CN110013874B - Catalyst for preparing hydrocarbon fuel by hydrodeoxygenation of animal and vegetable oil and preparation method thereof - Google Patents

Catalyst for preparing hydrocarbon fuel by hydrodeoxygenation of animal and vegetable oil and preparation method thereof Download PDF

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CN110013874B
CN110013874B CN201910209966.9A CN201910209966A CN110013874B CN 110013874 B CN110013874 B CN 110013874B CN 201910209966 A CN201910209966 A CN 201910209966A CN 110013874 B CN110013874 B CN 110013874B
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catalyst
metal element
perovskite
solution
active component
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CN110013874A (en
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高群仰
刘营
胡胜
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Beijing Haixin Energy Technology Co.,Ltd.
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Beijing SJ Environmental Protection and New Material Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7876—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7892—MTT-type, e.g. ZSM-23, KZ-1, ISI-4 or EU-13
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates (SAPO compounds)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
    • C11C3/126—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation using catalysts based principally on other metals or derivates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Abstract

The invention relates to the field of catalysts, in particular to a catalyst for preparing hydrocarbon fuel by hydrodeoxygenation of animal and vegetable oil, which comprises the following components: the active component comprises at least one metal element in VIB group and at least one metal element in VIII group; perovskite of the formula A1‑xA'xB1‑yB'yO3In the formula, A is a rare earth metal element, A 'is an alkaline earth metal element, B and B' are transition metal elements, x is more than or equal to 0.1 and less than or equal to 0.9, and y is more than or equal to 0.1 and less than or equal to 0.9; acidic carrier comprising gamma-Al2O3Or at least one of amorphous silicon and aluminum and the molecular sieve have proper acidity, proper pore channel structure and hydrothermal aging resistance, and can complete the hydrodeoxygenation and hydroisomerization reactions of raw materials such as animal and vegetable oil and the like in one reactor in one step, thereby obtaining isoparaffin with low condensation point, reducing operation procedures and energy consumption.

Description

Catalyst for preparing hydrocarbon fuel by hydrodeoxygenation of animal and vegetable oil and preparation method thereof
Technical Field
The invention relates to the field of catalysts, in particular to a catalyst for preparing hydrocarbon fuel by hydrodeoxygenation of animal and vegetable oil and a preparation method thereof.
Background
At present, the main sources of energy in the world and fossil energy are the non-renewable energy, but the fossil energy is limited in resource amount, so with the continuous development of the world economy and the increasing pressure of carbon dioxide emission reduction, the market demand for renewable green energy emitted by low-temperature room gas is also increasing.
Currently, various countries in the world, especially industrially developed countries, are actively engaged in developing various new alternative petroleum energy sources such as coal-based oil and bio-oil to alleviate the oil shortage, however, the primary products of these new alternative energy sources also have inherent defects, such as low combustion heat, poor stability and corrosiveness. All these drawbacks are related to their excessive oxygen content, some biooils even up to 50 wt%. In order to solve this problem, it is necessary to further subject the catalyst to hydrodeoxygenation purification treatment, and therefore, the catalytic hydrodeoxygenation process becomes one of the key technologies for developing this new energy.
In recent years, many research institutes have studied the hydrodeoxygenation of grease, and high-quality diesel fuel with high cetane number and low condensation point is obtained. The catalyst used for hydrodeoxygenation of the grease at present is usually NiMo/gamma-Al subjected to vulcanization2O3、CoMo/γ-Al2O3The catalyst is mainly used for generating long-chain normal paraffin after the raw materials are subjected to hydrogenation and deoxidation reactions, and the product needs to be isomerized to improve the low-temperature performance of the product, wherein the catalyst used in the paraffin isomerization process is generally a noble metal or transition metal loaded molecular sieve, a ZSM molecular sieve or an SAPO molecular sieve. Therefore, the current process for producing high quality hydrocarbon fuels is mainly realized by means of a two-step process.
In the two-step process, the first step is that the oil is subjected to carbon-carbon double bond hydrogenation saturation and hydrogenation deoxidation to produce n-alkane, water and other byproducts; the second step is the normal paraffin hydrogenation isomerization reaction to produce isoparaffin. In the two-step method, the processes of oil hydrogenation, deoxidation and alkane isomerization need to be respectively carried out on different reactors and different catalysts, the whole process needs a plurality of reactors and a plurality of steps of operation procedures, the process is complex, the hydrogen consumption and the energy consumption are high, and the investment on production equipment is large.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects that the preparation of hydrocarbon fuel by grease hydrodeoxygenation in the prior art needs a two-step method, the whole process needs a plurality of reactors and a plurality of operation procedures, the process is complex, the hydrogen consumption and the energy consumption are high, and the investment on production equipment is large, so that the catalyst for preparing the hydrocarbon fuel by animal and vegetable grease hydrodeoxygenation and the preparation method are provided.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a catalyst for preparing hydrocarbon fuel by hydrodeoxygenation of animal and vegetable oil comprises the following components:
the active component comprises at least one metal element in VIB group and at least one metal element in VIII group;
perovskite of the formula A1-xA'xB1-yB'yO3In the formula, A is a rare earth metal element, A 'is an alkaline earth metal element, B and B' are transition metal elements, x is more than or equal to 0.1 and less than or equal to 0.9, and y is more than or equal to 0.1 and less than or equal to 0.9;
acidic carrier comprising gamma-Al2O3Or at least one of amorphous silicon aluminum and a molecular sieve.
Furthermore, the VIB group elements are Mo and/or W, and the VIII group metal elements are Co and/or Ni.
Further, the active component accounts for 5-25 wt% (calculated by oxide) in the catalyst.
Further, the rare earth metal element is La, the alkaline earth metal element is Ca or Sr, and the transition metal element is Fe and Mn, or Cu and Mn.
Further, the perovskite is 15-50 wt% in the catalyst.
Further, the acidic carrier also comprises amorphous silicon-aluminum.
Further, the molecular sieve is at least one of ZSM-5, ZSM-22, ZSM-23, SAPO-11, SAPO-31 and SAPO-41.
Further, the acidic carrier accounts for 45-65 wt% of the catalyst.
The invention also adopts the following technical scheme: a method for preparing a catalyst according to any of the above embodiments, comprising the steps of: the active component is loaded on a composite carrier prepared from perovskite and an acidic carrier.
Further, the preparation of the composite carrier specifically comprises the following steps:
and adding a binder into the perovskite and the acidic carrier to prepare a mixture, then adding a peptizing agent and water into the mixture, kneading and molding after mixing, and drying and roasting the molded product to obtain the composite carrier.
