CN109395770B - Iron-based hydrogenation catalyst and preparation method thereof - Google Patents
Iron-based hydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN109395770B CN109395770B CN201710704765.7A CN201710704765A CN109395770B CN 109395770 B CN109395770 B CN 109395770B CN 201710704765 A CN201710704765 A CN 201710704765A CN 109395770 B CN109395770 B CN 109395770B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
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- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
Abstract
The invention provides an iron-based hydrogenation catalyst and a preparation method thereof. The catalyst comprises a carrier and an oxide of an active metal, the carrier comprising alumina and iron and molybdenumModified AlPO4-5 molecular sieve, the active metal comprising a main active metal and an auxiliary active metal, the main active metal being Fe and the auxiliary active metal being Zn; iron and molybdenum modified AlPO4-5 mass ratio of molecular sieve to alumina (5-12): 50, the molar ratio of active metals Fe element and Zn element is (2-10): 1, taking the total weight of the catalyst as 100 percent and the total weight of the active metal oxide as 15 to 50 percent; the preparation method of the molecular sieve comprises the following steps: fe is introduced into AlPO4-5 molecular sieves to obtain Fe/AlPO4-5 molecular sieves; soaking the mixture in Fe/AlPO with Mo water solution in the same volume4On-5 molecular sieves to obtain Mo-Fe/AlPO4-5 molecular sieves.
Description
Technical Field
The invention relates to the field of hydrogenation catalysis, in particular to an iron-based hydrogenation catalyst and a preparation method thereof.
Background
The hydrogenation technology is the core technology of heavy oil lightening, and plays an important role in deep processing of heavy raw oil, product quality improvement, raw material adaptability enhancement and operation flexibility enhancement, and a plurality of new oil refining hydrogenation catalysts and preparation methods thereof are developed successively.
CN104588116A discloses a hydrotreating catalyst, which is prepared by using alumina as a carrier, using Co, Mo, Ni and W as active metal components, unsaturated impregnating a wetting solution containing an adsorbent I, then impregnating a solution containing the active metal Mo and Co, drying and roasting, then saturated impregnating or excessively impregnating a solution containing an adsorbent II, namely polyethylene glycol, and then impregnating W, Ni active metal. Patent CN103769118A discloses a heavy oil hydrogenation catalyst, wherein a carrier is alumina, and active components are metals of VIII group and/or VIB group, wherein VIII metal is Co or Ni, VIB group metal is Mo or W, the catalyst is prepared by molding pseudo-boehmite with dry basis content of below 50%, and the catalyst prepared by the method has high activity of demetallization, desulfurization and carbon residue removal. CN103212432A adopts alumina and HY molecular sieve as carriers, surface acid treatment is carried out on the alumina and the HY molecular sieve, the alumina after the acid treatment and the HY after the acid treatment are mechanically compounded to be used as carriers, active components of the catalyst are loaded by dipping liquid containing the active components of the catalyst, the active components comprise Mo and/or W and Co and/or Ni, and complexing agent is also contained in the dipping liquid, and the catalyst has high hydrodenitrogenation and hydrodesulfurization performance on inferior heavy oil distillate oil. CN105582948A discloses a preparation method of a residual oil hydrogenation catalyst, which comprises the steps of dipping an alumina carrier by using a urea aqueous solution, drying the dipped alumina carrier, preparing at least two dipping solutions containing polyalcohol and/or monosaccharide and hydrogenation active metal components with different concentrations, spraying and dipping the dipping solutions on the alumina carrier in a sequence from high concentration to low concentration to ensure that the concentration of the hydrogenation metal components is distributed on the carrier in a gradient from low concentration to high concentration from outside to inside, and carrying out hydrothermal treatment, drying and oxygen-free high-temperature treatment in a sealed container.
The hydrogenation active components in the above patents are mainly Co (Ni) Mo (W) series oxides or sulfides; the carrier mainly comprises alumina, amorphous silica-alumina, molecular sieve materials and the like. In order to further improve the hydrogenation activity of the catalyst, the composite oxide hydrogenation metal active phase catalyst and the preparation method thereof are successively disclosed.
Patent CN00110017.3 adds fluorine into aluminum chloride solution or aluminum sulfate solution, then adds compounds containing boron, silicon, phosphorus, magnesium, titanium, zirconium, gallium; adding Ni and W; heating the mixed solution to 40-80 ℃, precipitating with ammonia water, and drying the precipitate; adding a binder, a molecular sieve and an auxiliary agent into the dried precipitate, molding, drying and roasting to obtain the catalyst, wherein the catalyst contains 30-70% of oxide, 5-30% of Y-type molecular sieve, 2-8% of fluorine and 0.5-5% of one or more than one of oxides of boron, silicon, phosphorus, magnesium, titanium, zirconium and gallium by mass of active components of metals of VIB group and VIII group. CN103801317A discloses a preparation method of a hydrogenation catalyst containing W, Ni, Al, Mg composite oxides and Mo, Co composite oxides, which comprises the steps of preparing a precursor of the W, Ni, Al, Mg composite oxides through coprecipitation, forming, washing, drying and roasting to obtain a catalyst intermediate, impregnating the catalyst intermediate with an impregnating solution containing Co and Mo, drying and roasting to obtain the catalyst. Patent CN103801318A prepares W, Ni composite oxide precursor through coprecipitation, and macromolecule polyethylene glycol is introduced in the precipitation process, after molding, washing, drying and roasting, catalyst intermediate is obtained, the catalyst is impregnated by specific impregnation liquid containing Co and Mo, and after drying and roasting, the hydrotreating catalyst is obtained, so that the catalyst has smaller particles and larger surface area, and under the premise of uniform dispersion of active metal, a mixed type active center with excellent matching of hydrogenation performance and hydrogenolysis performance is formed, and the better synergistic play of the hydrogenation and hydrogenolysis desulfurization functions of the active components of the catalyst is realized.
In the patent, the hydrogenation active component is mainly Co (Ni) xMo (W) y composite oxide or sulfide; the hydrogenation metal active phase has higher hydrogenation activity than the supported Co (Ni) Mo (W) oxide or sulfide of the traditional impregnation method, but the high cost is another problem to be solved urgently. Especially, the development of low-cost hydrogenation catalysts has wider significance in the face of increasing heavy oil production and heavy components in crude oil.
