,
It can be adjusted according to specific needs.
Contain Sn (II) AlPO above-mentioned4- 5 molecular sieves and γ-Al2O3Carrier in, it is preferable that with the total of the carrier
Weight is 100wt% meter, Sn (II) AlPO4The weight of -5 molecular sieves accounts for 15wt%-45wt%.
The present invention also provides a kind of Sn (II) AlPO4- 5 molecular sieves, wherein Sn (II) AlPO4- 5 molecular sieves are logical
It crosses following methods preparation: (1) divalent tin source and AlPO will be used to prepare4The raw material of -5 molecular sieves is mixed, preparation mixing
Gel；(2) Crystallizing treatment, calcination process are carried out to the mixed gel, the Sn (II) AlPO is made4- 5 molecular sieves.
In above-mentioned Sn (II) AlPO4In -5 molecular sieves, the divalent tin source of most of solubilities can be used.It is preferred real one
It applies in mode, the divalent tin source used is stannous chloride or stannous acetate.
In above-mentioned Sn (II) AlPO4In -5 molecular sieves, under normal circumstances, in preparation AlPO4The conventional method of -5 molecular sieves
In, divalent tin source is added in the feed and prepares gel, then common crystallization, can be prepared by Sn (II) AlPO4- 5 molecular sieves.It can be with
Using preparation AlPO4Commonly through Crystallizing treatment method when -5 molecular sieve.In a preferred embodiment, using conventional hydro-thermal
Crystallizing treatment mode can obtain the more stable product of quality in this way, furthermore, it is possible to which technique and equipment is made not to make larger change.
In above-mentioned Sn (II) AlPO4In -5 molecular sieves, it is preferable that the condition of hydrothermal crystallizing processing are as follows: brilliant at 140-200 DEG C
Change 14-36h.Preferably, the condition of the calcination process are as follows: roast 2-8h at 450-650 DEG C.
In above-mentioned Sn (II) AlPO4In -5 molecular sieves, in a preferred embodiment, Sn (II) AlPO4In -5 molecular sieves with
SnO meter, content 0.1wt%-4.0wt%；Preferably 0.2wt%-2.0wt%.
In above-mentioned Sn (II) AlPO4In -5 molecular sieves, gel can be by preparing AlPO in the prior art4- 5 molecular sieves it is normal
Rule method adds corresponding divalent tin source to prepare.In a preferred embodiment, it is used to prepare AlPO4The original of -5 molecular sieves
Material includes: water, silicon source, phosphorus source and template.Preferably, source of aluminium includes boehmite, and phosphorus source includes phosphoric acid (one
As be concentrated phosphoric acid), the template includes triethylamine, triethanolamine, tetraethylammonium bromide or tetraethyl ammonium hydroxide.Further
Preferably, the water, silicon source, phosphoric acid, tin source and template are respectively according to H2O、Al2O3、P2O5, SnO and template meter, each component
Molar ratio be 30-70:1:0.9-1.7:0.01-0.2:1-3.
In above-mentioned Sn (II) AlPO4In -5 molecular sieves, the Sn (II) AlPO is prepared4The step of -5 molecular sieve includes:
(1) in room temperature at 60 DEG C, after mixing by boehmite and water, phosphoric acid, divalent tin source is added, fills it
Divide dissolution, is added dropwise to phosphoric acid and continues to stir 0.3-3h, be then slowly added into template, after 1-10h is mixed, mixed
Close gel；
(2) by mixed gel 140-200 DEG C of crystallization 14-36h in a high pressure reaction kettle, crystallization product washed,
After filtering, dry, roasting, Sn (II) AlPO is obtained4- 5 molecular sieves.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention
Art scheme carries out described further below, but should not be understood as that limiting the scope of the invention.