Furthermore, the adhesive comprises an organic adhesive and an inorganic adhesive, wherein the organic adhesive is at least one of sesbania gum, guar gum, carboxymethyl cellulose, gum and pectin, and the inorganic adhesive is pseudo-boehmite.
Furthermore, the organic binder accounts for 2-10 wt% of the mixture, and the inorganic binder accounts for 2-10 wt% of the mixture.
Further, the peptizing agent is at least one of acetic acid, oxalic acid and nitric acid.
Further, the drying temperature of the molding is 100-150 ℃, and the drying time is 4-24 h; the roasting temperature is 500-650 ℃, and the roasting time is 3-6 h.
Further, the loading step specifically includes the following operations: and preparing soluble salt of the active component into aqueous solution, adding the aqueous solution into the composite carrier for impregnation to obtain an impregnation material, and finally drying and roasting the impregnation material to obtain the catalyst loaded with the active component.
Further, the drying temperature of the impregnating material is 60-150 ℃, the drying time is 3-24h, the roasting temperature is 500-650 ℃, and the roasting time is 3-6 h.
The technical scheme of the invention has the following advantages:
1. the catalyst for preparing the hydrocarbon fuel by the animal and vegetable oil hydrodeoxygenation comprises an active component, perovskite and an acid carrier, wherein the VIB group metal element and the VIII group metal have excellent catalytic activity of hydrodeoxygenation, and the active component can play a role in hydrodeoxygenation and carbon-carbon double bond hydrogenation saturation during preparation of the hydrocarbon fuel; the alumina in the acidic carrier has the advantages of high mechanical strength and large specific surface area, can play a main mechanical supporting role, and can improve the specific surface area of the catalyst, disperse active components and improve the mechanical strength of the catalyst by adding the alumina; amorphous silicon-aluminum is a porous substance and also has a large specific surface area, and the specific surface area of the catalyst can be increased by adding the amorphous silicon-aluminum into the acidic carrier, so that the catalytic activity of the catalyst is improved; the molecular sieve has a special pore channel structure and acid catalytic activity, and can isomerize normal paraffin so as to reduce the condensation point of a product, and the acidity and the pore channel structure of the carrier can be changed by compounding the molecular sieve carrier and an alumina carrier or an amorphous silicon-aluminum carrier to form an acidic carrier, so that the hydrodeoxygenation of animal and vegetable oil and the isomerization of paraffin can be carried out in one-step reaction; the perovskite has good oxygen storage and discharge capacity and good hydrothermal stability, is commonly used as an organic matter catalytic combustion catalyst, and can improve the hydrothermal aging resistance of the catalyst by introducing the rare earth metal and alkaline earth metal modified perovskite into the acidic carrier, thereby further improving the hydrodeoxygenation activity of the catalyst; in addition, perovskite has the defects of small specific surface area and low mechanical strength, and the perovskite and alumina are combined for use, so that the specific surface area and mechanical strength of the catalyst can be improved, the anti-sulfidation reaction of the sulfided catalyst can be reduced, and the hydrodeoxygenation activity of the catalyst can be further improved. The catalyst provided by the invention has proper acidity, a proper pore channel structure and hydrothermal aging resistance, can complete hydrodeoxygenation and hydroisomerization of raw materials such as animal and vegetable oil and the like in one reactor in one step, thereby obtaining isoparaffin with low condensation point, reducing operation procedures and energy consumption, and simultaneously has high hydrodeoxygenation, hydrodecarbonylation selectivity and hydroisomerization activity.
2. According to the catalyst provided by the invention, the VIB group metal element is at least one of Mo and W, and the VIII group metal element is at least one of Co and Ni, so that on one hand, Mo, W, Co and Ni have better catalytic activity of hydrodeoxygenation and can improve the catalytic activity of the finally prepared catalyst, and on the other hand, Mo, W, Co and Ni are common active components of the catalyst, so that the source is wide, the raw material cost is low, and the production cost of the catalyst can be reduced.
3. According to the catalyst provided by the invention, the rare earth metal element is La, the alkaline earth metal element is Ca or Sr, the transition metal element is Fe and Mn or Cu and Mn, and the selected metal elements are common elements in the rare earth metal element, the alkaline earth metal element or the transition metal element, so that the source is wide, the catalytic activity of the catalyst is ensured, and meanwhile, the raw material cost can be reduced, so that the production cost of the catalyst is further reduced.
4. According to the preparation method of the catalyst provided by the invention, the perovskite and the acid carrier are prepared into the composite carrier, and then the active component is loaded on the composite carrier, so that the perovskite and the alumina in the acid carrier can be better matched, and the preparation method is simple and easy to realize.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
The invention relates to a catalyst for preparing hydrocarbon fuel by hydrodeoxygenation of animal and vegetable oil, which comprises the following components: an active component comprising at least one metal element from group VIB and at least one metal element from group VIII; perovskite of the formula A1-xA'xB1-yB'yO3In the formula, A is a rare earth metal element, A 'is an alkaline earth metal element, B and B' are transition metal elements, x is more than or equal to 0.1 and less than or equal to 0.9, and y is more than or equal to 0.1 and less than or equal to 0.9; and, an acidic carrier comprising gamma-Al2O3Or at least one of amorphous silicon aluminum and a molecular sieve.
Wherein, the active component accounts for 5-25 wt% of the catalyst (calculated by oxide), the perovskite accounts for 15-50 wt% of the catalyst, the acidic carrier accounts for 15-50 wt% of the catalyst, and the total amount of the three is not more than 100%.
The active component mainly plays a role in hydrodeoxygenation and carbon-carbon double bond hydrogenation saturation, the alumina has the advantages of high mechanical strength and large specific surface area and plays a role in main mechanical support and active component dispersion, the amorphous silicon-aluminum is a porous substance and has a large specific surface area, and the specific surface area of the catalyst can be increased by adding the amorphous silicon-aluminum into the acidic carrier, so that the catalytic activity of the catalyst is improved; the molecular sieve can isomerize normal paraffin, the condensation point of the product is reduced, the perovskite can prevent the anti-sulfurization of the sulfurization catalyst, the hydrodeoxygenation activity and the hydrothermal aging resistance of the catalyst are improved, and the active components, the alumina, the molecular sieve and the perovskite are compounded to prepare the catalyst, so that the hydrodeoxygenation of animal and vegetable oil and the isomerization of the paraffin can be carried out in one reactor, the operation procedures are reduced, and the energy consumption is reduced.
