CN109395770A - A kind of iron-based hydrogenation catalyst and preparation method thereof - Google Patents
A kind of iron-based hydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN109395770A CN109395770A CN201710704765.7A CN201710704765A CN109395770A CN 109395770 A CN109395770 A CN 109395770A CN 201710704765 A CN201710704765 A CN 201710704765A CN 109395770 A CN109395770 A CN 109395770A
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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
- B01J29/83—Aluminophosphates (APO compounds)
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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
Abstract
The present invention provides a kind of iron-based hydrogenation catalysts and preparation method thereof.The catalyst includes the oxide of carrier and carrier loaded active metal, and the carrier includes aluminium oxide and the AlPO modified with iron and molybdenum4- 5 molecular sieves, the active metal include main active metal and help active metal, and the main active metal is Fe, described to help active metal for Zn；The AlPO modified with iron and molybdenum4- 5 molecular sieves and the mass ratio of aluminium oxide are (5-12): 50, be (2-10) as the Fe element of active metal and the molar ratio of Zn element: 1, it is in terms of 100% by total catalyst weight, the oxide total weight of active metal is 15-50%；The preparation method method of the molecular sieve includes: that ferro element is introduced into AlPO4In -5 molecular sieves, Fe/AlPO is obtained4- 5 molecular sieves, in terms of molecular sieve 100%, ferro element is with Fe2O3It is calculated as 0.5~5%；With the water-soluble salting liquid incipient impregnation Fe/AlPO of metal molybdenum4- 5 molecular sieves obtain Mo-Fe/AlPO then by washing, dry and roasting4- 5 molecular sieves, with Mo-Fe/AlPO4- 5 molecular sieve total weights 100% meter, MoO3It is 3~10%.
Description
Technical field
The present invention relates to hydrogenation catalyst fields, in particular to a kind of iron-based hydrogenation catalyst and preparation method thereof.
Background technique
Hydrogen addition technology is the core technology of heavy oil lighting, in heavy raw oil deep processing, improves product quality, enhancing
It is play an important role in adaptability to raw material and operating flexibility, has emerged many new oil refining hydrogenation catalysts and its system in succession
Preparation Method.
CN104588116A discloses a kind of hydrotreating catalyst, is to live with Co, Mo, Ni and W using aluminium oxide as carrier
Property metal component, the fountain solution containing adsorbent I is impregnated by unsaturation, then impregnates the solution of Mo containing active metal, Co, through dry
Dry and roasting then by saturation dipping or excessive dipping II containing adsorbent, that is, polyethylene glycol solution, then impregnates W, Ni activity
Metal and obtain.Patent CN103769118A discloses a kind of heavy-oil hydrogenation catalyst, and carrier is aluminium oxide, active component
The metal of VIII group and/or group vib, wherein VIII metal is Co or Ni, and group vib metal is Mo or W, is contained in preparation using butt
Amount is 50% boehmite molding preparation below, and the catalyst of this method preparation has high demetalization, desulfurization, de- carbon residue
Activity.CN103212432A uses aluminium oxide and HY molecular sieve for carrier, and carries out surface acid etching to the two, after acid processing
Aluminium oxide and acid treated HY it is mechanical it is compound be used as carrier, it is negative by maceration extract of the dipping containing catalyst activity component
Carried catalyst active component, active component includes Mo and/or W and Co and/or Ni, and also contains complexing agent in dipping, this is urged
Agent has high hydrodenitrogeneration and hydrodesulfurization performance to inferior heavy oil distillate.CN105582948A discloses a kind of residual oil and adds
The preparation method of hydrogen catalyst, with aqueous solution of urea oxide impregnation alumina supporter, alumina support is matched by being dried after dipping
Set at least two various concentrations containing polyalcohol and or monosaccharide and hydrogenation active metal component maceration extract, according to concentration by
High to Low sequence sprays on above-mentioned alumina support so that the concentration of hydrogenation metal component formed on carrier by outside to
The interior gradient distribution in from low to high, later hydro-thermal process in sealing container, drying, anaerobic high-temperature process and obtain, the catalyst
Show excellent residuum hydrogenating and metal-eliminating activity.
Hydrogenation active component is mainly the oxide or sulfide of Co (Ni) Mo (W) series in above-mentioned patent；Carrier master
There are aluminium oxide, amorphous silica-alumina, molecular screen material etc..In order to further increase the hydrogenation activity of catalyst, composite oxides
Hydrogenation metal activity phase catalyst and preparation method thereof is in succession open.
Fluorine will be added in patent CN00110017.3 in liquor alumini chloridi or aluminum sulfate solution, then be added boracic, silicon, phosphorus,
Magnesium, titanium, zirconium, gallium compound；Ni and W is added；Above-mentioned mixed liquor is heated to 40-80 DEG C, with ammonia precipitation process, sediment is dry
It is dry；Molding after binder, molecular sieve, auxiliary agent is added in sediment after drying, dry, roasting obtains catalyst, with group VIB and
Group VIII metal active constituent, in mass, oxycompound 30-70%, Y type molecular sieve 5-30%, fluorine 2- in the catalyst
8%, boron, silicon, phosphorus, magnesium, titanium, zirconium, gallium one of oxide or more than one 0.5-5%.CN103801317A is disclosed
A kind of hydrogenation catalyst preparation method containing W, Ni, Al, Mg composite oxides and Mo, Co composite oxides, passes through co-precipitation
W, Ni, Al, Mg composite oxides precursor are prepared, through overmolding, washing, dry and roasting obtains catalyst intermediate, with containing
The maceration extract of Co, Mo impregnate, and obtain through dry and roasting.Patent CN103801318A prepares W, Ni composite oxygen by coprecipitation
Compound precursor, and macromolecular polyethylene glycol is introduced in precipitation process, it is formed, is washed, dry and roasting obtains catalyst
Intermediate is impregnated with the maceration extract specifically containing Co, Mo, through dry and roasting, hydrotreating catalyst is obtained, so that catalyst
With smaller particle, bigger surface area, active metal forms Hydrogenation and hydrogenolysis performance under the premise of evenly dispersed
Excellent mixed type activated centre is matched, realizes that catalyst activity component adds hydrogen and hydrogenolysis desulfidation preferably to cooperate with performance.
Hydrogenation active component is mainly Co (Ni) xMo (W) y composite oxides or sulfide in above-mentioned patent；Add hydrogen golden
Belong to activity mutually has higher plus hydrogen living with load type Co (Ni) Mo (W) oxide or testing sulphide ratio of traditional infusion process
Property, however high cost is another question urgently to be resolved.The heavy ingredient day especially in heavy oil yield and crude oil
Benefit increases, and the exploitation of low-cost hydrogenation catalyst has wider meaning.
CN104918698B discloses a kind of iron-based heavy-oil hydrogenation catalyst, with iron for main activity component metal, with zinc and
Potassium helps activity component metal for first, and main activity component metal is 0.5-200:1 with the molar ratio for helping active metal.