CN104918698B discloses an iron-based heavy oil hydrogenation catalyst, which takes iron as a main active component metal and zinc and potassium as first auxiliary active component metals, and the molar ratio of the main active component metal to the auxiliary active component metals is 0.5-200: 1. CN1965061A contacting a feed oil with a source of hydrogen in the presence of one or more catalysts to produce a crude product, wherein one or more of the catalysts comprises a catalyst comprising K3Fe10S14The catalyst of (1). CN1245255C discloses a Fischer-Tropsch synthesis iron-based catalyst and a preparation method thereof, wherein the catalyst comprises the following components: zn: cu: k: SiO 22100: (0.01-8): (0.5-15): (0.5-10): (5-40), coprecipitating a mixed solution of ferric nitrate, zinc nitrate and copper acetate by taking a sodium carbonate solution as a precipitant to obtain a precipitate slurry, adding a mixed solution of a potassium silicate aqueous solution and silica sol into the precipitate slurry to obtain a catalyst slurry, feeding the catalyst slurry into a spray dryer to obtain powder, and then roasting to obtain the catalyst.
CN104588108A discloses a heavy oil hydrogenation catalyst, which comprises, by weight, 10-50% of iron oxyhydroxide, 20-70% of macroporous alumina and 5-40% of pseudo-boehmite, wherein the content of organic polycarboxylic acid is 0.05-0.40g/g of iron oxyhydroxide, an aluminum-containing alkaline solution and a ferrous salt solution are stirred and mixed to obtain a suspension of ferrous hydroxide, and then oxygen and CO are introduced into the lower part of a reactor2The introduction of CO is stopped when the pH value is 9-112And continuously introducing oxygen-containing gas to obtain aluminum hydroxide slurry containing iron oxyhydroxide, then treating with organic polybasic acid, adding macroporous alumina into the obtained filter cake, mixing and molding, and drying to obtain the heavy oil hydrogenation catalyst.
In view of the above, researchers have made a lot of research on the modification of the supported catalyst carrier and the auxiliary agent for gasoline and diesel oil and heavy oil, and the preparation of the breakthrough unsupported catalyst, which has appeared in recent years, and also made many efforts to reduce the production and preparation costs of the catalyst. But the basic combination of metals of molybdenum and tungsten as main active components is not broken by taking nickel and cobalt as assistants. Therefore, the development of a gasoline-diesel oil and heavy oil hydrogenation catalyst with both cost and activity is still one of the problems to be solved in the field.
Disclosure of Invention
It is an object of the present invention to provide an iron-based hydrogenation catalyst;
the invention also aims to provide a preparation method of the iron-based hydrogenation catalyst.
In order to achieve the above object, in one aspect, the present invention provides an iron-based hydrogenation catalyst, wherein the catalyst comprises a carrier comprising alumina and AlPO modified with iron and molybdenum, and an oxide of an active metal supported on the carrier4-5 molecular sieves, the active metals comprising a primary active metal and a co-active metal, the primary active metal being Fe and the co-active metal being Zn; the AlPO modified with iron and molybdenum4-5 mass ratio of molecular sieve to alumina (5-12): 50, the molar ratio of Fe element and Zn element as active metals is (2-10): 1, taking the total weight of the catalyst as 100 percent, and taking the total weight of the oxide of the active metal as 15 to 50 percent; the AlPO modified with iron and molybdenum4The preparation method of the molecular sieve comprises the following steps:
(a) introduction of iron element into AlPO4-5 molecular sieves to obtain Fe/AlPO4-5 molecular sieves to obtain Fe/AlPO4-5 molecular sieve weight 100%, iron element is Fe2O30.5-5%;
(b) isovolumetrically impregnating Fe/AlPO obtained in step (a) with a molybdenum metal water-soluble salt solution4-5 molecular sieve, then drying and roasting to obtain Mo-Fe/AlPO4-5 molecular sieves, in Mo-Fe/AlPO4-5 MoO, based on 100% of the total weight of the molecular sieve33 to 10 percent.
It is understood that the Fe element of the iron-based hydrogenation catalyst of the present invention is divided into two portions: fe element as active metal and for AlPO4-5 molecular sieve modified Fe element.
According to some embodiments of the invention, wherein the AlPO modified with iron and molybdenum4-5 mass ratio of molecular sieve to alumina (8-10): 50.
according to some embodiments of the present invention, the molar ratio of Fe element and Zn element is (6-10): 1.
according to some embodiments of the invention, the iron element in step (a) is Fe2O3Calculated as 2-4%.
According to some embodiments of the present invention, wherein Mo-Fe/AlPO is used in step (b)4-5 MoO, based on 100% of the total weight of the molecular sieve3Is 3-8%.
According to some embodiments of the invention, the water-soluble salt of metallic molybdenum in step (b) is ammonium molybdate tetrahydrate.
According to some embodiments of the present invention, wherein the calcination temperature in step (b) is 450-550 ℃.
According to some embodiments of the invention, wherein the drying temperature of step (b) is 90-120 ℃.
According to some embodiments of the invention, wherein step (a) is an equal volume impregnation of AlPO with an iron water-soluble salt solution4-5 molecular sieve, then drying and roasting to obtain the Fe/AlPO4-5 molecular sieves.
According to some embodiments of the invention, wherein the drying temperature in step (a) is 90-120 ℃.
According to some embodiments of the present invention, wherein the calcination temperature in step (a) is 450-550 ℃.
According to some embodiments of the invention, the water-soluble salt of iron in step (a) is iron nitrate nonahydrate.
According to some embodiments of the present invention, the preparation method of the iron-based hydrogenation catalyst comprises the following steps:
preparing co-impregnation solution of main active metal and auxiliary active metal, then loading the main active metal and the auxiliary active metal on pseudo-boehmite by an isometric impregnation method, and roasting to obtain the iron-based hydrogenation catalyst;
or uniformly mixing main active metal oxide powder and auxiliary active metal oxide powder with a carrier to obtain the iron-based hydrogenation catalyst;
or uniformly mixing the main active metal oxide powder and the auxiliary active metal oxide powder with the pseudo-boehmite, and roasting to obtain the iron-based hydrogenation catalyst.
According to some embodiments of the present invention, the calcination temperature after loading the primary active metal and the secondary active metal to the pseudo-boehmite is 450-550 ℃.
According to some embodiments of the present invention, the calcination temperature after uniformly mixing the primary active metal oxide and the auxiliary active metal oxide powder with the pseudo-boehmite is 450-550 ℃.
According to some embodiments of the present invention, the roasting time after the primary active metal and the secondary active metal are loaded to the pseudo-boehmite is 2 to 12 hours; of these, 4 to 8 hours are preferred.
According to some embodiments of the present invention, the roasting time after uniformly mixing the main active metal oxide and the auxiliary active metal oxide powder with the pseudo-boehmite is 2-12 hours; of these, 4 to 8 hours are preferred.
According to some embodiments of the present invention, the step of loading the carrier with the primary active metal and the secondary active metal comprises: preparing co-impregnation solution of main active metal and auxiliary active metal, then loading the main active metal and the auxiliary active metal on the pseudo-boehmite by an equal-volume impregnation method, drying the pseudo-boehmite loaded with the main active metal and the auxiliary active metal, and then roasting to obtain the iron-based hydrogenation catalyst.