Because the chemical properties of the same group of elements are relatively similar, in order to ensure the catalytic activity of the catalyst and reduce the preparation cost of the catalyst as much as possible, the VIB group element selects at least one of Mo and W, the VIII group metal element selects at least one of Co and Ni, the rare earth metal element is La, the alkaline earth metal element is Ca or Sr, and the transition metal element is Fe and Mn or Cu and Mn. The molecular sieve in the acidic carrier is at least one of ZSM-5, ZSM-22, ZSM-23, SAPO-11, SAPO-31 and SAPO-41.
The invention also relates to a preparation method of the catalyst for preparing the hydrocarbon fuel by hydrodeoxygenation of the animal and vegetable oil, which comprises the following steps: the active component is loaded on a composite carrier prepared from perovskite and an acidic carrier.
The preparation method of the composite carrier specifically comprises the following steps: and adding a binder into the perovskite and the acidic carrier to prepare a mixture, then adding a peptizing agent and water into the mixture, kneading and molding after mixing, and drying and roasting the molded product to obtain the composite carrier.
The perovskite is prepared by adopting the method which is commercially available or according to the following method: dissolving soluble rare earth metal salt, soluble alkaline earth metal salt and soluble transition metal salt in water to prepare a solution with the concentration of 0.25-2.5mol/L, adding a complexing agent into the solution, finally placing the solution added with the complexing agent into a drying oven, evaporating excessive water to obtain gel, and placing the gel into a muffle furnace for roasting to obtain the perovskite. If the rare earth metal in the perovskite is La, the soluble rare earth metal salt is at least one of lanthanum nitrate and lanthanum acetate, the alkaline earth metal in the perovskite is Ca, the soluble alkaline earth metal salt is at least one of calcium acetate and calcium nitrate, the transition metal in the perovskite is Fe, the soluble transition metal salt is at least one of ferric nitrate and ferric acetate, the transition metal in the perovskite is Mn, the soluble transition metal salt is at least one of manganese nitrate and manganese acetate, the transition metal in the perovskite is Cu, and the soluble transition metal salt is at least one of copper nitrate and copper acetate. The complexing agent is at least one of citric acid and hydroxide, and the molar ratio of the complexing agent to the metal ions in the solution is 0.5-3.0. The drying temperature is 100-150 ℃, the drying time is 4-24h, the roasting temperature is 700-900 ℃, and the roasting time is 1-6 h.
The adhesive comprises an organic adhesive and an inorganic adhesive, wherein the inorganic adhesive can enable the composite carrier to have certain plasticity and certain strength after being heated at high temperature, and the organic adhesive can enable the surface of the composite carrier to be smoother, so that the composite carrier is more suitable for use. The organic adhesive is at least one of sesbania gum, guar gum, carboxymethyl cellulose, gum and pectin, and the inorganic adhesive is pseudo-boehmite. The organic binder accounts for 2-10 wt% of the mixture, and the inorganic binder accounts for 2-10 wt% of the mixture. Among the inorganic adhesives, the pseudo-boehmite is selected as the inorganic adhesive without introducing other substances into the reciprocating carrier because the component remained after the pseudo-boehmite is heated at high temperature is alumina, so the pseudo-boehmite is preferred as the inorganic adhesive.
The peptizing agent is at least one of acetic acid, oxalic acid and nitric acid.
The drying temperature of the formed product is 100-150 ℃, and the drying time is 4-24 h; the roasting temperature is 500-650 ℃, and the roasting time is 3-6h, thus finally obtaining the composite carrier.
The active component can be loaded on the composite carrier by adopting an impregnation method or a precipitation method. In order to simplify the preparation process of the catalyst, in the present invention, the preferred method is an impregnation method, which comprises the following steps: dissolving soluble salt of metal elements selected as an active component in water to prepare a solution with the concentration of 0.25-2.5mol/L, adding the solution into a composite carrier, stirring, fully soaking to obtain a soaking material, placing the soaking material in an oven for drying, and placing the dried soaking material in a muffle furnace for roasting to obtain the catalyst for preparing hydrocarbon fuel by hydrodeoxygenation of animal and vegetable oil. Wherein the drying temperature is 60-150 ℃, the drying time is 3-24h, the roasting temperature is 500-650 ℃, and the roasting time is 3-6 h.
Example 1
1) Preparation of perovskites
Lanthanum nitrate, calcium nitrate, ferric nitrate and manganese nitrate are prepared into a precursor aqueous solution A of a perovskite type active component, wherein the molar ratio of metal ions La: ca: fe: the molar weight ratio of Mn is 9:1:1:9, and the total molar weight concentration of metal ions is 1.0 mol/L; adding a certain amount of citric acid into the solution A, wherein the molar ratio of the citric acid to La, Ca, Fe and Mn is 1.0, stirring, and fully dissolving to obtain a solution B; putting the solution B in an oven to dry for 24 hours at 100 ℃, and evaporating excessive water to obtain gel A; placing the gel A in a muffle furnace to be roasted for 3h at 800 ℃ to obtain the perovskite La0.9Ca0.1Fe0.1Mn0.9O3。
2) Shaping of composite carriers
150gLa0.9Ca0.1Fe0.1Mn0.9O3、100gγ-Al2O350g of ZSM-5, 20g of sesbania powder and 30g of pseudo-boehmite; adding 100g of deionized water and 10g of acetic acid into the dry mixture, fully kneading, and extruding and molding by a strip extruding machine to obtain a molding A; molding A was set at 130 ℃ CDrying for 6h, and roasting at 500 ℃ for 4h to obtain the composite carrier.
3) Loading of active components as per Co: ni: mo: weighing a certain amount of cobalt nitrate, nickel nitrate, ammonium molybdate and ammonium tungstate according to the molar weight ratio of 1:1:1:1, and adding deionized water to prepare an aqueous solution C, wherein the total molar weight concentration of metal ions is 2.0 mol/L; adding a certain amount of calculated solution C into the composite carrier according to the loading capacity of the active components of cobalt, nickel, molybdenum and tungsten oxide of 15% and the mass of the composite carrier of 100g, stirring, and fully soaking to obtain a soaking material A; placing the impregnating material A in an oven to be dried for 5 hours at 140 ℃; and (3) placing the dried impregnating compound A in a muffle furnace to roast for 6h at 500 ℃ to obtain the catalyst with 15.0% of active component loading.