CN1965061A contacts feedstock oil under one or more catalyst with hydrogen source to produce crude oil products, wherein the one of catalyst
Kind is a variety of including containing K3Fe10S14Catalyst.CN1245255C discloses a kind of Fischer-Tropsch synthetic iron-based catalyst and its system
Preparation Method, catalyst group become Fe:Zn:Cu:K:SiO2=100:(0.01-8): (0.5-15): (0.5-10): (5-40) is adopted
It is that precipitating reagent is co-precipitated the mixed solution of ferric nitrate, zinc nitrate, copper acetate to obtain precipitate slurry with sodium carbonate liquor, by silicic acid
The mixed solution of aqueous solutions of potassium and silica solution, which is added in precipitate slurry, is made catalyst pulp, and catalyst pulp is sent to spraying
In drier, powder is obtained, is then roasted, catalyst is obtained.
CN104588108A discloses a kind of heavy-oil hydrogenation catalyst, including FeOOH, organic polycarboxylic acid, macropore oxygen
Change aluminium and boehmite, based on weight, the content of FeOOH is 10-50%, and the content of macroporous aluminium oxide is 20-
70%, the content of boehmite is that 5-40% will contain wherein organic polycarboxylic acid content is 0.05-0.40g/g FeOOH
The alkaline solution of aluminium is stirred with ferrous salt solution, obtains the suspension of ferrous hydroxide, then logical in the lower part of reactor
Enter oxygen and CO2Gaseous mixture, when pH value be 9-11 when stop be passed through CO2, continue to be passed through oxygen-containing gas, obtain hydroxyl oxidation
Then the aluminum hydroxide slurry of iron is handled with organic multicomponent acid again, macroporous aluminium oxide mixed-forming is added in obtained filter cake, through dry
It is dry, obtain heavy-oil hydrogenation catalyst.
In conclusion researchers go out in petrol and diesel oil and heavy oil supported catalyst agent carrier and additive modification and in recent years
A lot of research work is done in terms of the preparation of existing breakthrough unsupported catalyst, while in order to reduce catalyst production system
Standby cost, has also been made many effort.But using nickel, cobalt as auxiliary agent, the basic combination of molybdenum, tungsten as main active component metal
It is not broken.Therefore develop one kind and take into account cost and active petrol and diesel oil and heavy-oil hydrogenation catalyst, be still this field urgently
One of problem to be solved.
Summary of the invention
It is an object of the present invention to provide a kind of iron-based hydrogenation catalysts；
Another object of the present invention is to provide the preparation methods of the iron-based hydrogenation catalyst.
In order to achieve the above object, on the one hand, the present invention provides a kind of iron-based hydrogenation catalysts, wherein the catalyst packet
The oxide of carrier and carrier loaded active metal is included, the carrier includes aluminium oxide and the AlPO modified with iron and molybdenum4-5
Molecular sieve, the active metal include main active metal and help active metal, and the main active metal is Fe, described to help active gold
Belonging to is Zn；The AlPO modified with iron and molybdenum4- 5 molecular sieves and the mass ratio of aluminium oxide are (5-12): 50, as active gold
The Fe element of category and the molar ratio of Zn element are (2-10): 1, it is the oxide of active metal in terms of 100% by total catalyst weight
Total weight is 15-50%；The AlPO modified with iron and molybdenum4The preparation method method of -5 molecular sieves includes:
(a) ferro element is introduced into AlPO4In -5 molecular sieves, Fe/AlPO is obtained4- 5 molecular sieves, with obtained Fe/
AlPO4- 5 molecular sieves 100% meter, ferro element is with Fe2O3It is calculated as 0.5~5%；
(b) Fe/AlPO obtained with the water-soluble salting liquid incipient impregnation step (a) of metal molybdenum4- 5 molecular sieves, then pass through
Washing, dry and roasting are crossed, Mo-Fe/AlPO is obtained4- 5 molecular sieves, with Mo-Fe/AlPO4- 5 molecular sieve total weights 100% meter,
MoO3It is 3~10%.
Wherein it is understood that the Fe element in iron-based hydrogenation catalyst of the invention is divided into two parts: as work
Property metal Fe element and be used for AlPO4- 5 molecular sieve modified Fe elements.
Some specific embodiments according to the present invention, wherein the AlPO modified with iron and molybdenum4- 5 molecular sieves and oxidation
The mass ratio of aluminium is (8-10): 50.
Some specific embodiments according to the present invention, wherein the molar ratio of Fe element and Zn element is (6-10): 1.
Some specific embodiments according to the present invention, wherein ferro element is in step (a) with Fe2O3It is calculated as 2-4%.
Some specific embodiments according to the present invention, wherein with Mo-Fe/AlPO in step (b)4- 5 molecular sieve total weights
100% meter, MoO3For 3-8%.
Some specific embodiments according to the present invention, wherein the water-soluble salt of metal molybdenum described in step (b) is four hydration molybdenums
Sour ammonium.
Some specific embodiments according to the present invention, wherein the maturing temperature of step (b) is 450-550 DEG C.
Some specific embodiments according to the present invention, wherein the drying temperature of step (b) is 90-120 DEG C.
Some specific embodiments according to the present invention, wherein step (a) is the water-soluble salting liquid incipient impregnation with iron
AlPO4- 5 molecular sieves obtain the Fe/AlPO then by dry and roasting4- 5 molecular sieves.
Some specific embodiments according to the present invention, wherein the drying temperature in step (a) is 90-120 DEG C.
Some specific embodiments according to the present invention, wherein the maturing temperature in step (a) is 450-550 DEG C.
Some specific embodiments according to the present invention, wherein the water-soluble salt of iron described in step (a) is nine nitric hydrates
Iron.
Some specific embodiments according to the present invention, wherein the preparation method of the iron-based hydrogenation catalyst includes as follows
Step:
It prepares and main active metal and helps the co-impregnation solution of active metal, then by the method for incipient impregnation by main work
Property metal and active metal is helped to load on boehmite, obtain the iron-based hydrogenation catalyst by roasting；
Alternatively, by main reactive metal oxides and active metal oxide powder is helped to be uniformly mixed with carrier, obtain described
Iron-based hydrogenation catalyst；
Or by main reactive metal oxides and active metal oxide powder is helped to be uniformly mixed with boehmite, it roasts
Obtain the iron-based hydrogenation catalyst.
Some specific embodiments according to the present invention, wherein by main active metal and help active metal to load to intend thin water
The temperature of roasting after aluminium stone is 450-550 DEG C.
Some specific embodiments according to the present invention, wherein by main reactive metal oxides and help reactive metal oxides
Powder and the temperature of the roasting of boehmite after mixing are 450-550 DEG C.
Some specific embodiments according to the present invention, wherein by main active metal and help active metal to load to intend thin water
The time of roasting after aluminium stone is 2-12h；It is wherein preferably 4-8h.
Some specific embodiments according to the present invention, wherein by main reactive metal oxides and help reactive metal oxides
The time of powder and the roasting of boehmite after mixing is 2-12h；It is wherein preferably 4-8h.