Embodiment 1
A kind of hydrogenation catalyst is present embodiments provided, to be prepared using infusion process, specifically includes the following steps:
(1) by 5.87g boehmite, 10.00g concentrated phosphoric acid (mass fraction 85%), 6.00g triethylamine,
1.00gSnCl2·2H2In O and 29.00g deionized water, mixed gel is made into after agitated mixing, 100mL autoclave dynamic is brilliant
Change 20h, Sn (II) AlPO is made after washing, filtering, dry, roasting4- 5 molecular sieves, wherein molecular sieve quality is based on 100wt%
It calculates, SnO content is 1.1wt%；
(2) by Sn (II) AlPO4- 5 molecular sieves are mixed with boehmite according to mass ratio 4:6, and extrusion forming dries in the air naturally
Carrier is made in dry, 550 DEG C of roasting 4h；
(3) it takes 1.57g nickel nitrate, 3.16g ammonium metatungstate to be dissolved in 7.00g deionized water, is configured to co-impregnation solution；
It (4) is to be obtained in the above-mentioned carrier of 1.5mm by the diameter that the co-impregnation liquid is added dropwise to 7.00g extruded moulding
Catalyst semi-finished product；
(5) above-mentioned catalyst semi-finished product are stood 24 hours in air, are dried in 120 DEG C of baking oven, then with 4
DEG C/heating of the rate of min, it is roasted 4 hours under 500 DEG C, air atmosphere, obtains hydrogenation catalyst F-1.
The total amount for measuring nickel tungsten oxide in catalyst F-1 is 31.0wt% (using the total weight of catalyst F-1 as base
It is quasi-).The measurement of the oxide total content of activity component metal and aided metal and calculation method are known in this field in catalyst
Measurement and calculation method.
Comparative example 1
This comparative example provides a kind of diesel oil hydrogenation catalyst, as a comparison catalyst.
The preparation method of the comparative catalyst the following steps are included:
(1) 4.74g ammonium metatungstate and 2.26g nickel nitrate are dissolved in 10mL deionized water, are made into maceration extract；
It (2) is to be urged in the oxidation aluminum strip of 1.5mm by the diameter that the maceration extract is added dropwise to 10.0g extruded moulding
Agent semi-finished product；
(3) the catalyst semi-finished product are stood 24 hours in air, are dried in 120 DEG C of baking oven, then with 5
DEG C/heating of the rate of min, roast 4 hours under 500 DEG C, air atmosphere, obtain described in comparative catalyst 1.Measure the comparison
The total amount of nickel tungsten oxide is 31.0wt% in catalyst (on the basis of the total weight of catalyst F-1).
Embodiment 2
A kind of hydrogenation catalyst is present embodiments provided, to be prepared using infusion process, specifically includes the following steps:
(1) by 5.87g boehmite, 10.00g concentrated phosphoric acid (mass fraction 85%), 6.00g triethylamine,
2.00gSnCl2·2H2In O and 29.00g deionized water, mixed gel is made into after agitated mixing, 100mL autoclave dynamic is brilliant
Change 20h, Sn (II) AlPO is made after washing, filtering, dry, roasting4- 5 molecular sieves, wherein molecular sieve quality is based on 100wt%
It calculates, SnO content is 2.7wt%；
(2) by Sn (II) AlPO4- 5 molecular sieves are mixed with boehmite according to mass ratio 3:7, and extrusion forming dries in the air naturally
Carrier is made in dry, 550 DEG C of roasting 4h；
(3) it takes 1.57g nickel nitrate, 3.16g ammonium metatungstate to be dissolved in 4.00g deionized water, is configured to co-impregnation solution；
It (4) is to be urged in the above-mentioned carrier of 1.5mm by the diameter that the co-impregnation liquid is added dropwise to 4.0g extruded moulding
Agent semi-finished product；
(5) above-mentioned catalyst semi-finished product are stood 24 hours in air, are dried in 120 DEG C of baking oven, then with 4
DEG C/heating of the rate of min, it is roasted 4 hours under 500 DEG C, air atmosphere, obtains hydrogenation catalyst F-2.
The total amount for measuring nickel tungsten oxide in catalyst F-2 is 42.9wt% (using the total weight of catalyst F-2 as base
It is quasi-).The measurement of the oxide total content of activity component metal and aided metal and calculation method are known in this field in catalyst
Measurement and calculation method.
Comparative example 2
This comparative example provides a kind of diesel oil hydrogenation catalyst, as a comparison catalyst.