According to some embodiments of the invention, the step of preparing a co-impregnation solution of the primary active metal and the secondary active metal comprises: and dissolving the water-soluble salt of the main active metal and the water-soluble salt of the auxiliary active metal in water to obtain the co-impregnation solution.
According to some embodiments of the invention, the water-soluble salt of the primary reactive metal is a mixture of one or more of ferric nitrate nonahydrate, ferric chloride and ferric sulfate.
According to some embodiments of the invention, the water-soluble salt of the coactive metal is a mixture of one or more of zinc nitrate hexahydrate, zinc chloride and zinc sulfate.
According to some embodiments of the present invention, the temperature at which the pseudo-boehmite loaded with the primary active metal and the secondary active metal is dried is 90 to 120 ℃.
According to some embodiments of the present invention, the pseudo-boehmite loaded with the primary active metal and the secondary active metal is dried for 4 to 12 hours.
According to some embodiments of the present invention, after the pseudo-boehmite is impregnated with the primary active metal and the secondary active metal, the pseudo-boehmite impregnated with the primary active metal and the secondary active metal is allowed to stand, and then dried and calcined.
According to some embodiments of the invention, the time of standing is 4 to 24 hours.
According to some embodiments of the present invention, the step of uniformly mixing the primary active metal oxide and the secondary active metal oxide powders with the carrier or the pseudo-boehmite comprises: the water soluble salt of the main active metal and the water soluble salt of the auxiliary active metal are uniformly mixed in water to obtain a mixed solution, the mixed solution reacts under an alkaline condition to obtain a hydroxide precipitation mixture of the main active metal and the auxiliary active metal, then the hydroxide precipitation mixture is roasted to obtain an oxide mixture of the main active metal and the auxiliary active metal, and then the oxide mixture is uniformly mixed with the carrier or the pseudo-boehmite.
According to some embodiments of the invention, the water-soluble salt of the primary reactive metal is a mixture of one or more of ferric nitrate nonahydrate, ferric chloride and ferric sulfate.
According to some embodiments of the invention, the water-soluble salt of the coactive metal is a mixture of one or more of zinc nitrate hexahydrate, zinc chloride and zinc sulfate.
According to some embodiments of the invention, the alkaline condition is that the pH of the mixed solution is 10 or more.
According to some embodiments of the present invention, the calcination temperature after the reaction under alkaline conditions to obtain the hydroxide precipitate mixture of the primary active metal and the secondary active metal is 450-550 ℃.
According to some embodiments of the present invention, the calcination time after the reaction under alkaline conditions to obtain the hydroxide precipitation mixture of the main active metal and the auxiliary active metal is 2 to 12 hours; preferably 4-8 h.
According to some embodiments of the present invention, the step of uniformly mixing the primary active metal oxide and the secondary active metal oxide powders with the carrier or the pseudo-boehmite comprises: dissolving water soluble salt of main active metal and water soluble salt of auxiliary active metal in water, adding alkali to react to obtain precipitate, filtering after complete reaction, roasting the precipitate to obtain iron-zinc oxide powder, and mixing the iron-zinc oxide powder with carrier or pseudo-boehmite uniformly.
According to some embodiments of the invention, the base is ammonia or urea.
According to some embodiments of the invention, the water-soluble salt of the primary reactive metal is a mixture of one or more of ferric nitrate nonahydrate, ferric chloride and ferric sulfate.
According to some embodiments of the invention, the water-soluble salt of the coactive metal is a mixture of one or more of zinc nitrate hexahydrate, zinc chloride and zinc sulfate.
According to some embodiments of the invention, wherein the reaction temperature of the reaction is 75-95 ℃.
According to some embodiments of the invention, the reaction time of the reaction is 4 to 8 hours.
According to some embodiments of the invention, the precipitate is obtained after aging after the reaction is completed.
According to some embodiments of the invention, wherein the aging is standing at 50-80 ℃ for 20-30 h; preferably, the mixture is allowed to stand at 60 ℃ for 24 hours.
According to some embodiments of the present invention, the step of uniformly mixing the iron-zinc oxide powder and the carrier further comprises a step of tabletting the mixed iron-zinc oxide powder and the carrier.
According to some embodiments of the present invention, before the co-impregnation of the carrier with the co-impregnation solution of the primary active metal and the co-active metal in the same volume, alumina and AlPO modified with iron and molybdenum are further included4-5 a step of mixing the molecular sieves.
According to some embodiments of the invention, wherein the alumina and the AlPO modified with iron and molybdenum are mixed45 after the molecular sieve is mixed, the step of extruding the mixture into strips is also included.
In another aspect, the invention also provides a preparation method of the iron-based hydrogenation catalyst, which comprises the step of using iron and molybdenum to perform reaction on AlPO4-5 a step of modifying the molecular sieve, said step comprising:
(a) introduction of iron element into AlPO4-5 molecular sieves to obtain Fe/AlPO4-5 molecular sieves to obtain Fe/AlPO4-5 molecular sieve weight 100%, iron element is Fe2O30.5-5%;
(b) isovolumetrically impregnating Fe/AlPO obtained in step (a) with a molybdenum metal water-soluble salt solution4-5 molecular sieve, then washing, drying and roasting to obtain Mo-Fe/AlPO4-5 molecular sieves, in Mo-Fe/AlPO4-5 MoO, based on 100% of the total weight of the molecular sieve33 to 10 percent.
In conclusion, the invention provides an iron-based hydrogenation catalyst and a preparation method thereof. The catalyst of the invention has the following advantages:
the invention adopts an iron-based hydrogenation catalyst to replace the traditional hydrogenation catalyst which takes molybdenum and tungsten of VIB group as active component metals and cobalt and nickel of VIII group as auxiliary metals. The iron is used as a main active component metal, and the zinc is used as an auxiliary active component metal; and modified Mo-Fe/AlPO4The introduction of the-5 molecular sieve into the alumina carrier can effectively improve the carrierThe catalyst has interaction with the active component FeZn of the hydrogenation metal, so that the activity of the catalyst is improved. Compared with the traditional hydrogenation catalyst, the iron-based catalyst has the advantages of cheap and easily obtained raw materials, simple manufacturing process and the like, can greatly reduce the production cost of the hydrogenation catalyst, has higher hydrogenation activity, and has long-term industrial application value.
Detailed Description
The following detailed description is provided for the purpose of illustrating the embodiments and the advantageous effects thereof, and is not intended to limit the scope of the present disclosure.
Example 1
An iron-based hydrogenation catalyst, the preparation method comprises the following steps:
Fe/AlPO4-5(1) preparation: 1.27g of iron nitrate nonahydrate (Fe (NO)3)3·9H2O) is dissolved in 42.5g of distilled water to prepare a solution, and the solution is slowly dripped into 50g of AlPO by an equal-volume immersion method4Standing in-5 molecular sieve with air for 3 hr, drying at 110 deg.C for 12 hr, and calcining at 540 deg.C for 3 hr. Elemental analysis showed Fe/AlPO4Fe in (5), (1)2O3The mass percentage of (B) is 0.51 wt%.