Some specific embodiments according to the present invention, wherein to carrier loaded main active metal and the step for helping active metal
It suddenly include: the co-impregnation solution prepared main active metal and help active metal, then by the method for incipient impregnation by main work
Property metal and active metal is helped to load on boehmite, main active metal will have been loaded and that helps active metal intends thin water aluminium
Stone is dried, and then roasts, and obtains the iron-based hydrogenation catalyst.
Some specific embodiments according to the present invention, wherein prepare main active metal and help the co-impregnation of active metal molten
The step of liquid includes: by the water-soluble salt of main active metal and the water-soluble salt of active metal to be helped to be dissolved in water to obtain the co-impregnation
Solution.
Some specific embodiments according to the present invention, wherein the water-soluble salt of main active metal is Fe(NO3)39H2O, chlorination
One of iron and ferric sulfate or a variety of mixing.
Some specific embodiments according to the present invention, wherein the water-soluble salt for helping active metal is zinc nitrate hexahydrate, chlorination
One of zinc and zinc sulfate or a variety of mixing.
Some specific embodiments according to the present invention, wherein by loaded main active metal and help active metal intend it is thin
The temperature that diaspore is dried is 90-120 DEG C.
Some specific embodiments according to the present invention, wherein by loaded main active metal and help active metal intend it is thin
The time that diaspore is dried is 4-12h.
Some specific embodiments according to the present invention, wherein boehmite is impregnated into main active metal and helps active gold
After category, further include the steps that impregnated of main active metal and the boehmite of active metal being helped to stand, then again into
Row is dry and roasts.
Some specific embodiments according to the present invention, wherein the time of standing is 4-24h.
Some specific embodiments according to the present invention, wherein by main reactive metal oxides and help reactive metal oxides
The step that powder is uniformly mixed with carrier or boehmite includes: the water-soluble salt of main active metal and helps the water-soluble of active metal
Salt is uniformly mixed obtains mixed solution in water, and reaction obtains main active metal and helps the hydrogen-oxygen of active metal under alkaline condition
Compound precipitation mixture, then roasting obtains main active metal and helps the oxide mixture of active metal, then by oxide
Mixture and carrier or boehmite are uniformly mixed.
Some specific embodiments according to the present invention, wherein the water-soluble salt of main active metal is Fe(NO3)39H2O, chlorination
One of iron and ferric sulfate or a variety of mixing.
Some specific embodiments according to the present invention, wherein the water-soluble salt for helping active metal is zinc nitrate hexahydrate, chlorination
One of zinc and zinc sulfate or a variety of mixing.
Some specific embodiments according to the present invention, wherein the alkaline condition is that the pH value of mixed solution is more than or equal to
10。
Some specific embodiments according to the present invention, wherein reaction obtains main active metal and helps work under alkaline condition
Property metal hydroxide precipitation mixture after roasting temperature be 450-550 DEG C.
Some specific embodiments according to the present invention, wherein reaction obtains main active metal and helps work under alkaline condition
Property metal hydroxide precipitation mixture after roasting time be 2-12h；Preferably 4-8h.
Some specific embodiments according to the present invention, wherein by main reactive metal oxides and help reactive metal oxides
The step that powder is uniformly mixed with carrier or boehmite includes: the water-soluble salt with main active metal and the water for helping active metal
Dissolved salt is soluble in water, and addition alkali, which is reacted, to be precipitated, and filters after fully reacting, roasts the precipitating being obtained by filtration to obtain iron
Iron zinc oxide powder is uniformly mixed by zinc oxide powder with carrier or boehmite.
Some specific embodiments according to the present invention, wherein the alkali is ammonium hydroxide or urea.
Some specific embodiments according to the present invention, wherein the water-soluble salt of main active metal is Fe(NO3)39H2O, chlorination
One of iron and ferric sulfate or a variety of mixing.
Some specific embodiments according to the present invention, wherein the water-soluble salt for helping active metal is zinc nitrate hexahydrate, chlorination
One of zinc and zinc sulfate or a variety of mixing.
Some specific embodiments according to the present invention, wherein the reaction temperature of the reaction is 75-95 DEG C.
Some specific embodiments according to the present invention, wherein the reaction time of the reaction is 4-8h.
Some specific embodiments according to the present invention, wherein also precipitated again by aging after reaction.
Some specific embodiments according to the present invention, wherein aging is to stand 20-30h at 50-80 DEG C；Preferably exist
It is stood for 24 hours at 60 DEG C.
Some specific embodiments according to the present invention, wherein also wrap iron zinc oxide powder after mixing with carrier
Include the step of mixed iron zinc oxide powder and carrier are subjected to tabletting.
Some specific embodiments according to the present invention, wherein with the main active metal of preparation and helping being total to for active metal
It further include by aluminium oxide and the AlPO modified with iron and molybdenum before dipping solution incipient impregnation carrier4The step of -5 molecular sieves mixing
Suddenly.
Some specific embodiments according to the present invention, wherein by aluminium oxide and the AlPO modified with iron and molybdenum4- 5 molecular sieves
After mixing, further include the steps that mixture extruded moulding.
On the other hand, the present invention also provides the preparation method of the iron-based hydrogenation catalyst, the method includes institutes
It states with iron and molybdenum to AlPO4The step of -5 molecular sieves are modified, the step include:
(a) ferro element is introduced into AlPO4In -5 molecular sieves, Fe/AlPO is obtained4- 5 molecular sieves, with obtained Fe/
AlPO4- 5 molecular sieves 100% meter, ferro element is with Fe2O3It is calculated as 0.5~5%；
(b) Fe/AlPO obtained with the water-soluble salting liquid incipient impregnation step (a) of metal molybdenum4- 5 molecular sieves, then pass through
Washing, dry and roasting are crossed, Mo-Fe/AlPO is obtained4- 5 molecular sieves, with Mo-Fe/AlPO4- 5 molecular sieve total weights 100% meter,
MoO3It is 3~10%.
In conclusion the present invention provides a kind of iron-based hydrogenation catalysts and preparation method thereof.Catalyst tool of the invention
It has the following advantages:
The present invention use iron-based hydrogenation catalyst, instead of using the molybdenum of group vib, tungsten as activity component metal, with VIII
Traditional hydrogenation catalyst of the cobalt, nickel of race as aided metal.For iron of the present invention as main activity component metal, zinc is to help active component
Metal；And modified Mo-Fe/AlPO4- 5 molecular sieves, which are introduced into alumina support, can be effectively improved carrier and add hydrogen gold
The interaction for belonging to active component FeZn, improves the activity of catalyst.Compared to traditional hydrogenation catalyst, of the invention is iron-based
Catalyst has many advantages, such as that raw material is cheap and easy to get, manufacture craft is simple, in the production cost that can substantially reduce hydrogenation catalyst
While, also there is higher hydrogenation activity, there is long-range industrial application value.
Specific embodiment
Below by way of the beneficial effect of the specific embodiment implementation process that the present invention will be described in detail and generation, it is intended to which help is read
Reader more fully understands essence and feature of the invention, does not limit the scope of the present invention.