Example 2
1) Preparation of perovskites
Lanthanum nitrate, calcium nitrate, ferric nitrate and manganese nitrate are prepared into a precursor aqueous solution A of a perovskite type active component, wherein the molar ratio of metal ions La: ca: fe: the molar weight ratio of Mn is 5:5:5:5, and the total molar weight concentration of metal ions is 2.0 mol/L; adding a certain amount of citric acid into the solution A, wherein the molar ratio of the citric acid to La, Ca, Fe and Mn is 0.5, stirring, and fully dissolving to obtain a solution B; putting the solution B in an oven to dry for 4h at 120 ℃, and evaporating excessive water to obtain gel A; placing the gel A in a muffle furnace to be roasted for 6h at 700 ℃ to obtain the perovskite La0.5Ca0.5Fe0.5Mn0.5O3。
2) Shaping of composite carriers
Will 100gLa0.5Ca0.5Fe0.5Mn0.5O3100g amorphous silica-alumina, 100g ZSM-22, 10g gum, 15g pseudo-boehmite; adding 90g of deionized water and 5g of oxalic acid into the dry mixture, fully kneading, and extruding and molding by a strip extruder to obtain a molding A; and drying the formed product A at 120 ℃ for 6h, and roasting at 550 ℃ for 5h to obtain the composite carrier.
3) Loading of active ingredients
According to the weight ratio of Co: ni: mo: weighing a certain amount of cobalt nitrate, nickel nitrate, ammonium molybdate and ammonium tungstate according to the molar weight ratio of 1:2:3:4, and adding deionized water to prepare an aqueous solution C, wherein the total molar weight concentration of metal ions is 1.0 mol/L; adding a certain amount of calculated solution C into the composite carrier according to the loading capacity of active components of cobalt, nickel, molybdenum and tungsten oxide of 12.5% and the mass of the composite carrier of 100g, stirring, and fully soaking to obtain a soaking material A; placing the impregnating material A in an oven to be dried for 24 hours at 100 ℃; and (3) placing the dried impregnating compound A in a muffle furnace to roast for 4h at the temperature of 600 ℃ to obtain the catalyst with the active component load of 12.5%.
Example 3
1) Preparation of perovskites
Lanthanum nitrate, calcium nitrate, ferric nitrate and manganese nitrate are prepared into a precursor aqueous solution A of a perovskite type active component, wherein the molar ratio of metal ions La: ca: fe: the molar weight ratio of Mn is 3:7:7:3, and the total molar weight concentration of metal ions is 2.5 mol/L; adding a certain amount of citric acid into the solution A, wherein the molar ratio of the citric acid to La, Ca, Fe and Mn is 3.0, stirring, and fully dissolving to obtain a solution B; putting the solution B in an oven to dry for 8h at 130 ℃, and evaporating excessive water to obtain gel A; placing the gel A in a muffle furnace to be roasted for 1h at 900 ℃ to obtain the perovskite La0.3Ca0.7Fe0.7Mn0.3O3。
2) Shaping of composite carriers
75gLa0.3Ca0.7Fe0.7Mn0.3O3、75gγ-Al2O3150g of ZSM-23 molecular sieve, 30g of pectin and 10g of pseudo-boehmite are fully mixed; adding 80g of deionized water and 6g of nitric acid into the mixture dry material, fully kneading, and extruding into strips by using a strip extruding machine to obtain a formed object A; and drying the formed product A at 100 ℃ for 24h, and roasting at 600 ℃ for 3.5h to obtain the carrier.
3) Loading of active ingredients
According to the weight ratio of Co: ni: mo: weighing a certain amount of cobalt nitrate, nickel nitrate, ammonium molybdate and ammonium tungstate according to the molar weight ratio of W being 3:1:2:4, and adding deionized water to prepare an aqueous solution C, wherein the total molar weight concentration of metal ions is 1.5 mol/L; adding a certain amount of calculated solution C into the composite carrier according to the loading capacity of the active components of cobalt, nickel, molybdenum and tungsten oxide of 20.0% and the mass of the composite carrier of 100g, stirring, and fully soaking to obtain a soaking material A; placing the impregnating material A in an oven to be dried for 3h at the temperature of 150 ℃; and placing the dried impregnating compound A in a muffle furnace for roasting at 650 ℃ for 3h to obtain the catalyst with 20.0% of active component loading.
Example 4
1) Preparation of perovskites
Lanthanum nitrate, calcium nitrate, ferric nitrate and manganese nitrate are prepared into a precursor aqueous solution A of a perovskite type active component, wherein the molar ratio of metal ions La: ca: fe: the molar weight ratio of Mn is 1:9:9:1, and the total molar weight concentration of metal ions is 1.5 mol/L; adding a certain amount of citric acid into the solution A, wherein the molar ratio of the citric acid to La, Ca, Fe and Mn is 2.0, stirring, and fully dissolving to obtain a solution B; putting the solution B in an oven to dry for 20h at 105 ℃, and evaporating excessive water to obtain gel A; placing the gel A in a muffle furnace to roast for 2h at 850 ℃ to obtain the perovskite La0.1Ca0.9Fe0.9Mn0.1O3。
2) Shaping of composite carriers
75gLa0.1Ca0.9Fe0.9Mn0.1O3、50gγ-Al2O3175g of SAPO-11 molecular sieve, 15g of guar gum and 50g of pseudo-boehmite are fully mixed; adding 60g of deionized water and 12g of acetic acid into the dry mixture, fully kneading, and extruding and molding by using a bar extruding machine to obtain a molding A; and drying the formed product A at 150 ℃ for 4h, and roasting at 650 ℃ for 3h to obtain the composite carrier.
3) Loading of active ingredients
According to the weight ratio of Co: ni: mo: weighing a certain amount of cobalt nitrate, nickel nitrate, ammonium molybdate and ammonium tungstate according to the molar weight ratio of 2:3:1:2, and adding deionized water to prepare an aqueous solution C, wherein the total molar weight concentration of metal ions is 2.5 mol/L; adding a certain amount of calculated solution C into the composite carrier according to the loading capacity of active components of cobalt, nickel, molybdenum and tungsten oxide of 10.0% and the mass of the composite carrier of 100g, stirring, and fully soaking to obtain a soaking material A; placing the impregnating material A in an oven to be dried for 12h at 100 ℃; and (3) placing the dried impregnating compound A in a muffle furnace to roast for 4h at 550 ℃ to obtain the catalyst with 10.0% of active component loading.