Mo-Fe/AlPO4-5(1) preparation: 0.92g of ammonium molybdate tetrahydrate (H)32Mo7N6O28) Dissolving in 21g distilled water to obtain solution, and slowly adding dropwise 25g Fe/AlPO by equal volume immersion method4And (5) standing in air for 3h, drying at 110 ℃ for 12h, and roasting at 500 ℃ for 3 h. Elemental analysis showed Mo-Fe/AlPO4MoO in (5) or (1)3The mass percentage of (B) is 3.2 wt%.
Preparing a catalyst carrier: pseudo-boehmite 63.5g (in terms of weight percent of alumina content in consideration of loss on ignition) and 5g of Mo-Fe/AlPO45(1) mechanically mixing, extruding and forming to obtain the catalyst carrier, wherein the mass ratio of the molecular sieve to the alumina is 5.2: 50.
Preparing an iron-based hydrogenation catalyst: 18.7g of ferric nitrate nonahydrate (Fe (NO)3)3·9H2O) and 6.3g of zinc nitrate hexahydrate (Zn (NO)3)2·6H2O) dissolving in a proper amount of deionized water to prepare a co-impregnation solution, slowly pouring the co-impregnation solution into 30g of the prepared catalyst carrier, continuously stirring to realize equal-volume impregnation, standing in air for 4 hours, drying at 110 ℃ for 9 hours, and roasting at 480 ℃ for 4 hours to obtain the hydrogenation catalyst, which is marked as catalyst CAT-1; iron oxide (Fe) in the catalyst CAT-12O3) And zinc oxide (ZnO) 15.2 wt%, with a metal molar ratio of Fe to Zn of 2.2: 1.
Example 2
Fe/AlPO4-5(2) preparation: the hydrothermal synthesis method of patent CN200710009684.1 is adopted to prepare the AlPO containing iron4-5 molecular sieves. The iron source is ferric nitrate nonahydrate (Fe (NO)3)3·9H2O), using triethylamine (Et)3N) is a template agent; the proportion of the synthetic gel is (atomic ratio): 0.04Fe:1Al2O3:1.06P2O5:1.47Et3N:45H2O, the crystallization temperature is 190 ℃, and the crystallization time is 16 hours. Filtering, washing, drying (90 ℃) and roasting the obtained product at 500 ℃; elemental analysis shows that the product is Fe2O3The mass content is 1.6 wt%.
Mo-Fe/AlPO4-5(2) preparation: 2.2g of ammonium molybdate tetrahydrate (H)32Mo7N6O28) Dissolving in 21g distilled water to obtain solution, and slowly adding dropwise 25g Fe/AlPO by equal volume immersion method4-5(2), standing for 4h in air, drying at 100 ℃ for 12h, and roasting at 500 ℃ for 4h to obtain MoO in the product3The mass percentage of (B) is 7.1 wt%.
Preparing a catalyst carrier: a mixture of 63.5g of pseudoboehmite (calculated as the alumina content of 78.1 wt% in view of loss on ignition) and 12.1g of Mo-Fe/AlPO45(2) mechanically mixing, extruding and forming to obtain the catalyst carrier, wherein the mass ratio of the molecular sieve to the alumina is 11.9: 50.
Preparing an iron-based hydrogenation catalyst: mixing 38.8g ferric nitrate nonahydrate (Fe (NO)3)3·9H2O) and 3.60g of zinc nitrate hexahydrate (Zn (NO)3)2·6H2O) dissolving in a proper amount of deionized water to prepare a co-impregnation solution, slowly pouring the co-impregnation solution into 30g of the prepared catalyst carrier, continuously stirring to realize equal-volume impregnation, standing for 5 hours in air, drying for 6 hours at 100 ℃, and roasting for 5 hours at 500 ℃ to obtain the hydrogenation catalyst, which is marked as catalyst CAT-2; iron oxide (Fe) in the catalyst CAT-22O3) And zinc oxide (ZnO) in an amount of 22.5 wt%, with a metal molar ratio of Fe to Zn of 8.1: 1.
Example 3
Fe/AlPO4-5(3) preparation: the hydrothermal synthesis method of patent CN200710009684.1 is adopted to prepare the AlPO containing iron4-5 molecular sieves. The iron source is ferric nitrate nonahydrate (Fe (NO)3)3·9H2O), using triethylamine (Et)3N) is a template agent; the proportion of the synthetic gel is (atomic ratio): 0.065Fe:1Al2O3:1.06P2O5:1.47Et3N:45H2O, the crystallization temperature is 190 ℃, and the crystallization time is 16 hours. Filtering, washing, drying (90 ℃) and roasting the obtained product at 500 ℃; elemental analysis shows that the product is Fe2O3The mass content is 2.9 wt%.
Mo-Fe/AlPO4-5(3) preparation: 2.76g of ammonium molybdate tetrahydrate (H)32Mo7N6O28) Dissolving in 21g distilled water to obtain solution, and slowly adding dropwise 25g Fe/AlPO by equal volume immersion method4-5(3), standing for 4h in air, drying at 100 ℃ for 12h, and roasting at 500 ℃ for 4h to obtain MoO in the product3The mass percentage of the component (B) is 8.8 wt%.
Preparing a catalyst carrier: 63.5g of pseudoboehmite (calculated as the alumina content of 78.1 wt% in consideration of loss on ignition) and 10.3g of Mo-Fe/AlPO45, (3) mechanically mixing, extruding and forming to obtain the catalyst carrier, wherein the mass ratio of the molecular sieve to the alumina is 9.9: 50.
Preparing an iron-based hydrogenation catalyst: 22.9g of ferric nitrate nonahydrate (Fe (NO)3)3·9H2O) and 3.10g of zinc nitrate hexahydrate (Zn (NO)3)2·6H2O) is dissolved in a proper amount of deionized water to prepare a co-dipping solutionSlowly pouring the co-impregnation solution into 30g of the prepared catalyst carrier, continuously stirring to realize equal-volume impregnation, standing in air for 6 hours, drying at 110 ℃ for 6 hours, and roasting at 520 ℃ for 5 hours to obtain the hydrogenation catalyst, which is marked as catalyst CAT-3; iron oxide (Fe) in the catalyst CAT-32O3) And zinc oxide (ZnO) 15.6 wt%, with a metal molar ratio of Fe to Zn of 5.0: 1.