Embodiment 1
A kind of iron-based hydrogenation catalyst, preparation method includes the following steps:
Fe/AlPO4- 5 (1) preparation: by nine water ferric nitrate (Fe (NO of 1.27g3)3·9H2O it) is dissolved in 42.5g distilled water
It is configured to solution, using equi-volume impregnating, is slowly dropped to 50g AlPO4In -5 molecular sieves, after air stands 3h, 110
Dry 12h at DEG C, then 3h is roasted at 540 DEG C.Elemental analysis shows Fe/AlPO4Fe in -5 (1)2O3Mass percentage be
0.51wt%.
Mo-Fe/AlPO4- 5 (1) preparation: by 0.92g Ammonium Molybdate Tetrahydrate (H32Mo7N6O28) be dissolved in 21g distilled water
It is configured to solution, using equi-volume impregnating, is slowly dropped to 25g Fe/AlPO4- 5 (1) are inner, after air stands 3h, 110
Dry 12h at DEG C, then 3h is roasted at 500 DEG C.Elemental analysis shows Mo-Fe/AlPO4MoO in -5 (1)3Mass percentage be
3.2wt%.
Prepare catalyst carrier: by boehmite 63.5g (loss on ignition being considered, in terms of alumina content 78.1wt%)
With 5g Mo-Fe/AlPO4- 5 (1) carry out mechanical mixture, extruded moulding, obtain catalyst carrier, molecular sieve and quality of alumina
Ratio is 5.2:50.
Prepare iron-based hydrogenation catalyst: by nine water ferric nitrate (Fe (NO of 18.7g3)3·9H2) and 6.3g zinc nitrate hexahydrate O
(Zn(NO3)2·6H2O it) is dissolved in appropriate amount of deionized water and is made into co-impregnation solution, it is above-mentioned that co-impregnation solution is poured slowly into 30g
In the catalyst carrier of preparation, it is stirred continuously, after realizing that incipient impregnation, air stand 4h, the dry 9h at 110 DEG C, then
4h is roasted at 480 DEG C, the hydrogenation catalyst is obtained, is denoted as catalyst CAT-1；Iron oxide in catalyst CAT-1
(Fe2O3) and the weight content of zinc oxide (ZnO) be the metal molar ratio of 15.2wt%, Fe and Zn be 2.2:1.
Embodiment 2
Fe/AlPO4- 5 (2) preparation: it using the hydrothermal synthesis method of patent CN200710009684.1, prepares iron-containing
AlPO4- 5 molecular sieves.Source of iron used is nine water ferric nitrate (Fe (NO3)3·9H2O), using triethylamine (Et3It N) is template；It closes
It is (atomic ratio): 0.04Fe:1Al at gel proportion2O3:1.06P2O5:1.47Et3N:45H2O, crystallization temperature are 190 DEG C, crystallization
Time is 16 hours.Products obtained therefrom is filtered, washed, dries (90 DEG C), 500 DEG C of roasting；Elemental analysis shows, product F e2O3Matter
Measure content 1.6wt%.
Mo-Fe/AlPO4- 5 (2) preparation: by 2.2g Ammonium Molybdate Tetrahydrate (H32Mo7N6O28) be dissolved in 21g distilled water and match
It is set to solution, using equi-volume impregnating, is slowly dropped to 25g Fe/AlPO4- 5 (2) are inner, after air stands 4h, at 100 DEG C
Lower dry 12h, then 4h is roasted at 500 DEG C, MoO in product3Mass percentage be 7.1wt%.
Prepare catalyst carrier: by boehmite 63.5g (loss on ignition being considered, in terms of alumina content 78.1wt%)
With 12.1g Mo-Fe/AlPO4- 5 (2) carry out mechanical mixture, extruded moulding, obtain catalyst carrier, molecular sieve and aluminum oxide
Amount ratio is 11.9:50.
Prepare iron-based hydrogenation catalyst: by nine water ferric nitrate (Fe (NO of 38.8g3)3·9H2) and 3.60g zinc nitrate hexahydrate O
(Zn(NO3)2·6H2O it) is dissolved in appropriate amount of deionized water and is made into co-impregnation solution, it is above-mentioned that co-impregnation solution is poured slowly into 30g
In the catalyst carrier of preparation, it is stirred continuously, after realizing that incipient impregnation, air stand 5h, the dry 6h at 100 DEG C, then
5h is roasted at 500 DEG C, the hydrogenation catalyst is obtained, is denoted as catalyst CAT-2；Iron oxide in catalyst CAT-2
(Fe2O3) and the weight content of zinc oxide (ZnO) be the metal molar ratio of 22.5wt%, Fe and Zn be 8.1:1.
Embodiment 3
Fe/AlPO4- 5 (3) preparation: it using the hydrothermal synthesis method of patent CN200710009684.1, prepares iron-containing
AlPO4- 5 molecular sieves.Source of iron used is nine water ferric nitrate (Fe (NO3)3·9H2O), using triethylamine (Et3It N) is template；It closes
It is (atomic ratio): 0.065Fe:1Al at gel proportion2O3:1.06P2O5:1.47Et3N:45H2O, crystallization temperature is 190 DEG C, brilliant
Changing the time is 16 hours.Products obtained therefrom is filtered, washed, dries (90 DEG C), 500 DEG C of roasting；Elemental analysis shows, product F e2O3
Mass content 2.9wt%.
Mo-Fe/AlPO4- 5 (3) preparation: by 2.76g Ammonium Molybdate Tetrahydrate (H32Mo7N6O28) be dissolved in 21g distilled water
It is configured to solution, using equi-volume impregnating, is slowly dropped to 25g Fe/AlPO4- 5 (3) are inner, after air stands 4h, 100
Dry 12h at DEG C, then 4h is roasted at 500 DEG C, MoO in product3Mass percentage be 8.8wt%.
Prepare catalyst carrier: by boehmite 63.5g (loss on ignition being considered, in terms of alumina content 78.1wt%)
With 10.3g Mo-Fe/AlPO4- 5 (3) carry out mechanical mixture, extruded moulding, obtain catalyst carrier, molecular sieve and aluminum oxide
Amount ratio is 9.9:50.
Prepare iron-based hydrogenation catalyst: by nine water ferric nitrate (Fe (NO of 22.9g3)3·9H2) and 3.10g zinc nitrate hexahydrate O
(Zn(NO3)2·6H2O it) is dissolved in appropriate amount of deionized water and is made into co-impregnation solution, it is above-mentioned that co-impregnation solution is poured slowly into 30g
In the catalyst carrier of preparation, it is stirred continuously, after realizing that incipient impregnation, air stand 6h, the dry 6h at 110 DEG C, then
5h is roasted at 520 DEG C, the hydrogenation catalyst is obtained, is denoted as catalyst CAT-3；Iron oxide in catalyst CAT-3
(Fe2O3) and the weight content of zinc oxide (ZnO) be the metal molar ratio of 15.6wt%, Fe and Zn be 5.0:1.
Embodiment 4
Fe/AlPO4- 5 (4) preparation: by nine water ferric nitrate (Fe (NO of 10.1g3)3·9H2O it) is dissolved in 42.5g distilled water
It is configured to solution, using equi-volume impregnating, is slowly dropped to 50g AlPO4In -5 molecular sieves, after air stands 3h, 110
Dry 12h at DEG C, then 3h is roasted at 500 DEG C.Elemental analysis shows Fe/AlPO4Fe in -5 (4)2O3Mass percentage be
3.9wt%.