Example 5
1) Preparation of perovskites
Lanthanum nitrate, calcium nitrate, iron acetate and manganese acetate are prepared into a precursor aqueous solution A of a perovskite type active component, wherein the molar ratio of metal ions La: ca: fe: the molar weight ratio of Mn is 8:2:2:8, and the total molar weight concentration of metal ions is 1.2 mol/L; adding a certain amount of citric acid into the solution A, wherein the molar ratio of the citric acid to La, Ca, Fe and Mn is 0.8, stirring, and fully dissolving to obtain a solution B; putting the solution B in an oven for drying for 6h at 140 ℃, and evaporating excessive water to obtain gel A; placing the gel A in a muffle furnace to be roasted for 5h at 750 ℃ to obtain the perovskite La0.8Ca0.2Fe0.2Mn0.8O3。
2) Shaping of composite carriers
Will 90gLa0.8Ca0.2Fe0.2Mn0.8O3、10gγ-Al2O3200g of SAPO-31 molecular sieve, 20g of carboxymethyl cellulose and 30g of pseudo-boehmite are fully mixed; adding 100g of deionized water and 10g of acetic acid into the dry mixture, fully kneading, and extruding into strips by using a strip extruding machine to obtain a formed object A; and drying the formed product A at 105 ℃ for 20h, roasting at 575 ℃ for 6h, and carrying out grease hydrodeoxygenation on the catalyst A to obtain the composite carrier.
3) Loading of active ingredients
According to the weight ratio of Co: ni: mo: weighing a certain amount of cobalt nitrate, nickel nitrate, ammonium molybdate and ammonium tungstate according to the molar weight ratio of 1:1:1:1, and adding deionized water to prepare an aqueous solution C, wherein the total molar weight concentration of metal ions is 2.5 mol/L; adding a certain amount of calculated solution C into the composite carrier according to the loading capacity of the active components of cobalt, nickel, molybdenum and tungsten oxide of 25% and the mass of the composite carrier of 100g, stirring, and fully soaking to obtain a soaking material A; placing the impregnating material A in an oven to be dried for 15h at 110 ℃; and (3) placing the dried impregnating compound A in a muffle furnace to roast for 3h at the temperature of 575 ℃, thus obtaining the catalyst with 25.0 percent of loading of active components.
Example 6
1) Preparation of perovskites
Lanthanum acetate, calcium acetate, ferric nitrate and manganese nitrate are prepared into a precursor aqueous solution A of a perovskite type active component, wherein the molar ratio of metal ions La: ca: fe: the molar weight ratio of Mn is 4:6:6:4, and the total molar weight concentration of metal ions is 2.0 mol/L; adding a certain amount of citric acid into the solution A, wherein the molar ratio of the citric acid to La, Ca, Fe and Mn is 1.5, stirring, and fully dissolving to obtain a solution B; putting the solution B in an oven to dry for 4h at 150 ℃, and evaporating excessive water to obtain gel A; placing the gel A in a muffle furnace for roasting at 775 ℃ for 4h to obtain the perovskite La0.4Ca0.6Fe0.6Mn0.4O3。
2) Shaping of composite carriers
125gLa0.4Ca0.6Fe0.6Mn0.4O3、75gγ-Al2O3Fully mixing 100g of SAPO-34 molecular sieve, 10g of gum and 15g of pseudo-boehmite; adding 90g of deionized water and 5g of oxalic acid into the dry mixture, fully kneading, and extruding and molding by using a bar extruding machine to obtain a molding A; and drying the formed product A at 140 ℃ for 6h, and roasting at 625 ℃ for 5h to obtain the composite carrier.
3) Loading of active ingredients
According to the weight ratio of Co: ni: mo: weighing a certain amount of cobalt nitrate, nickel nitrate, ammonium molybdate and ammonium tungstate, and adding deionized water to prepare an aqueous solution C, wherein the molar weight ratio of W is 1:2:3:4, and the total molar weight concentration of metal ions is 1.5 mol/L; adding a certain amount of calculated solution C into the composite carrier according to the loading capacity of active components of cobalt, nickel, molybdenum and tungsten oxide of 5.0% and the mass of the composite carrier of 100g, stirring, and fully soaking to obtain a soaking material A; placing the impregnating material A in an oven to be dried for 9h at 120 ℃; and placing the dried impregnating compound A in a muffle furnace for roasting at 625 ℃ for 2.5h to obtain the catalyst with 5.0% of active component load.
Example 7
1) Preparation of perovskites
Lanthanum acetate, calcium acetate, iron acetate and manganese acetate are prepared into a precursor aqueous solution A of a perovskite type active component, wherein gold is contained in the precursor aqueous solution AThe metal ions La: ca: fe: the molar weight ratio of Mn is 7:3:3:7, and the total molar weight concentration of metal ions is 2.5 mol/L; adding a certain amount of citric acid into the solution A, wherein the molar ratio of the citric acid to La, Ca, Fe and Mn is 2.4, stirring, and fully dissolving to obtain a solution B; putting the solution B in an oven, drying for 12h at 115 ℃, and evaporating excessive water to obtain gel A; placing the gel A in a muffle furnace to be roasted for 1h at 900 ℃ to obtain the perovskite La0.7Ca0.3Fe0.3Mn0.7O3。
2) Shaping of composite carriers
140gLa0.7Ca0.3Fe0.3Mn0.7O3、50gγ-Al2O350g of amorphous silicon-aluminum, 60g of ZSM-22 molecular sieve, 30g of pectin and 10g of pseudo-boehmite are fully mixed; adding 80g of deionized water and 6g of nitric acid into the mixture dry material, fully kneading, and extruding into strips by using a strip extruding machine to obtain a formed object A; and drying the formed product A at 115 ℃ for 12h, and roasting at 500 ℃ for 6h to obtain the composite carrier.
3) Loading of active ingredients
According to the weight ratio of Co: ni: mo: weighing a certain amount of cobalt nitrate, nickel nitrate, ammonium molybdate and ammonium tungstate according to the molar weight ratio of W being 3:1:2:4, and adding deionized water to prepare an aqueous solution C, wherein the total molar weight concentration of metal ions is 1.0 mol/L; adding a certain amount of calculated solution C into the composite carrier according to the loading capacity of the active components of cobalt, nickel, molybdenum and tungsten oxide of 18.0% and the mass of the composite carrier of 100g, stirring, and fully soaking to obtain a soaking material A; placing the impregnating material A in an oven to be dried for 4h at the temperature of 150 ℃; and placing the dried impregnating compound A in a muffle furnace for roasting at 650 ℃ for 3h to obtain the catalyst with 18.0% of active component loading.