Example 4
Fe/AlPO4-5(4) preparation: 10.1g of ferric nitrate nonahydrate (Fe (NO)3)3·9H2O) is dissolved in 42.5g of distilled water to prepare a solution, and the solution is slowly dripped into 50g of AlPO by an equal-volume immersion method4Standing in-5 molecular sieve with air for 3 hr, drying at 110 deg.C for 12 hr, and calcining at 500 deg.C for 3 hr. Elemental analysis showed Fe/AlPO4Fe in (5), (4)2O3The mass percentage of (B) is 3.9 wt%.
Mo-Fe/AlPO4-5(4) preparation: 1.53g of ammonium molybdate tetrahydrate (H)32Mo7N6O28) Dissolving in 21g distilled water to obtain solution, and slowly adding dropwise 25g Fe/AlPO by equal volume immersion method4-5(4), standing for 4h in air, drying at 100 ℃ for 12h, and roasting at 500 ℃ for 4h to obtain MoO in the product3The mass percentage of (B) is 5.1 wt%.
Preparing a catalyst carrier: pseudo-boehmite 63.5g (in terms of weight percent of alumina content in consideration of loss on ignition) and 9gMo-Fe/AlPO45(4) mechanically mixing, extruding and forming to obtain the catalyst carrier, wherein the mass ratio of the molecular sieve to the alumina is 8.8: 50.
Preparing an iron-based hydrogenation catalyst: 43.5g of iron nitrate nonahydrate (Fe (NO)3)3·9H2O) and 4.1g of zinc nitrate hexahydrate (Zn (NO)3)2·6H2O) dissolving in a proper amount of deionized water to prepare a co-impregnation solution, slowly pouring the co-impregnation solution into 30g of the prepared catalyst carrier, continuously stirring to realize equal-volume impregnation, standing in air for 6h, drying at 110 ℃ for 6h, and roasting at 520 ℃ for 5h to obtain the hydrogenation catalyst, which is marked as catalyst CAT-4; the catalyst CAT-4 iron oxide (Fe)2O3) And zinc oxide (ZnO) in an amount of 24.2 wt%, with a metal molar ratio of Fe to Zn of 8: 1.
Example 5
Fe/AlPO4-5(5) preparation: 12.5g of ferric nitrate nonahydrate (Fe (NO)3)3·9H2O) is dissolved in 42.5g of distilled water to prepare a solution, and the solution is slowly dripped into 50g of AlPO by an equal-volume immersion method4Standing in-5 molecular sieve with air for 3 hr, drying at 110 deg.C for 12 hr, and calcining at 500 deg.C for 3 hr. Elemental analysis showed Fe/AlPO4Fe in (5), (5)2O3The mass percentage of (B) is 4.8 wt%.
Mo-Fe/AlPO4-5(5) preparation: 3.0g of ammonium molybdate tetrahydrate (H)32Mo7N6O28) Dissolving in 21g distilled water to obtain solution, and slowly adding dropwise 25g Fe/AlPO by equal volume immersion method4-5(5), standing for 4h in air, drying at 100 ℃ for 12h, and roasting at 500 ℃ for 4h to obtain MoO in the product3The mass percentage of the component (A) is 9.8 wt%.
Dissolving 32.2g of ferric chloride and 5.22g of zinc chloride in 250mL of deionized water to obtain an aqueous solution of the ferric chloride and the zinc chloride; slowly adding 62g of ammonia water solution into the aqueous solution of ferric chloride and zinc chloride while stirring; stirring and reacting for 4 hours in a water bath at the temperature of 80 ℃, then cooling to 60 ℃, standing and aging for 24 hours to obtain a precipitate; filtering the precipitate while the precipitate is hot, washing the precipitate with deionized water until the pH value is about 9, drying the precipitate in a drying oven at 120 ℃, heating the dried precipitate at the speed of 5 ℃/min, and roasting the dried precipitate for 2 hours at 500 ℃ in the air atmosphere to obtain iron-zinc oxide powder; wherein the metal molar ratio of Fe to Zn in the resulting oxide is 5.4: 1.
9.8g of oxide powder of iron-based hydrogenation catalyst, 8.2g of alumina, 1.8g of Mo-Fe/AlPO45, (5) mixing and stirring uniformly, adding into a tablet press, pressing and forming, and marking as catalyst CAT-5; iron oxide (Fe) in the catalyst CAT-52O3) And the weight content of zinc oxide (ZnO) was 49.9 wt%.
Comparative example 1
The present comparative example provides a hydrogenation catalyst, the method of preparation comprising the steps of:
with Fe/AlPO prepared as in example 24-5(2) AlPO as modification4-type 5 molecular sieves.
Preparing a catalyst carrier: pseudo-boehmite 63.5g (in terms of weight percent of alumina content considering loss on ignition) and 12.1g Fe/AlPO45(2) mechanically mixing, extruding and forming to obtain the catalyst carrier, wherein the mass ratio of the molecular sieve to the alumina is 11.9: 50.
Preparing an iron-based hydrogenation catalyst: mixing 38.8g ferric nitrate nonahydrate (Fe (NO)3)3·9H2O) and 3.60g of zinc nitrate hexahydrate (Zn (NO)3)2·6H2O) dissolving in a proper amount of deionized water to prepare a co-impregnation solution, slowly pouring the co-impregnation solution into 30g of the prepared catalyst carrier, continuously stirring to realize equal-volume impregnation, standing for 5 hours in air, drying for 6 hours at 100 ℃, and roasting for 5 hours at 500 ℃ to obtain the hydrogenation catalyst, which is marked as catalyst CAT-R1; iron oxide (Fe) in the catalyst CAT-R12O3) And zinc oxide (ZnO) in an amount of 22.5 wt%, with a metal molar ratio of Fe to Zn of 8.1: 1.
Comparative example 2
The present comparative example provides a hydrogenation catalyst, the method of preparation comprising the steps of:
with Mo/AlPO4-5 AlPO as modification4-type 5 molecular sieves.
Mo/AlPO4-5 preparation: 2.76g of ammonium molybdate tetrahydrate (H)32Mo7N6O28) Dissolving in 21g distilled water to obtain solution, and slowly adding dropwise 25g AlPO by equivalent volume immersion method4Standing in air for 4h in-5, drying at 100 deg.C for 12h, and calcining at 500 deg.C for 4h to obtain MoO3The mass percentage of the component (B) is 8.8 wt%.
Preparing a catalyst carrier: pseudo-boehmite 63.5g (in terms of weight percent of alumina content in consideration of loss on ignition) and 10.3gMo/AlPO4And 5, mechanically mixing, extruding and molding to obtain the catalyst carrier, wherein the mass ratio of the molecular sieve to the alumina is 9.9: 50.