The preparation method of the comparative catalyst the following steps are included:
(1) 3.16g ammonium metatungstate and 1.57g nickel nitrate are dissolved in 4.0mL deionized water, are made into maceration extract；
It (2) is to be catalyzed in the oxidation aluminum strip of 1.5mm by the diameter that the maceration extract is added dropwise to 4.0g extruded moulding
Agent semi-finished product；
(3) the catalyst semi-finished product are stood 24 hours in air, are dried in 120 DEG C of baking oven, then with 5
DEG C/heating of the rate of min, roast 4 hours under 500 DEG C, air atmosphere, obtain described in comparative catalyst 2.Measure the comparison
The total content of nickel tungsten oxide is 42.9wt% in catalyst (on the basis of the total weight of the comparative catalyst).
Embodiment 3
A kind of hydrogenation catalyst is present embodiments provided, to be prepared using infusion process, specifically includes the following steps:
(1) by 5.97g boehmite, 10.5g concentrated phosphoric acid, 6.4g triethylamine, 4.0g stannous acetate and 29.9g deionization
In water, mixed gel is made into after agitated mixing, 100mL autoclave dynamic crystallization 20h makes after washing, filtering, dry, roasting
Obtain Sn (II) AlPO4- 5 molecular sieves, wherein molecular sieve quality is calculated by 100wt%, and SnO content is 3.5wt%；；
(2) by Sn (II) AlPO4- 5 molecular sieves are mixed with boehmite according to mass ratio 5:5, and extrusion forming dries in the air naturally
Carrier is made in dry, 550 DEG C of roasting 4h；
(3) it takes 1.57g nickel nitrate, 3.16g ammonium metatungstate to be dissolved in 7.0g deionized water, is configured to co-impregnation solution；
It (4) is to be urged in the above-mentioned carrier of 1.5mm by the diameter that the co-impregnation liquid is added dropwise to 9.0g extruded moulding
Agent semi-finished product；
(5) above-mentioned catalyst semi-finished product are stood 24 hours in air, are dried in 120 DEG C of baking oven, then with 4
DEG C/heating of the rate of min, it is roasted 4 hours under 500 DEG C, air atmosphere, obtains hydrogenation catalyst F-3.
The total amount for measuring nickel tungsten oxide in catalyst F-3 is 25.0wt% (using the total weight of catalyst F-3 as base
It is quasi-).The measurement of the oxide total content of activity component metal and aided metal and calculation method are known in this field in catalyst
Measurement and calculation method.
Comparative example 3
This comparative example provides a kind of diesel oil hydrogenation catalyst, as a comparison catalyst.
The preparation method of the comparative catalyst the following steps are included:
(1) 3.16g ammonium metatungstate and 1.57g nickel nitrate are dissolved in 9.0mL deionized water, are made into maceration extract；
It (2) is to be catalyzed in the oxidation aluminum strip of 1.5mm by the diameter that the maceration extract is added dropwise to 9.0g extruded moulding
Agent semi-finished product；
(3) the catalyst semi-finished product are stood 24 hours in air, are dried in 120 DEG C of baking oven, then with 5
DEG C/heating of the rate of min, roast 4 hours under 500 DEG C, air atmosphere, obtain described in comparative catalyst 3.Measure the comparison
The total content of nickel tungsten tungsten oxide is 25.0wt% in catalyst (on the basis of the total weight of the comparative catalyst).
Embodiment 4
A kind of hydrogenation catalyst is present embodiments provided, to be prepared using infusion process, specifically includes the following steps:
(1) 5.97g boehmite, 10.5g concentrated phosphoric acid (mass fraction 85%), 6.4g triethylamine, 0.5g acetic acid is sub-
In tin and 29.9g deionized water, mixed gel, 100mL autoclave dynamic crystallization 20h, washing, mistake are made into after agitated mixing
Sn (II) AlPO is made after filter, dry, roasting4- 5 molecular sieves, are calculated by molecular sieve quality 100wt%, and SnO content is
0.3wt%；；
(2) by Sn (II) AlPO4- 5 molecular sieves are mixed with boehmite according to mass ratio 2:8, and extrusion forming dries in the air naturally
Carrier is made in dry, 550 DEG C of roasting 4h；
(3) it takes 1.57g nickel nitrate, 3.16g ammonium metatungstate to be dissolved in 7.0g deionized water, is configured to co-impregnation solution；
It (4) is to be urged in the above-mentioned carrier of 1.5mm by the diameter that the co-impregnation liquid is added dropwise to 9.0g extruded moulding
Agent semi-finished product；
(5) above-mentioned catalyst semi-finished product are stood 24 hours in air, are dried in 120 DEG C of baking oven, then with 4
DEG C/heating of the rate of min, it is roasted 4 hours under 500 DEG C, air atmosphere, obtains hydrogenation catalyst F-4.