Example 8
1) Preparation of perovskites
Lanthanum nitrate, calcium acetate, iron acetate and manganese nitrate are prepared into a precursor aqueous solution A of a perovskite type active component, wherein the molar ratio of metal ions La: ca: fe: the molar weight ratio of Mn is 2:8:8:2, and the total molar weight concentration of metal ions is 1.8 mol/L; adding a certain amount of citric acid, and adding a certain amount of citric acid, La, Ca, Fe and M into the solution AThe molar ratio of n metal is 2.8, stirring and fully dissolving to obtain a solution B; putting the solution B in an oven to dry for 12h at 100 ℃, and evaporating excessive water to obtain gel A; placing the gel A in a muffle furnace to roast for 2h at 850 ℃ to obtain the perovskite La0.2Ca0.8Fe0.8Mn0.2O3。
2) Shaping of composite carriers
Will 100gLa0.2Ca0.8Fe0.8Mn0.2O3、80gγ-Al2O330g of amorphous silicon aluminum, 90g of SAPO-31, 25g of guar gum and 50g of pseudo-boehmite are fully mixed; adding 120g of deionized water and 12g of acetic acid into the dry mixture, fully kneading, and extruding and molding by using a bar extruding machine to obtain a molding A; and drying the formed product A at 135 ℃ for 8h, and roasting at 650 ℃ for 4h to obtain the composite carrier.
3) Loading of active ingredients
According to the weight ratio of Co: ni: mo: weighing a certain amount of cobalt nitrate, nickel nitrate, ammonium molybdate and ammonium tungstate according to the molar weight ratio of 2:3:1:2, and adding deionized water to prepare an aqueous solution C, wherein the total molar weight concentration of metal ions is 2.0 mol/L; adding a certain amount of calculated solution C into the composite carrier according to the loading capacity of the active components of cobalt, nickel, molybdenum and tungsten oxide of 7.5% and the mass of the composite carrier of 100g, stirring, and fully soaking to obtain a soaking material A; placing the impregnating material A in an oven to be dried for 10h at 130 ℃; and (3) placing the dried impregnating compound A in a muffle furnace for roasting at 525 ℃ for 5h to obtain the catalyst with 7.5% of active component load.
Example 9
1) Preparation of perovskites
Lanthanum acetate, calcium nitrate, ferric nitrate and manganese nitrate are prepared into a precursor aqueous solution A of a perovskite type active component, wherein the molar ratio of metal ions La: ca: fe: the molar weight ratio of Mn is 9:1:1:9, and the total molar weight concentration of metal ions is 1.8 mol/L; adding a certain amount of citric acid into the solution A, wherein the molar ratio of the citric acid to La, Ca, Fe and Mn is 2.0, stirring, and fully dissolving to obtain a solution B; putting the solution B in an oven to dry for 24 hours at 100 ℃, and evaporating excessive water to obtain gel A; placing gel A in muffleRoasting in a furnace at 850 ℃ for 3h to obtain perovskite La0.9Ca0.1Fe0.1Mn0.9O3。
2) Shaping of composite carriers
140g of La0.9Ca0.1Fe0.1Mn0.9O3、60gγ-Al2O340g of amorphous silicon-aluminum, 60g of ZSM-22 molecular sieve, 30g of pectin and 50g of pseudo-boehmite are fully mixed; adding 120g of deionized water and 12g of nitric acid into the mixture dry material, fully kneading, and extruding into strips by using a strip extruding machine to obtain a formed object A; and drying the formed product A at 120 ℃ for 12h, and roasting at 650 ℃ for 3h to obtain the composite carrier.
3) Loading of active ingredients
According to the weight ratio of Co: weighing a certain amount of cobalt nitrate and ammonium molybdate, and adding deionized water to prepare an aqueous solution C, wherein the molar weight ratio of Mo is 1:1, and the total molar weight concentration of metal ions is 2.0 mol/L; adding a certain amount of calculated solution C into the composite carrier according to the loading capacity of the cobalt and molybdenum oxides as active components of 15% and the mass of the composite carrier of 100g, stirring, and fully soaking to obtain a soaking material A; placing the impregnating material A in an oven to be dried for 5 hours at 140 ℃; and (3) placing the dried impregnating compound A in a muffle furnace to roast for 6h at 500 ℃ to obtain the catalyst with 15.0% of active component loading.
Example 10
1) Preparation of perovskites
Lanthanum nitrate, calcium nitrate, ferric nitrate and manganese nitrate are prepared into a precursor aqueous solution A of a perovskite type active component, wherein the molar ratio of metal ions La: ca: fe: the molar weight ratio of Mn is 5:5:5:5, and the total molar weight concentration of metal ions is 2.5 mol/L; adding a certain amount of citric acid into the solution A, wherein the molar ratio of the citric acid to La, Ca, Fe and Mn is 1.0, stirring, and fully dissolving to obtain a solution B; putting the solution B in an oven to dry for 8 hours at 115 ℃, and evaporating excessive water to obtain gel A; placing the gel A in a muffle furnace to be roasted for 1h at 900 ℃ to obtain the perovskite La0.5Ca0.5Fe0.5Mn0.5O3。
2) Shaping of composite carriers
50gL of the solution is addeda0.5Ca0.5Fe0.5Mn0.5O3、100gγ-Al2O3150g of ZSM-23 molecular sieve, 10g of pectin and 10g of pseudo-boehmite are fully mixed; adding 100g of deionized water and 10g of nitric acid into the mixture dry material, fully kneading, and extruding into strips by using a strip extruding machine to obtain a formed object A; and drying the formed product A at 100 ℃ for 24h, and roasting at 600 ℃ for 3.5h to obtain the composite carrier.
3) Loading of active ingredients
According to the weight ratio of Ni: weighing a certain amount of nickel nitrate and ammonium tungstate according to the molar weight ratio of 2:1, and adding deionized water to prepare an aqueous solution C, wherein the total molar weight concentration of metal ions is 1.0 mol/L; adding a certain amount of calculated solution C into the composite carrier according to the loading capacity of active components of nickel and tungsten oxide being 12.5% and the mass of the composite carrier being 100g, stirring, and fully soaking to obtain a soaking material A; placing the impregnating material A in an oven to be dried for 24 hours at 100 ℃; and (3) placing the dried impregnating compound A in a muffle furnace to roast for 4h at the temperature of 600 ℃ to obtain the catalyst with the active component load of 12.5%.