Mo-Fe/AlPO4- 5 (4) preparation: by 1.53g Ammonium Molybdate Tetrahydrate (H32Mo7N6O28) be dissolved in 21g distilled water
It is configured to solution, using equi-volume impregnating, is slowly dropped to 25g Fe/AlPO4- 5 (4) are inner, after air stands 4h, 100
Dry 12h at DEG C, then 4h is roasted at 500 DEG C, MoO in product3Mass percentage be 5.1wt%.
Prepare catalyst carrier: by boehmite 63.5g (loss on ignition being considered, in terms of alumina content 78.1wt%)
With 9gMo-Fe/AlPO4- 5 (4) carry out mechanical mixture, extruded moulding, obtain catalyst carrier, molecular sieve and quality of alumina ratio
Example is 8.8:50.
Prepare iron-based hydrogenation catalyst: by nine water ferric nitrate (Fe (NO of 43.5g3)3·9H2) and 4.1g zinc nitrate hexahydrate O
(Zn(NO3)2·6H2O it) is dissolved in appropriate amount of deionized water and is made into co-impregnation solution, it is above-mentioned that co-impregnation solution is poured slowly into 30g
In the catalyst carrier of preparation, it is stirred continuously, after realizing that incipient impregnation, air stand 6h, the dry 6h at 110 DEG C, then
5h is roasted at 520 DEG C, the hydrogenation catalyst is obtained, is denoted as catalyst CAT-4；Iron oxide in catalyst CAT-4
(Fe2O3) and the weight content of zinc oxide (ZnO) be the metal molar ratio of 24.2wt%, Fe and Zn be 8:1.
Embodiment 5
Fe/AlPO4- 5 (5) preparation: by nine water ferric nitrate (Fe (NO of 12.5g3)3·9H2O it) is dissolved in 42.5g distilled water
It is configured to solution, using equi-volume impregnating, is slowly dropped to 50g AlPO4In -5 molecular sieves, after air stands 3h, 110
Dry 12h at DEG C, then 3h is roasted at 500 DEG C.Elemental analysis shows Fe/AlPO4Fe in -5 (5)2O3Mass percentage be
4.8wt%.
Mo-Fe/AlPO4- 5 (5) preparation: by 3.0g Ammonium Molybdate Tetrahydrate (H32Mo7N6O28) be dissolved in 21g distilled water and match
It is set to solution, using equi-volume impregnating, is slowly dropped to 25g Fe/AlPO4- 5 (5) are inner, after air stands 4h, at 100 DEG C
Lower dry 12h, then 4h is roasted at 500 DEG C, MoO in product3Mass percentage be 9.8wt%.
32.2g iron chloride and 5.22g zinc chloride are dissolved in 250mL deionized water, the water of iron chloride and zinc chloride is obtained
Solution；62g ammonia spirit is slowly added into while stirring in the aqueous solution of iron chloride and zinc chloride；It is stirred in 80 DEG C of water-bath
Reaction 4 hours is mixed, 60 DEG C of standings is then cooled to aging 24 hours, obtains sediment；The sediment is filtered while hot, spend from
Sub- water washing to pH value is approximately equal to 9, then dries in 120 DEG C of baking oven, then is heated up with the rate of 5 DEG C/min, 500 DEG C,
It is roasted 2 hours under air atmosphere, obtains iron zinc oxide powder；Metal molar ratio of Fe and Zn is in oxide obtained in it
5.4:1。
By the oxide powder 9.8g of iron-based hydrogenation catalyst, aluminium oxide 8.2g, 1.8g Mo-Fe/AlPO4- 5 (5) are mixed
Conjunction stirs evenly, and compression molding in tablet press machine is added, is denoted as catalyst CAT-5；Iron oxide (Fe in catalyst CAT-52O3) and
The weight content of zinc oxide (ZnO) is 49.9wt%.
Comparative example 1
This comparative example provides a kind of hydrogenation catalyst, and preparation method includes the following steps:
With the Fe/AlPO prepared in embodiment 24- 5 (2) are as modified AlPO4- 5 type molecular sieves.
Prepare catalyst carrier: by boehmite 63.5g (loss on ignition being considered, in terms of alumina content 78.1wt%)
With 12.1gFe/AlPO4- 5 (2) carry out mechanical mixture, extruded moulding, obtain catalyst carrier, molecular sieve and quality of alumina ratio
Example is 11.9:50.
Prepare iron-based hydrogenation catalyst: by nine water ferric nitrate (Fe (NO of 38.8g3)3·9H2) and 3.60g zinc nitrate hexahydrate O
(Zn(NO3)2·6H2O it) is dissolved in appropriate amount of deionized water and is made into co-impregnation solution, it is above-mentioned that co-impregnation solution is poured slowly into 30g
In the catalyst carrier of preparation, it is stirred continuously, after realizing that incipient impregnation, air stand 5h, the dry 6h at 100 DEG C, then
5h is roasted at 500 DEG C, the hydrogenation catalyst is obtained, is denoted as catalyst CAT-R1；Iron oxide in catalyst CAT-R1
(Fe2O3) and the weight content of zinc oxide (ZnO) be the metal molar ratio of 22.5wt%, Fe and Zn be 8.1:1.
Comparative example 2
This comparative example provides a kind of hydrogenation catalyst, and preparation method includes the following steps:
With Mo/AlPO4- 5 as modified AlPO4- 5 type molecular sieves.
Mo/AlPO4- 5 preparations: by 2.76g Ammonium Molybdate Tetrahydrate (H32Mo7N6O28) be dissolved in 21g distilled water and be configured to
Solution is slowly dropped to 25g AlPO using equi-volume impregnating4In -5, after air stands 4h, the dry 12h at 100 DEG C,
4h, MoO in product are roasted at 500 DEG C again3Mass percentage be 8.8wt%.
Prepare catalyst carrier: by boehmite 63.5g (loss on ignition being considered, in terms of alumina content 78.1wt%)
With 10.3gMo/AlPO4- 5 carry out mechanical mixture, extruded moulding, obtain catalyst carrier, molecular sieve and quality of alumina ratio
For 9.9:50.
Prepare iron-based hydrogenation catalyst: by nine water ferric nitrate (Fe (NO of 22.9g3)3·9H2) and 3.10g zinc nitrate hexahydrate O
(Zn(NO3)2·6H2O it) is dissolved in appropriate amount of deionized water and is made into co-impregnation solution, it is above-mentioned that co-impregnation solution is poured slowly into 30g
In the catalyst carrier of preparation, it is stirred continuously, after realizing that incipient impregnation, air stand 6h, the dry 6h at 110 DEG C, then
5h is roasted at 520 DEG C, the hydrogenation catalyst is obtained, is denoted as catalyst CAT-R2；Iron oxide in catalyst CAT-R2
(Fe2O3) and the weight content of zinc oxide (ZnO) be the metal molar ratio of 17.4wt%, Fe and Zn be 5.0:1.