The total amount for measuring nickel tungsten oxide in catalyst F-4 is 25.0wt% (using the total weight of catalyst F-4 as base
It is quasi-).The measurement of the oxide total content of activity component metal and aided metal and calculation method are known in this field in catalyst
Measurement and calculation method.
Comparative example 4
This comparative example provides a kind of diesel oil hydrogenation catalyst, as a comparison catalyst.
The preparation method of the comparative catalyst the following steps are included:
(1) 3.16g ammonium metatungstate and 1.57g nickel nitrate are dissolved in 9.0mL deionized water, are made into maceration extract；
It (2) is to be catalyzed in the oxidation aluminum strip of 1.5mm by the diameter that the maceration extract is added dropwise to 9.0g extruded moulding
Agent semi-finished product；
(3) the catalyst semi-finished product are stood 24 hours in air, are dried in 120 DEG C of baking oven, then with 5
DEG C/heating of the rate of min, roast 4 hours under 500 DEG C, air atmosphere, obtain described in comparative catalyst 4.Measure the comparison
The total content of nickel tungsten tungsten oxide is 25.0wt% in catalyst (on the basis of the total weight of the comparative catalyst).
Embodiment 5
A kind of hydrogenation catalyst is present embodiments provided, to be prepared using infusion process, specifically includes the following steps:
(1) 5.97g boehmite, 10.5g concentrated phosphoric acid (mass fraction 85%), 6.4g triethylamine, 0.5g acetic acid is sub-
In tin and 29.9g deionized water, mixed gel, 100mL autoclave dynamic crystallization 20h, washing, mistake are made into after agitated mixing
Sn (II) AlPO is made after filter, dry, roasting4- 5 molecular sieves, are calculated by molecular sieve quality 100wt%, and SnO content is
0.3wt%；；
(2) by Sn (II) AlPO4- 5 molecular sieves are mixed with boehmite according to mass ratio 2:8, and extrusion forming dries in the air naturally
Carrier is made in dry, 550 DEG C of roasting 4h；
(3) it takes 1.57g cobalt nitrate, 2.27g ammonium molybdate to be dissolved in 8.0g deionized water, is configured to dipping solution；
It (4) is to be catalyzed in the above-mentioned carrier of 1.5mm by the diameter that the maceration extract is added dropwise to 8.5g extruded moulding
Agent semi-finished product；
(5) above-mentioned catalyst semi-finished product are stood 24 hours in air, are dried in 120 DEG C of baking oven, then with 4
DEG C/heating of the rate of min, it is roasted 4 hours under 500 DEG C, air atmosphere, obtains hydrogenation catalyst F-5.
The total amount for measuring cobalt molybdenum oxide in catalyst F-5 is 20.5wt% (using the total weight of catalyst F-5 as base
It is quasi-).The measurement of the oxide total content of activity component metal and aided metal and calculation method are known in this field in catalyst
Measurement and calculation method.
Comparative example 5
This comparative example provides a kind of diesel oil hydrogenation catalyst, as a comparison catalyst.
The preparation method of the comparative catalyst the following steps are included:
(1) 2.27g ammonium molybdate and 1.57g cobalt nitrate are dissolved in 9.0mL deionized water, are made into maceration extract；
It (2) is to be catalyzed in the oxidation aluminum strip of 1.5mm by the diameter that the maceration extract is added dropwise to 8.5g extruded moulding
Agent semi-finished product；
(3) the catalyst semi-finished product are stood 24 hours in air, are dried in 120 DEG C of baking oven, then with 5
DEG C/heating of the rate of min, roast 4 hours under 500 DEG C, air atmosphere, obtain described in comparative catalyst 5.Measure the comparison
The total content of nickel tungsten tungsten oxide is 20.5wt% in catalyst (on the basis of the total weight of the comparative catalyst).