Example 11
1) Preparation of perovskites
Lanthanum nitrate, calcium nitrate, ferric nitrate and manganese nitrate are prepared into a precursor aqueous solution A of a perovskite type active component, wherein the molar ratio of metal ions La: ca: fe: the molar weight ratio of Mn is 3:7:7:3, and the total molar weight concentration of metal ions is 2.0 mol/L; adding a certain amount of citric acid into the solution A, wherein the molar ratio of the citric acid to La, Ca, Fe and Mn is 0.5, stirring, and fully dissolving to obtain a solution B; putting the solution B in an oven to dry for 4h at 150 ℃, and evaporating excessive water to obtain gel A; placing the gel A in a muffle furnace for roasting at 775 ℃ for 4h to obtain the perovskite La0.3Ca0.7Fe0.7Mn0.3O3。
2) Shaping of composite carriers
150g of La0.3Ca0.7Fe0.7Mn0.3O3、10gγ-Al2O3200g of SAPO-31 molecular sieve, 15g of carboxymethyl cellulose and 30g of pseudo-boehmite are fully mixed; deionized water 9 is added to the dry mixture0g of acetic acid and 6g of acetic acid, fully kneading, and extruding and molding by using a bar extruding machine to obtain a molding A; and drying the formed product A at 140 ℃ for 6h, and roasting at 500 ℃ for 4h to obtain the composite carrier.
3) Loading of active ingredients
According to the weight ratio of Co: ni: weighing a certain amount of cobalt nitrate, nickel nitrate and ammonium molybdate according to the molar weight ratio of Mo being 1:1:1, and adding deionized water to prepare an aqueous solution C, wherein the total molar weight concentration of metal ions is 1.5 mol/L; adding a certain amount of calculated solution C into the composite carrier according to the loading capacity of the active components of cobalt, nickel and molybdenum oxide of 20.0% and the mass of the composite carrier of 100g, stirring, and fully soaking to obtain a soaking material A; placing the impregnating material A in an oven to be dried for 1h at the temperature of 150 ℃; and placing the dried impregnating compound A in a muffle furnace for roasting at 650 ℃ for 3h to obtain the catalyst with 20.0% of active component loading.
Example 12
1) Preparation of perovskites
Lanthanum nitrate, calcium nitrate, ferric nitrate and manganese nitrate are prepared into a precursor aqueous solution A of a perovskite type active component, wherein the molar ratio of metal ions La: ca: fe: the molar weight ratio of Mn is 1:9:9:1, and the total molar weight concentration of metal ions is 1.1 mol/L; adding a certain amount of citric acid into the solution A, wherein the molar ratio of the citric acid to La, Ca, Fe and Mn is 3.0, stirring, and fully dissolving to obtain a solution B; putting the solution B in an oven to dry for 4h at 150 ℃, and evaporating excessive water to obtain gel A; placing the gel A in a muffle furnace to be roasted for 5h at 750 ℃ to obtain the perovskite La0.1Ca0.9Fe0.9Mn0.1O3。
2) Shaping of composite carriers
Will 90gLa0.1Ca0.9Fe0.9Mn0.1O3、100gγ-Al2O350g of ZSM-5 molecular sieve, 20g of sesbania powder and 15g of pseudo-boehmite are fully mixed; adding 80g of deionized water and 5g of acetic acid into the dry mixture, fully kneading, and extruding and molding by using a bar extruding machine to obtain a molding A; and drying the formed product A at 130 ℃ for 3h, and roasting at 550 ℃ for 5h to obtain the composite carrier.
3) Loading of active ingredients
According to the weight ratio of Co: ni: weighing a certain amount of cobalt nitrate, nickel nitrate and ammonium tungstate and adding deionized water to prepare an aqueous solution C, wherein the molar weight ratio of W is 1:2:3, and the total molar weight concentration of metal ions is 2.5 mol/L; adding a certain amount of calculated solution C into the composite carrier according to the loading capacity of active components of cobalt, nickel and tungsten oxide being 10.0% and the mass of the composite carrier being 100g, stirring, and fully soaking to obtain a soaking material A; placing the impregnating material A in an oven to be dried for 12h at 100 ℃; and (3) placing the dried impregnating compound A in a muffle furnace to roast for 4h at 550 ℃ to obtain the catalyst with 10.0% of active component loading.
Example 13
1) Preparation of perovskites
Lanthanum nitrate, calcium nitrate, ferric nitrate and manganese nitrate are prepared into a precursor aqueous solution A of a perovskite type active component, wherein the molar ratio of metal ions La: ca: fe: the molar weight ratio of Mn is 8:2:2:8, and the total molar weight concentration of metal ions is 1.5 mol/L; adding a certain amount of citric acid into the solution A, wherein the molar ratio of the citric acid to La, Ca, Fe and Mn is 2.8, stirring, and fully dissolving to obtain a solution B; putting the solution B in an oven to dry for 20h at 100 ℃, and evaporating excessive water to obtain gel A; placing the gel A in a muffle furnace to be roasted for 3h at 800 ℃ to obtain the perovskite La0.8Ca0.2Fe0.2Mn0.8O3。
2) Shaping of composite carriers
75gLa0.8Ca0.2Fe0.2Mn0.8O3、50gγ-Al2O3175g of SAPO-11 molecular sieve, 30g of guar gum and 30g of pseudo-boehmite are fully mixed; adding 100g of deionized water and 12g of acetic acid into the dry mixture, fully kneading, and extruding into strips by using a strip extruding machine to obtain a formed object A; and drying the formed product A at 150 ℃ for 4h, and roasting at 625 ℃ for 5h to obtain the composite carrier.
3) Loading of active ingredients
According to the weight ratio of Co: ni: weighing a certain amount of cobalt nitrate, nickel nitrate and ammonium tungstate according to the molar weight ratio of 1:1:1:1, and adding deionized water to prepare an aqueous solution C, wherein the total molar weight concentration of metal ions is 2.5 mol/L; adding a certain amount of calculated solution C into the composite carrier according to the loading capacity of the active components of cobalt, nickel, molybdenum and tungsten oxide of 25% and the mass of the composite carrier of 100g, stirring, and fully soaking to obtain a soaking material A; placing the impregnating material A in an oven to be dried for 15h at 110 ℃; and (3) placing the dried impregnating compound A in a muffle furnace to roast for 3h at the temperature of 575 ℃, thus obtaining the catalyst with 25.0 percent of loading of active components.