Comparative example 3
This comparative example provides a kind of hydrogenation catalyst, and preparation method includes the following steps:
Prepare catalyst carrier: by boehmite 63.5g (loss on ignition being considered, in terms of alumina content 78.1wt%)
With 5gAlPO4- 5 carry out mechanical mixture, extruded moulding, obtain catalyst carrier, molecular sieve and quality of alumina ratio are 5.2:
50。
Prepare iron-based hydrogenation catalyst: by nine water ferric nitrate (Fe (NO of 18.7g3)3·9H2) and 6.3g zinc nitrate hexahydrate O
(Zn(NO3)2·6H2O it) is dissolved in appropriate amount of deionized water and is made into co-impregnation solution, it is above-mentioned that co-impregnation solution is poured slowly into 30g
In the catalyst carrier of preparation, it is stirred continuously, after realizing that incipient impregnation, air stand 4h, the dry 9h at 110 DEG C, then
4h is roasted at 480 DEG C, the hydrogenation catalyst is obtained, is denoted as catalyst CAT-R3；Iron oxide in catalyst CAT-R3
(Fe2O3) and the weight content of zinc oxide (ZnO) be the metal molar ratio of 15.2wt%, Fe and Zn be 2.2:1.
Comparative example 4
This comparative example provides a kind of hydrogenation catalyst, and preparation method includes the following steps:
Mo-Fe/AlPO4- 5 (4) are Modification on Al PO4- 5 molecular sieves
Prepare catalyst carrier: by boehmite 68.5g (loss on ignition being considered, in terms of alumina content 78.1wt%)
With 9gMo-Fe/AlPO4- 5 (4) carry out mechanical mixture, extruded moulding, obtain catalyst carrier, molecular sieve and quality of alumina ratio
Example is 8.8:50.
Prepare iron-based hydrogenation catalyst: by nine water ferric nitrate (Fe (NO of 15g3)3·9H2) and 7.5g zinc nitrate hexahydrate (Zn O
(NO3)2·6H2O it) is dissolved in appropriate amount of deionized water and is made into co-impregnation solution, co-impregnation solution is poured slowly into the above-mentioned system of 30g
In standby catalyst carrier, it is stirred continuously, after realizing that incipient impregnation, air stand 6h, the dry 6h at 110 DEG C, then 520
5h is roasted at DEG C, is obtained the hydrogenation catalyst, is denoted as catalyst CAT-R4；Iron oxide (Fe in catalyst CAT-R42O3)
Weight content with zinc oxide (ZnO) is that the metal molar ratio of 14.3wt%, Fe and Zn are 1.4:1.
Comparative example 5
This comparative example provides a kind of hydrogenation catalyst, and preparation method includes the following steps:
With Mo-Fe/AlPO in embodiment 54- 5 (5) are Modification on Al PO4- 5 molecular sieves.
34.2g iron chloride and 5.92g zinc chloride are dissolved in 250mL deionized water, the water of iron chloride and zinc chloride is obtained
Solution；62g ammonia spirit is slowly added into while stirring in the aqueous solution of iron chloride and zinc chloride；It is stirred in 80 DEG C of water-bath
Reaction 5 hours is mixed, 60 DEG C of standings is then cooled to aging 24 hours, obtains sediment；The sediment is filtered while hot, spend from
Sub- water washing to pH value is approximately equal to 9, then dries in 110 DEG C of baking oven, then is heated up with the rate of 5 DEG C/min, 500 DEG C,
It is roasted 2 hours under air atmosphere, obtains iron zinc oxide powder；Metal molar ratio of Fe and Zn is in oxide obtained in it
4.9:1。
By the oxide powder 12.2g of iron-based hydrogenation catalyst, 550 DEG C of boehmite 8.2g, 1.8g after roasting 4 hours
Mo-Fe/AlPO4- 5 (5), are mixed evenly, and compression molding in tablet press machine is added, is denoted as catalyst CAT-5；The catalyst
Iron oxide (Fe in CAT-R52O3) and zinc oxide (ZnO) weight content be 54.6wt%.
Comparative example 6
Prepare catalyst carrier: by boehmite 63.5g (loss on ignition being considered, in terms of alumina content 78.1wt%)
Mechanical mixture, extruded moulding are carried out with 10.3g USY, obtains catalyst carrier, molecular sieve and quality of alumina ratio are 9.9:
50。
Prepare iron-based hydrogenation catalyst: by nine water ferric nitrate (Fe (NO of 22.9g3)3·9H2) and 3.10g zinc nitrate hexahydrate O
(Zn(NO3)2·6H2O it) is dissolved in appropriate amount of deionized water and is made into co-impregnation solution, it is above-mentioned that co-impregnation solution is poured slowly into 30g
In the catalyst carrier of preparation, it is stirred continuously, after realizing that incipient impregnation, air stand 6h, the dry 6h at 110 DEG C, then
5h is roasted at 520 DEG C, the hydrogenation catalyst is obtained, is denoted as catalyst CAT-R6；Iron oxide in catalyst CAT-R6
(Fe2O3) and the weight content of zinc oxide (ZnO) be the metal molar ratio of 15.6wt%, Fe and Zn be 5.0:1.
Comparative example 7
A kind of iron-based hydrogenation catalyst, preparation method includes the following steps:
Prepare catalyst carrier: by boehmite 63.5g (loss on ignition being considered, in terms of alumina content 78.1wt%)
Extruded moulding is carried out, catalyst carrier is obtained.
Prepare iron-based hydrogenation catalyst: by nine water ferric nitrate (Fe (NO of 18.7g3)3·9H2) and 6.3g zinc nitrate hexahydrate O
(Zn(NO3)2·6H2O it) is dissolved in appropriate amount of deionized water and is made into co-impregnation solution, it is above-mentioned that co-impregnation solution is poured slowly into 30g
In the catalyst carrier of preparation, it is stirred continuously, after realizing that incipient impregnation, air stand 4h, the dry 9h at 110 DEG C, then
4h is roasted at 480 DEG C, the hydrogenation catalyst is obtained, is denoted as catalyst CAT-R7；Iron oxide in catalyst CAT-R7
(Fe2O3) and the weight content of zinc oxide (ZnO) be the metal molar ratio of 15.2wt%, Fe and Zn be 2.2:1.
Comparative example 8
Prepare catalyst carrier: by boehmite 63.5g (loss on ignition being considered, in terms of alumina content 78.1wt%)
With 12.1g AlPO4- 5 carry out mechanical mixture, extruded moulding, obtain catalyst carrier, molecular sieve and quality of alumina ratio are
11.9:50。
Prepare iron-based hydrogenation catalyst: by nine water ferric nitrate (Fe (NO of 38.8g3)3·9H2O), 3.60g zinc nitrate hexahydrate
(Zn(NO3)2·6H2) and 0.42g Ammonium Molybdate Tetrahydrate (H O32Mo7N6O28) it is dissolved in appropriate amount of deionized water that be made into co-impregnation molten
Co-impregnation solution is poured slowly into the catalyst carrier of the above-mentioned preparation of 30g, is stirred continuously by liquid, realizes incipient impregnation, air
After standing 5h, the dry 6h at 100 DEG C, then 5h is roasted at 500 DEG C, the hydrogenation catalyst is obtained, catalyst is denoted as
CAT-R8；Iron oxide (Fe in catalyst CAT-R82O3) and the weight content of zinc oxide (ZnO) be 22.5wt%, Fe and Zn
Metal molar ratio is 8.1:1, MoO3Weight content be 0.87wt%.