Test case 1
This test case provides the test experiments that above-mentioned catalyst carries out hydrotreating to coker gas oil.
Above-mentioned five kinds of embodiment catalyst and corresponding five kinds of comparative catalysts are subjected to test experiments, reaction process
It is as follows: to have carried out presulfurization processing before application, there is catalyst and preferably add hydrogen effect.Presulfurization uses 10mL high temperature
High-pressure hydrogenation micro-reactor carries out, and is the presulfurization of wet process original position, that is, uses wet process presulfurization, and presulfurization rear catalyst does not unload
Out, directly continue hydrogenation reaction in the reactor.Presulfurization oil is containing 5wt%CS2N-decane solution, the temperature of presulfurization
Degree is 300 DEG C, pressure 4MPa, liquid hourly space velocity (LHSV) 1.5h-1, hydrogen to oil volume ratio 300.
The hydrotreating of this test case is carried out using 10mL high-temperature and high-pressure hydrogenation micro-reaction device.It evaluates raw material and uses grand celebration
Coker gas oil, the specific gravity (d of the coker gas oil4 20) it is 0.8196, sulfur content 1187ppm, total nitrogen content 837ppm.Raw material
It is pumped into using plunger pump, the oil sample after reaction is after high separator is cooling, in low separator collection analysis.The temperature of hydrotreating
It is 280 DEG C, pressure 4MPa, liquid hourly space velocity (LHSV) 1.0h-1, hydrogen to oil volume ratio 800.In the condition of identical active metallic content
Under, hydrogenation catalyst evaluation result is as shown in table 1.
Evaluating catalyst result after 1 hydrotreating of table
By 1 data of table it is found that showing superior desulfurization removing nitric activity using catalyst prepared by complex carrier.It says
Bright the type catalytic activity has higher catalytic activity compared to existing catalyst.
Test case 2
This test case provides the test experiments that above-mentioned catalyst carries out hydrotreating to catalytic cracking diesel oil.
Above-mentioned five kinds of embodiment catalyst and corresponding five kinds of comparative catalysts are subjected to test experiments, reaction process is such as
Under: presulfurization processing has been carried out before application, and there is catalyst and preferably add hydrogen effect.Presulfurization is high using 10mL high temperature
Pressure plus hydrogen micro-reactor carry out, and are the presulfurization of wet process original position, that is, use wet process presulfurization, and presulfurization rear catalyst does not unload
Out, directly continue hydrogenation reaction in the reactor.Presulfurization oil is containing 5wt%CS2N-decane solution, the temperature of presulfurization
Degree is 300 DEG C, pressure 4MPa, liquid hourly space velocity (LHSV) 1.5h-1, hydrogen to oil volume ratio 300.
The hydrotreating of this test case is carried out using 10mL high-temperature and high-pressure hydrogenation micro-reactor.Evaluation raw material is urged using grand celebration
Change cracked diesel oil, the specific gravity (d of the catalytic cracking diesel oil4 20) it is 0.8796, sulfur content 1078ppm, total nitrogen content is
829ppm.Raw material is pumped into using plunger pump, and the oil sample after reaction is after high separator is cooling, in low separator collection analysis.Add
The temperature of hydrogen processing is 280 DEG C, pressure 4MPa, liquid hourly space velocity (LHSV) 1.0h-1, hydrogen to oil volume ratio 800.Urging after hydrotreating
Agent evaluation result is as shown in table 2.
Evaluating catalyst result after 2 hydrotreating of table
By 2 data of table it is found that showing superior desulfurization removing nitric activity using catalyst prepared by complex carrier.It says
Bright the type catalytic activity has higher catalytic activity compared to existing catalyst.
Claims (10)
1. a kind of Hydrobon catalyst, wherein by the gross weight of catalyst for 100wt% in terms of, the catalyst includes 50wt%-
The carrier of 95wt% and the active metal component of 5wt%-50wt%；
The carrier includes Sn (II) AlPO4- 5 molecular sieves and γ-Al2O3；
The active metal component includes the oxide and/or sulfide of one or more of Co, Mo, Ni and W.