Preparing an iron-based hydrogenation catalyst: 22.9g of ferric nitrate nonahydrate (Fe (NO)3)3·9H2O) and 3.10g of zinc nitrate hexahydrate (Zn (NO)3)2·6H2O) dissolving in a proper amount of deionized water to prepare a co-impregnation solution, slowly pouring the co-impregnation solution into 30g of the prepared catalyst carrier, continuously stirring to realize equal-volume impregnation, standing in air for 6h, drying at 110 ℃ for 6h, and roasting at 520 ℃ for 5h to obtain the hydrogenation catalyst, which is marked as catalyst CAT-R2; iron oxide (Fe) in the catalyst CAT-R22O3) And the weight content of zinc oxide (ZnO) was 17.4 wt%, and the metal molar ratio of Fe to Zn was 5.0: 1.
Comparative example 3
The present comparative example provides a hydrogenation catalyst, the method of preparation comprising the steps of:
preparing a catalyst carrier: pseudo-boehmite 63.5g (in terms of weight percent of alumina content in consideration of loss on ignition) and 5g of AlPO were mixed4And 5, mechanically mixing, extruding and molding to obtain the catalyst carrier, wherein the mass ratio of the molecular sieve to the alumina is 5.2: 50.
Preparing an iron-based hydrogenation catalyst: 18.7g of ferric nitrate nonahydrate (Fe (NO)3)3·9H2O) and 6.3g of zinc nitrate hexahydrate (Zn (NO)3)2·6H2O) dissolving in a proper amount of deionized water to prepare a co-impregnation solution, slowly pouring the co-impregnation solution into 30g of the prepared catalyst carrier, continuously stirring to realize equal-volume impregnation, standing in air for 4 hours, drying at 110 ℃ for 9 hours, and roasting at 480 ℃ for 4 hours to obtain the hydrogenation catalyst, which is marked as catalyst CAT-R3; iron oxide (Fe) in the catalyst CAT-R32O3) And zinc oxide (ZnO) 15.2 wt%, with a metal molar ratio of Fe to Zn of 2.2: 1.
Comparative example 4
The present comparative example provides a hydrogenation catalyst, the method of preparation comprising the steps of:
Mo-Fe/AlPO4-5(4) is modified AlPO4-5 molecular sieves
Preparing a catalyst carrier: 68.5g of pseudoboehmite (in consideration of loss on ignition, in terms of alumina content of 7)8.1 wt.%) with 9gMo-Fe/AlPO45(4) mechanically mixing, extruding and forming to obtain the catalyst carrier, wherein the mass ratio of the molecular sieve to the alumina is 8.8: 50.
Preparing an iron-based hydrogenation catalyst: 15g of iron nitrate nonahydrate (Fe (NO)3)3·9H2O) and 7.5g of zinc nitrate hexahydrate (Zn (NO)3)2·6H2O) dissolving in a proper amount of deionized water to prepare a co-impregnation solution, slowly pouring the co-impregnation solution into 30g of the prepared catalyst carrier, continuously stirring to realize equal-volume impregnation, standing in air for 6h, drying at 110 ℃ for 6h, and roasting at 520 ℃ for 5h to obtain the hydrogenation catalyst, which is marked as catalyst CAT-R4; iron oxide (Fe) in the catalyst CAT-R42O3) And zinc oxide (ZnO) in an amount of 14.3 wt%, with a metal molar ratio of Fe to Zn of 1.4: 1.
Comparative example 5
The present comparative example provides a hydrogenation catalyst, the method of preparation comprising the steps of:
with Mo-Fe/AlPO of example 54-5(5) is modified AlPO4-5 molecular sieves.
Dissolving 34.2g of ferric chloride and 5.92g of zinc chloride in 250mL of deionized water to obtain an aqueous solution of the ferric chloride and the zinc chloride; slowly adding 62g of ammonia water solution into the aqueous solution of ferric chloride and zinc chloride while stirring; stirring and reacting for 5 hours in a water bath at the temperature of 80 ℃, then cooling to 60 ℃, standing and aging for 24 hours to obtain a precipitate; filtering the precipitate while the precipitate is hot, washing the precipitate with deionized water until the pH value is about 9, drying the precipitate in a drying oven at 110 ℃, heating the dried precipitate at the speed of 5 ℃/min, and roasting the dried precipitate for 2 hours at 500 ℃ in the air atmosphere to obtain iron-zinc oxide powder; wherein the metal molar ratio of Fe to Zn in the obtained oxide is 4.9: 1.
Roasting 12.2g of oxide powder of iron-based hydrogenation catalyst at 550 ℃ for 4 hours to obtain 8.2g of pseudo-boehmite, 1.8gMo-Fe/AlPO45, (5) mixing and stirring uniformly, adding into a tablet press, pressing and forming, and marking as catalyst CAT-5; iron oxide (Fe) in the catalyst CAT-R52O3) And the weight content of zinc oxide (ZnO) was 54.6 wt%.
Comparative example 6
Preparing a catalyst carrier: 63.5g of pseudo-boehmite (considering loss on ignition, calculated by alumina content of 78.1 wt%) and 10.3g of USY are mechanically mixed and extruded to form a catalyst carrier, and the weight ratio of the molecular sieve to the alumina is 9.9: 50.
Preparing an iron-based hydrogenation catalyst: 22.9g of ferric nitrate nonahydrate (Fe (NO)3)3·9H2O) and 3.10g of zinc nitrate hexahydrate (Zn (NO)3)2·6H2O) dissolving in a proper amount of deionized water to prepare a co-impregnation solution, slowly pouring the co-impregnation solution into 30g of the prepared catalyst carrier, continuously stirring to realize equal-volume impregnation, standing in air for 6h, drying at 110 ℃ for 6h, and roasting at 520 ℃ for 5h to obtain the hydrogenation catalyst, which is marked as catalyst CAT-R6; iron oxide (Fe) in the catalyst CAT-R62O3) And zinc oxide (ZnO) 15.6 wt%, with a metal molar ratio of Fe to Zn of 5.0: 1.
Comparative example 7
An iron-based hydrogenation catalyst, the preparation method comprises the following steps:
preparing a catalyst carrier: 63.5g of pseudo-boehmite (in consideration of loss on ignition, in terms of alumina content of 78.1 wt%) was subjected to extrusion molding to obtain a catalyst carrier.
Preparing an iron-based hydrogenation catalyst: 18.7g of ferric nitrate nonahydrate (Fe (NO)3)3·9H2O) and 6.3g of zinc nitrate hexahydrate (Zn (NO)3)2·6H2O) dissolving in a proper amount of deionized water to prepare a co-impregnation solution, slowly pouring the co-impregnation solution into 30g of the prepared catalyst carrier, continuously stirring to realize equal-volume impregnation, standing in air for 4 hours, drying at 110 ℃ for 9 hours, and roasting at 480 ℃ for 4 hours to obtain the hydrogenation catalyst, which is marked as catalyst CAT-R7; iron oxide (Fe) in the catalyst CAT-R72O3) And zinc oxide (ZnO) 15.2 wt%, with a metal molar ratio of Fe to Zn of 2.2: 1.