Test case 1
The iron-based hydrogenation catalyst of embodiment 1-5 and comparative example 1-8 is carried out to the evaluation of Hydrogenation.This test case
Hydrotreating is carried out using 50mL high-temperature and high-pressure hydrogenation micro-reactor, and evaluation raw material presses residual oil, density (20 using normal pressure in sand
℃)0.987g/cm3, sulfur content 3.8wt%, total nitrogen content 0.34wt%.Catalyst has carried out vulcanizing treatment before application,
Make it have hydrogenation activity.Sulfurized oil is containing 5wt%CS2N-decane solution, the temperature of vulcanization is 360 DEG C, time 10h,
Pressure is 4MPa, liquid hourly space velocity (LHSV) 1.5h-1, hydrogen to oil volume ratio 300.Hydrogenation reaction raw material is pumped into using plunger pump, after reaction
Oil sample after high separator is cooling, in low separator collection analysis.The temperature of hydrotreating is 390 DEG C, pressure 10MPa,
Liquid hourly space velocity (LHSV) is 1h-1, hydrogen to oil volume ratio 800.Evaluating catalyst after embodiment catalyst and comparative catalyst's hydrotreating
As a result as shown in Tables 1 and 2.
1 embodiment evaluating catalyst result of table
| CAT-1 | CAT-2 | CAT-3 | CAT-4 | CAT-5 | |
| Desulfurization degree, % | 48.5 | 48.7 | 47.8 | 49.8 | 51.4 |
| Denitrification percent, % | 31.7 | 31.3 | 31.6 | 32.0 | 30.9 |
2 comparative example evaluating catalyst result of table
| CAT-R1 | CAT-R2 | CAT-R3 | CAT-R4 | CAT-R5 | |
| Desulfurization degree, % | 46.1 | 45.3 | 43.8 | 41.8 | 42.4 |
| Denitrification percent, % | 29.2 | 29.3 | 28.5 | 28 | 28.9 |
| CAT-R6 | CAT-R7 | CAT-R8 | |||
| Desulfurization degree, % | 42.7 | 39.2 | 46.3 | ||
| Denitrification percent, % | 26.7 | 24.3 | 29.7 |
Test case 2
The iron-based hydrogenation catalyst of embodiment 1-5 and comparative example 1-5 is carried out to the evaluation of Hydrogenation.This test case
Hydrotreating is carried out using 10mL high-temperature and high-pressure hydrogenation micro-reactor, and evaluation raw material uses grand celebration catalytic cracking diesel oil, the catalysis
Cracked diesel oil specific gravity () it is 0.8796, sulfur content 890ppm, total nitrogen content 920ppm, total arene content is
55.2v%.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 380 DEG C, pressure 6MPa, liquid hourly space velocity (LHSV) 1.0h-1, hydrogen to oil volume ratio 800.Urging after hydrotreating
Agent evaluation result is as shown in Tables 3 and 4.
3 embodiment evaluating catalyst result of table
| CAT-1 | CAT-2 | CAT-3 | CAT-4 | CAT-5 | |
| Desulfurization degree, % | 78.2 | 76.3 | 77.5 | 82.4 | 80.6 |
| Denitrification percent, % | 57.6 | 56.8 | 58.2 | 57.3 | 56.9 |
| De- virtue rate, % | 41.4 | 42.6 | 41.2 | 42.0 | 41.9 |
4 comparative example evaluating catalyst result of table
| CAT-R1 | CAT-R2 | CAT-R3 | CAT-R4 | CAT-R5 | |
| Desulfurization degree, % | 63.2 | 66.1 | 70.4 | 71.6 | 62.7 |
| Denitrification percent, % | 50.1 | 51.8 | 49.0 | 52.9 | 54.1 |
| De- virtue rate, % | 38.0 | 37.8 | 38.2 | 35.9 | 38.2 |
| CAT-R6 | CAT-R7 | CAT-R8 | |||
| Desulfurization degree, % | 70.8 | 59.4 | 72.3 | ||
| Denitrification percent, % | 53.1 | 43.7 | 54.7 | ||
| De- virtue rate, % | 38.8 | 31.4 | 39.0 |
It can be seen that compared with the iron-based hydrogenation catalyst of comparative example from the evaluation result of table 1-4, the iron-based of embodiment adds
Hydrogen catalyst has very high catalytic hydrogenation activity.And the iron-based hydrogenation catalyst of the embodiment of the present invention breaches tradition and adds
Hydrogen catalyst continues to use the limitation of the activity component metal of many decades, has important theoretical research value and industrial application value.
Claims (10)
1. a kind of iron-based hydrogenation catalyst, wherein the catalyst includes the oxide of carrier and carrier loaded active metal,
The carrier includes aluminium oxide and the AlPO modified with iron and molybdenum4- 5 molecular sieves, the active metal include main active metal and
Active metal is helped, the main active metal is Fe, described to help active metal for Zn；The AlPO modified with iron and molybdenum4- 5 points
The mass ratio of son sieve and aluminium oxide is (5-12): 50 (preferably (8-10): 50), Fe element and Zn element as active metal
Molar ratio be (2-10): 1 (preferably (6-10): 1), by total catalyst weight be 100% in terms of, the oxide of active metal is total
Weight is 15-50%；The AlPO modified with iron and molybdenum4The preparation method method of -5 molecular sieves includes:
(a) ferro element is introduced into AlPO4In -5 molecular sieves, Fe/AlPO is obtained4- 5 molecular sieves, with obtained Fe/AlPO4- 5 points
Son sieve weight 100% is counted, and ferro element is with Fe2O3It is calculated as 0.5~5% (preferably 2-4%)；
(b) Fe/AlPO obtained with the water-soluble salting liquid incipient impregnation step (a) of metal molybdenum4- 5 molecular sieves, then by washing
It washs, dry and roasts, obtain Mo-Fe/AlPO4- 5 molecular sieves, with Mo-Fe/AlPO4- 5 molecular sieve total weights 100% meter, MoO3
For 3~10% (preferably 3-8%).
2. iron-based hydrogenation catalyst according to claim 1, wherein the water-soluble salt of the metal molybdenum is four molybdic acid hydrates
Ammonium.
3. iron-based hydrogenation catalyst according to claim 1, wherein the maturing temperature of step (b) is 450-550 DEG C (excellent
The drying temperature for selecting step (b) is 90-120 DEG C).
4. iron-based hydrogenation catalyst according to claim 1, wherein step (a) is isometric with the water-soluble salting liquid of iron
Impregnate AlPO4- 5 molecular sieves, then by dry (preferably drying temperature is 90-120 DEG C) and roasting, (preferably maturing temperature is
450-550 DEG C), obtain the Fe/AlPO4- 5 molecular sieves；It is preferred that the water-soluble salt of the iron is Fe(NO3)39H2O.