2. Hydrobon catalyst according to claim 1, wherein by the gross weight of the carrier for 100wt% in terms of, it is described
Sn(II)AlPO4The content of -5 molecular sieves is 5wt%-60wt%；Preferably 15wt%-45wt%.
3. Hydrobon catalyst according to claim 1, wherein the carrier is prepared by the following method:
By Sn (II) AlPO4- 5 molecular sieves and preparation γ-Al2O3Predecessor mixing, then formed, roast the load is made
Body.
4. Hydrobon catalyst according to claim 1, wherein in the Sn (II) AlPO4In -5 molecular sieves, with SnO
Meter, content 0.1wt%-4.0wt%；Preferably 0.2wt%-2.0wt%.
5. Hydrobon catalyst according to claim 1, wherein the active metal component is the oxide of Co and Mo
And/or sulfide, the oxide and/or sulfide of Ni and W, Co and Mo and W oxide and/or sulfide；
Preferably, the active metal component is selected from the oxide of corresponding active metal；
Preferably, the content of the active metal group is the 20wt%-40wt% of overall catalyst weight.
6. the preparation method of the described in any item Hydrobon catalysts of claim 1-5, wherein this method includes following step
It is rapid:
By Sn (II) AlPO4- 5 molecular sieves and preparation γ-Al2O3Predecessor mixing, then formed, roast obtained carrier；
The carrier is impregnated with the soluble metal salt solution containing Co, Mo, Ni and/or W, is then made described through drying, roasting
Hydrobon catalyst.
7. application of the described in any item Hydrobon catalysts of claim 1-5 in gasoline, diesel oil hydrofining reaction；
Preferably, the active metal component in the Hydrobon catalyst be Co and Mo oxide and/or sulfide, Ni and
The oxide and/or sulfide of the oxide and/or sulfide of W, Co and Mo and W.
8. one kind contains Sn (II) AlPO4- 5 molecular sieves and γ-Al2O3Carrier, wherein the gross weight with the carrier is
100wt% meter, Sn (II) AlPO4The weight of -5 molecular sieves accounts for 5wt%-60wt%；Preferably 15wt%-45wt%；
The carrier is prepared by the following method:
By Sn (II) AlPO4- 5 molecular sieves and preparation γ-Al2O3Predecessor mixing, the carrier is made after roasting；
Preferably, the predecessor is boehmite；
It is further preferred that the condition of the roasting are as follows: roast 2-8h at 450-650 DEG C.
9. a kind of Sn (II) AlPO4- 5 molecular sieves, wherein Sn (II) AlPO4- 5 molecular sieves are prepared by the following method:
(1) divalent tin source and AlPO will be used to prepare4The raw material of -5 molecular sieves is mixed, and mixed gel is prepared；
(2) Crystallizing treatment, calcination process are carried out to the mixed gel, the Sn (II) AlPO is made4- 5 molecular sieves；
Preferably, the divalent tin source includes stannous chloride or stannous acetate；
It is further preferred that the Crystallizing treatment is hydrothermal crystallizing processing；
It is highly preferred that the condition of the hydrothermal crystallizing processing are as follows: crystallization 14-36h at 140-200 DEG C；
It is highly preferred that the condition of the calcination process are as follows: roast 2-8h at 450-650 DEG C.
10. Sn (II) AlPO according to claim 94- 5 molecular sieves, wherein described to be used to prepare in step (1)
AlPO4The raw material of -5 molecular sieves includes:
Water, silicon source, phosphorus source and template；
Preferably, source of aluminium includes boehmite, and phosphorus source includes phosphoric acid, and the template includes triethylamine, three second
Hydramine, tetraethylammonium bromide or tetraethyl ammonium hydroxide；
It is further preferred that the water, silicon source, phosphoric acid, tin source and template are respectively according to H2O、Al2O3、P2O5, SnO and template
Agent meter, the molar ratio of each component are 30-70:1:0.9-1.7:0.01-0.2:1-3.
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| CN114768863A (en) * | 2022-06-02 | 2022-07-22 | 润和科华催化剂(上海)有限公司 | Heavy oil hydrodesulfurization catalyst and preparation method thereof |
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