Comparative example 8
Preparing a catalyst carrier: 63.5g of pseudoboehmite (considering loss on ignition, and taking the content of alumina as 78.1 w)t% basis) with 12.1g AlPO4And 5, mechanically mixing, extruding and molding to obtain the catalyst carrier, wherein the mass ratio of the molecular sieve to the alumina is 11.9: 50.
Preparing an iron-based hydrogenation catalyst: mixing 38.8g ferric nitrate nonahydrate (Fe (NO)3)3·9H2O), 3.60g zinc nitrate hexahydrate (Zn (NO)3)2·6H2O) and 0.42g of ammonium molybdate tetrahydrate (H)32Mo7N6O28) Dissolving in a proper amount of deionized water to prepare a co-impregnation solution, slowly pouring the co-impregnation solution into 30g of the prepared catalyst carrier, continuously stirring to realize equal-volume impregnation, standing in air for 5 hours, drying at 100 ℃ for 6 hours, and roasting at 500 ℃ for 5 hours to obtain the hydrogenation catalyst, which is marked as catalyst CAT-R8; iron oxide (Fe) in the catalyst CAT-R82O3) And zinc oxide (ZnO) 22.5 wt%, a metal molar ratio of Fe to Zn 8.1:1, MoO3The content of (B) is 0.87 wt%.
Test example 1
The iron-based hydrogenation catalysts of examples 1-5 and comparative examples 1-8 were evaluated for hydrogenation performance. The hydrotreatment of the test example is carried out by adopting a 50mL high-temperature high-pressure hydrogenation micro-reaction device, the evaluation raw material adopts sand medium-pressure and normal-pressure residual oil, and the density (20 ℃) is 0.987g/cm33.8 wt% of sulfur and 0.34 wt% of total nitrogen. Before application, the catalyst is sulfurized to make it have hydrogenation activity. The sulfurized oil is a mixture containing 5 wt% of CS2The sulfuration temperature is 360 ℃, the time is 10h, the pressure is 4MPa, and the liquid hourly space velocity is 1.5h-1The volume ratio of hydrogen to oil was 300. The hydrogenation reaction raw material is pumped by a plunger pump, and the oil sample after reaction is cooled by a high separator and then is collected and analyzed by a low separator. The temperature of the hydrotreatment is 390 ℃, the pressure is 10MPa, and the liquid hourly space velocity is 1h-1The volume ratio of hydrogen to oil was 800. The evaluation results of the catalysts after hydrotreating of the example catalysts and the comparative catalysts are shown in tables 1 and 2.
Table 1 evaluation results of catalysts in examples
| CAT-1 | CAT-2 | CAT-3 | CAT-4 | CAT-5 | |
| Desulfurization rate% | 48.5 | 48.7 | 47.8 | 49.8 | 51.4 |
| Denitrification rate% | 31.7 | 31.3 | 31.6 | 32.0 | 30.9 |
Table 2 evaluation results of comparative example catalysts
| CAT-R1 | CAT-R2 | CAT-R3 | CAT-R4 | CAT-R5 | |
| Desulfurization rate% | 46.1 | 45.3 | 43.8 | 41.8 | 42.4 |
| Denitrification rate% | 29.2 | 29.3 | 28.5 | 28 | 28.9 |
| CAT-R6 | CAT-R7 | CAT-R8 | |||
| Desulfurization rate% | 42.7 | 39.2 | 46.3 | ||
| Denitrification rate% | 26.7 | 24.3 | 29.7 |
Test example 2
The iron-based hydrogenation catalysts of examples 1-5 and comparative examples 1-5 were evaluated for hydrogenation performance. The hydrotreatment of the test example is carried out by adopting a 10mL high-temperature high-pressure hydrogenation micro-reaction device, the evaluation raw material adopts Daqing catalytic cracking diesel oil, and the specific gravity of the catalytic cracking diesel oil
0.8796, sulfur content 890ppm, total nitrogen content 920ppm, total aromatics content 55.2 v%. The raw materials are pumped by a plunger pump, and the reacted oil sample is cooled by a high separator and then collected and analyzed by a low separator. The temperature of the hydrotreatment is 380 ℃, the pressure is 6MPa, and the liquid hourly space velocity is 1.0h-1The volume ratio of hydrogen to oil was 800. The results of evaluation of the catalyst after hydrotreatment are shown in tables 3 and 4.
Table 3 evaluation results of catalysts in examples
| CAT-1 | CAT-2 | CAT-3 | CAT-4 | CAT-5 | |
| Desulfurization rate% | 78.2 | 76.3 | 77.5 | 82.4 | 80.6 |
| Denitrification rate% | 57.6 | 56.8 | 58.2 | 57.3 | 56.9 |
| Dearomatization ratio of% | 41.4 | 42.6 | 41.2 | 42.0 | 41.9 |
Table 4 evaluation results of comparative example catalysts
| CAT-R1 | CAT-R2 | CAT-R3 | CAT-R4 | CAT-R5 | |
| Desulfurization rate% | 63.2 | 66.1 | 70.4 | 71.6 | 62.7 |
| Denitrification rate% | 50.1 | 51.8 | 49.0 | 52.9 | 54.1 |
| Dearomatization ratio of% | 38.0 | 37.8 | 38.2 | 35.9 | 38.2 |
| CAT-R6 | CAT-R7 | CAT-R8 | |||
| Desulfurization rate% | 70.8 | 59.4 | 72.3 | ||
| Denitrification rate% | 53.1 | 43.7 | 54.7 | ||
| Dearomatization ratio of% | 38.8 | 31.4 | 39.0 |
As can be seen from the evaluation results of tables 1 to 4, the iron-based hydrogenation catalysts of the examples have high catalytic hydrogenation activity as compared with the iron-based hydrogenation catalyst of the comparative example. The iron-based hydrogenation catalyst of the embodiment of the invention breaks through the limitation of active component metals of the traditional hydrogenation catalyst for decades, and has important theoretical research value and industrial application value.
Claims (30)
1. An iron-based hydrogenation catalyst, wherein the catalyst comprises a support and a supported oxide of an active metal, the support comprising alumina and AlPO modified with iron and molybdenum4-5 molecular sieves, the active metals comprising a primary active metal and a co-active metal, the primary active metal being Fe and the co-active metal being Zn; the AlPO modified with iron and molybdenum4-5 mass ratio of molecular sieve to alumina (5-12): 50, the molar ratio of Fe element and Zn element as active metals is (2-10): 1, taking the total weight of the catalyst as 100 percent, and taking the total weight of the oxide of the active metal as 15 to 50 percent; the AlPO modified with iron and molybdenum4The preparation method of the molecular sieve comprises the following steps:
(a) isovolumetric impregnation of AlPO with iron hydrosoluble salt solution4-5 molecular sieve, then drying and roasting to obtain Fe/AlPO4-5 molecular sieve, the roasting temperature is 450-4-5 molecular sieve weight 100%, iron element is Fe2O30.5-5%;
(b) isovolumetrically impregnating Fe/AlPO obtained in step (a) with a molybdenum metal water-soluble salt solution4-5 molecular sieve, then drying and roasting to obtain Mo-Fe/AlPO4-5 molecular sieves, in Mo-Fe/AlPO4-5 MoO, based on 100% of the total weight of the molecular sieve33 to 10 percent.