5. iron-based hydrogenation catalyst described in any one according to claim 1~4, wherein the iron-based hydrogenation catalyst
Preparation method includes the following steps:
It prepares main active metal and helps the co-impregnation solution of active metal, it is then by the method for incipient impregnation that main activity is golden
Belong to and active metal is helped to load on boehmite, (temperature preferably roasted is 450-550 DEG C, is further preferably roasted by roasting
The time of burning is 2-12h, and the time more preferably roasted is 4-8h) obtain the iron-based hydrogenation catalyst；
Alternatively, by main reactive metal oxides and active metal oxide powder is helped to be uniformly mixed with carrier, obtain described iron-based
Hydrogenation catalyst；
Or by main reactive metal oxides and active metal oxide powder is helped to be uniformly mixed with boehmite, it roasts (excellent
The temperature of choosing roasting is 450-550 DEG C, and the time further preferably roasted is 2-12h, and the time more preferably roasted obtains institute for 4-8h)
State iron-based hydrogenation catalyst.
6. iron-based hydrogenation catalyst according to claim 5, wherein to carrier loaded main active metal and help active metal
The step of include: to prepare main active metal and the co-impregnation solution of active metal is helped (preferably to prepare main active metal and help activity
The step of co-impregnation solution of metal includes: by water-soluble salt (preferably Fe(NO3)39H2O, iron chloride and the sulphur of main active metal
One of sour iron or a variety of mixing) and help water-soluble salt (preferably zinc nitrate hexahydrate, zinc chloride and the sulfuric acid of active metal
One of zinc or a variety of mixing) be dissolved in water to obtain the co-impregnation solution), then pass through the method for incipient impregnation
By main active metal and active metal is helped to load on boehmite, main active metal will have been loaded and helps the quasi- of active metal
Boehmite is dried that (preferably dry temperature is 90-120 DEG C；It is preferred that the dry time is 4-12h), it then roasts, obtains
To the iron-based hydrogenation catalyst, (preferably by the main active metal of carrier impregnation and after helping active metal, further including will be impregnated of master
It active metal and the step of helping the carrier of active metal to be stood, is then dried and roasts again；It is preferred that the time stood
For 4-24h).
7. iron-based hydrogenation catalyst according to claim 5, wherein by main reactive metal oxides and help active metal oxygen
The step that compound powder is uniformly mixed with carrier or boehmite includes: water-soluble salt (preferably nine hydrations of main active metal
One of ferric nitrate, iron chloride and ferric sulfate or a variety of mixing) and help active metal water-soluble salt (preferably six hydration nitre
One of sour zinc, zinc chloride and zinc sulfate or a variety of mixing) in water be uniformly mixed obtain mixed solution, in alkaline condition
Under (preferably the pH value of mixed solution be more than or equal to 10) reaction obtain main active metal and the hydroxide of active metal helped to precipitate
Mixture, then (preferably maturing temperature is 450-550 DEG C, and the time further preferably roasted is 2-12h, is more preferably roasted for roasting
Time is 4-8h) it obtains main active metal and helps the oxide mixture of active metal, then by oxide mixture and carrier
Or boehmite is uniformly mixed.
8. iron-based hydrogenation catalyst according to claim 7, wherein by main reactive metal oxides and help active metal oxygen
The step that compound powder is uniformly mixed with carrier or boehmite includes: the water-soluble salt with main active metal and helps active metal
Water-soluble salt it is soluble in water, be added alkali (preferably ammonium hydroxide or urea) reacted (preferable reaction temperature be 75-95 DEG C, it is more excellent
Selecting the reaction time is 4-8h) it is precipitated and (preferably also carries out aging after reaction and precipitate that (preferably aging is in 50- again
20-30h is stood at 80 DEG C)), it is filtered after fully reacting, the precipitating being obtained by filtration is roasted to obtain iron zinc oxide powder, by iron
Zinc oxide powder is uniformly mixed with carrier or boehmite.
9. iron-based hydrogenation catalyst according to claim 5, wherein with the main active metal of preparation and helping active metal
Co-impregnation solution incipient impregnation carrier before, further include by aluminium oxide and the AlPO modified with iron and molybdenum4The mixing of -5 molecular sieves
The step of；It is preferred that by aluminium oxide and the AlPO modified with iron and molybdenum4It further include by mixture extruded moulding after the mixing of -5 molecular sieves
The step of.
10. the preparation method of iron-based hydrogenation catalyst described in any one of claim 1 to 9, the method includes the use
Iron and molybdenum are to AlPO4The step of -5 molecular sieves are modified, the step include:
(a) ferro element is introduced into AlPO4In -5 molecular sieves, Fe/AlPO is obtained4- 5 molecular sieves, with obtained Fe/AlPO4- 5 points
Son sieve weight 100% is counted, and ferro element is with Fe2O3It is calculated as 0.5~5%；
(b) Fe/AlPO obtained with the water-soluble salting liquid incipient impregnation step (a) of metal molybdenum4- 5 molecular sieves, then by washing
It washs, dry and roasts, obtain Mo-Fe/AlPO4- 5 molecular sieves, with Mo-Fe/AlPO4- 5 molecular sieve total weights 100% meter, MoO3
It is 3~10%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111957341A (en) * | 2019-05-20 | 2020-11-20 | 中海石油炼化有限责任公司 | Catalyst for regulating and controlling CO hydrogenation reaction product rich in aromatic hydrocarbon and preparation method and application thereof |
| CN112745357A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Complex containing molybdenum and iron, preparation method thereof, hydrogenation catalyst and application thereof |
| CN114602472A (en) * | 2022-04-12 | 2022-06-10 | 福州大学 | Residual oil suspension bed hydrocracking catalyst, preparation method and application thereof |
| CN116510770A (en) * | 2023-01-18 | 2023-08-01 | 华东理工大学 | Composite catalyst and preparation method and application thereof |
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|---|---|---|---|---|
| CN1778874A (en) * | 2004-11-26 | 2006-05-31 | 中国石油天然气股份有限公司 | Hydrogenation dearomatization catalyst containing molecular screen |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1778874A (en) * | 2004-11-26 | 2006-05-31 | 中国石油天然气股份有限公司 | Hydrogenation dearomatization catalyst containing molecular screen |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111957341A (en) * | 2019-05-20 | 2020-11-20 | 中海石油炼化有限责任公司 | Catalyst for regulating and controlling CO hydrogenation reaction product rich in aromatic hydrocarbon and preparation method and application thereof |
| CN112745357A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Complex containing molybdenum and iron, preparation method thereof, hydrogenation catalyst and application thereof |
| CN114602472A (en) * | 2022-04-12 | 2022-06-10 | 福州大学 | Residual oil suspension bed hydrocracking catalyst, preparation method and application thereof |
| CN116510770A (en) * | 2023-01-18 | 2023-08-01 | 华东理工大学 | Composite catalyst and preparation method and application thereof |
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