2. The iron-based hydrogenation catalyst of claim 1, wherein the water-soluble salt of metallic molybdenum is ammonium molybdate tetrahydrate.
3. The iron-based hydrogenation catalyst of claim 1, wherein the AlPO modified with iron and molybdenum4-5 mass ratio of molecular sieve to alumina (8-10): 50; the molar ratio of Fe element and Zn element as active metals is (6-10): 1.
4. the iron-based hydrogenation catalyst of claim 1, wherein the calcination temperature in step (b) is 450-550 ℃.
5. The iron-based hydrogenation catalyst of claim 1, wherein the drying temperature of step (b) is 90-120 ℃.
6. The iron-based hydrogenation catalyst of claim 1, wherein the drying temperature of step (a) is 90-120 ℃.
7. The iron-based hydrogenation catalyst of claim 1, wherein the water-soluble salt of iron of step (a) is iron nitrate nonahydrate.
8. The iron-based hydrogenation catalyst of claim 1, wherein the iron element in step (a) is Fe2O3Calculated as 2-4%.
9. The iron-based hydrogenation catalyst of claim 1, wherein MoO in step (b)3Is 3-8%.
10. The iron-based hydrogenation catalyst of any one of claims 1-9, wherein the preparation method of the iron-based hydrogenation catalyst comprises the following steps:
preparing co-impregnation solution of main active metal and auxiliary active metal, then loading the main active metal and the auxiliary active metal on a carrier by an isometric impregnation method, and roasting to obtain the iron-based hydrogenation catalyst;
or uniformly mixing the main active metal oxide powder and the auxiliary active metal oxide powder with a carrier to obtain the iron-based hydrogenation catalyst.
11. The iron-based hydrogenation catalyst of claim 10, wherein the calcination temperature is 450-550 ℃.
12. The iron-based hydrogenation catalyst of claim 10, wherein the calcination time is 2-12 hours.
13. The iron-based hydrogenation catalyst of claim 10, wherein the step of loading the primary active metal and the secondary active metal on the support comprises: preparing co-impregnation solution of main active metal and auxiliary active metal, then loading the main active metal and the auxiliary active metal on a carrier by an equal-volume impregnation method, drying the carrier loaded with the main active metal and the auxiliary active metal, and then roasting to obtain the iron-based hydrogenation catalyst.
14. The iron-based hydrogenation catalyst of claim 13, wherein the step of formulating a co-impregnation solution of the primary active metal and the secondary active metal comprises: and dissolving the water-soluble salt of the main active metal and the water-soluble salt of the auxiliary active metal in water to obtain the co-impregnation solution.
15. The iron-based hydrogenation catalyst of claim 13, wherein the support loaded with the primary active metal and the co-active metal is dried at a drying temperature of 90-120 ℃; the drying time is 4-12 h.
16. The iron-based hydrogenation catalyst of claim 13, wherein, after impregnating the support with the primary active metal and the co-active metal, the method further comprises the step of allowing the support impregnated with the primary active metal and the co-active metal to stand, and then drying and calcining the support; standing for 4-24 h.
17. The iron-based hydrogenation catalyst of claim 10, wherein the step of uniformly mixing the primary and secondary active metal oxide powders with the support comprises: the water soluble salt of the main active metal and the water soluble salt of the auxiliary active metal are uniformly mixed in water to obtain a mixed solution, the mixed solution reacts under an alkaline condition to obtain a hydroxide precipitation mixture of the main active metal and the auxiliary active metal, then the hydroxide precipitation mixture is roasted at the temperature of 450-550 ℃ to obtain an oxide mixture of the main active metal and the auxiliary active metal, and then the oxide mixture and the carrier are uniformly mixed.
18. The iron-based hydrogenation catalyst of claim 14 or 17, wherein the water-soluble salt of the primary active metal is a mixture of one or more of ferric nitrate nonahydrate, ferric chloride, and ferric sulfate.
19. The iron-based hydrogenation catalyst of claim 14 or 17, wherein the water-soluble salt of a co-active metal is a mixture of one or more of zinc nitrate hexahydrate, zinc chloride, and zinc sulfate.
20. The iron-based hydrogenation catalyst of claim 17, wherein the pH of the mixed solution under alkaline conditions is 10 or greater.
21. The iron-based hydrogenation catalyst of claim 17, wherein the calcination time is 2-12 hours.
22. The iron-based hydrogenation catalyst of claim 17, wherein the step of uniformly mixing the primary and secondary active metal oxide powders with the support comprises: dissolving water soluble salt of main active metal and water soluble salt of auxiliary active metal in water, adding alkali to react to obtain precipitate, filtering after complete reaction, roasting the precipitate to obtain iron-zinc oxide powder, and mixing the iron-zinc oxide powder and the carrier uniformly.
23. The iron-based hydrogenation catalyst of claim 22, wherein the base is ammonia or urea.
24. The iron-based hydrogenation catalyst of claim 22, wherein the reaction temperature of the reaction is 75-95 ℃.
25. The iron-based hydrogenation catalyst of claim 22, wherein the reaction time of the reaction is 4-8 hours.
26. The iron-based hydrogenation catalyst of claim 22, wherein the iron-based hydrogenation catalyst is further aged to precipitate after the reaction is completed.
27. The iron-based hydrogenation catalyst of claim 26, wherein the aging is resting for 20-30 hours at 50-80 ℃.
28. The iron-based hydrogenation catalyst of claim 10, further comprising impregnating alumina and AlPO modified with iron and molybdenum prior to impregnating the support with equal volumes of co-impregnation solutions of the formulated primary and secondary active metals4-5 a step of mixing the molecular sieves.
29. The iron-based hydrogenation catalyst of claim 28, wherein alumina and AlPO modified with iron and molybdenum are mixed45 after the molecular sieve is mixed, the step of extruding the mixture into strips is also included.
30. A method of making the iron-based hydrogenation catalyst of any one of claims 1-29, the method comprising the pairing of AlPO with iron and molybdenum4-5 a step of modifying the molecular sieve, said step comprising:
(a) introduction of iron element into AlPO4-5 molecular sieves to obtain Fe/AlPO4-5 molecular sieves;
(b) isovolumetrically impregnating Fe/AlPO obtained in step (a) with a molybdenum metal water-soluble salt solution4-5 molecular sieve, then drying and roasting to obtain Mo-Fe/AlPO4-5 molecular sieves.
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