Example 14
1) Preparation of perovskites
Lanthanum nitrate, calcium nitrate, ferric nitrate and manganese nitrate are prepared into a precursor aqueous solution A of a perovskite type active component, wherein the molar ratio of metal ions La: ca: fe: the molar weight ratio of Mn is 4:6:6:4, and the total molar weight concentration of metal ions is 2.5 mol/L; adding a certain amount of citric acid into the solution A, wherein the molar ratio of the citric acid to La, Ca, Fe and Mn is 2.4, stirring, and fully dissolving to obtain a solution B; putting the solution B in an oven to dry for 4h at 120 ℃, and evaporating excessive water to obtain gel A; placing the gel A in a muffle furnace to be roasted for 6h at 700 ℃ to obtain the perovskite La0.4Ca0.6Fe0.6Mn0.4O3。
2) Shaping of composite carriers
125gLa0.4Ca0.6Fe0.6Mn0.4O3、75gγ-Al2O3100g of SAPO-41 molecular sieve, 10g of gum and 30g of pseudo-boehmite are fully mixed; adding 60g of deionized water and 10g of oxalic acid into the dry mixture, fully kneading, and extruding and molding by using a bar extruding machine to obtain a molding A; and drying the formed product A at 105 ℃ for 20h, and roasting at 575 ℃ for 6h to obtain the composite carrier.
3) Loading of active ingredients
According to the weight ratio of Ni: mo: weighing a certain amount of nickel nitrate, ammonium molybdate and ammonium tungstate according to the molar weight ratio of 1:2:3, and adding deionized water to prepare an aqueous solution C, wherein the total molar weight concentration of metal ions is 1.5 mol/L; adding a certain amount of calculated solution C into the composite carrier according to the loading capacity of active components of nickel, molybdenum and tungsten oxide being 5.0% and the mass of the composite carrier being 100g, stirring, and fully soaking to obtain a soaking material A; placing the impregnating material A in an oven to be dried for 9h at 120 ℃; and placing the dried impregnating compound A in a muffle furnace for roasting at 625 ℃ for 2.5h to obtain the catalyst with 5.0% of active component load.
Example 15
1) Preparation of perovskites
Lanthanum nitrate, calcium nitrate, ferric nitrate and manganese nitrate are prepared into a precursor aqueous solution A of a perovskite type active component, wherein the molar ratio of metal ions La: ca: fe: the molar weight ratio of Mn is 7:3:3:7, and the total molar weight concentration of metal ions is 2.0 mol/L; adding a certain amount of citric acid into the solution A, wherein the molar ratio of the citric acid to La, Ca, Fe and Mn is 1.5, stirring, and fully dissolving to obtain a solution B; putting the solution B in an oven to dry for 12h at 130 ℃, and evaporating excessive water to obtain gel A; placing the gel A in a muffle furnace to be roasted for 1h at 900 ℃ to obtain the perovskite La0.7Ca0.3Fe0.3Mn0.7O3。
2) Shaping of composite carriers
Will 100gLa0.7Ca0.3Fe0.3Mn0.7O3、80gγ-Al2O3Fully mixing 30g of amorphous silicon-aluminum, 90g of SAPO-31 molecular sieve, 20g of guar gum and 10g of pseudo-boehmite; adding 70g of deionized water and 5g of oxalic acid into the dry mixture, fully kneading, and extruding and molding by using a bar extruding machine to obtain a molding A; and drying the formed product A at 115 ℃ for 12h, and roasting at 650 ℃ for 4h to obtain the composite carrier.
3) Loading of active ingredients
According to the weight ratio of Co: weighing a certain amount of cobalt nitrate and ammonium tungstate according to the molar weight ratio of 2:1, and adding deionized water to prepare an aqueous solution C, wherein the total molar weight concentration of metal ions is 1.0 mol/L; adding a certain amount of calculated solution C into the composite carrier according to the loading capacity of the active components of cobalt and tungsten oxide being 18.0% and the mass of the composite carrier being 100g, stirring, and fully soaking to obtain a soaking material A; placing the impregnating material A in an oven to be dried for 4h at the temperature of 150 ℃; and placing the dried impregnating compound A in a muffle furnace for roasting at 650 ℃ for 3h to obtain the catalyst with 18.0% of active component loading.
Example 16
1) Preparation of perovskites
Lanthanum nitrate, calcium nitrate, ferric nitrate and manganese nitrate are prepared into a precursor aqueous solution A of a perovskite type active component, wherein the molar ratio of metal ions La: ca: fe: the molar weight ratio of Mn is 2:8:8:2, and the total molar weight concentration of metal ions is 1.0 mol/L; adding a certain amount of citric acid into the solution A, wherein the molar ratio of the citric acid to La, Ca, Fe and Mn is 0.8, stirring, and fully dissolving to obtain a solution B; putting the solution B in an oven to dry for 13h at 105 ℃, and evaporating excessive water to obtain gel A; placing the gel A in a muffle furnace to roast for 2h at 850 ℃ to obtain the perovskite La0.2Ca0.8Fe0.8Mn0.2O3。
2) Shaping of composite carriers
Will 100gLa0.2Ca0.8Fe0.8Mn0.2O3100g amorphous silica-alumina, 100g ZSM-22 molecular sieve, 40g gum and 50g pseudo-boehmite; adding 80g of deionized water and 13g of oxalic acid into the dry mixture, fully kneading, and extruding and molding by using a bar extruding machine to obtain a molding A; and drying the formed product A at 135 ℃ for 8h, and roasting at 500 ℃ for 6h to obtain the composite carrier.
3) Loading of active ingredients
According to the weight ratio of Ni: weighing a certain amount of nickel nitrate and ammonium molybdate according to the molar weight ratio of Mo being 1:1, and adding deionized water to prepare an aqueous solution C, wherein the total molar weight concentration of metal ions is 2.0 mol/L; adding a certain amount of calculated solution C into the composite carrier according to the loading capacity of the active components of cobalt, nickel, molybdenum and tungsten oxide of 7.5% and the mass of the composite carrier of 100g, stirring, and fully soaking to obtain a soaking material A; placing the impregnating material A in an oven to be dried for 10h at 130 ℃; and (3) placing the dried impregnating compound A in a muffle furnace for roasting at 525 ℃ for 5h to obtain the catalyst with 7.5% of active component load.
Example 17
1) Preparation of perovskites
Lanthanum acetate, strontium acetate, iron acetate and manganese acetate are prepared into a precursor aqueous solution A of a perovskite type active component, wherein the molar ratio of metal ions La: sr: fe: the molar weight ratio of Mn is 7:3:3:7,the total molar concentration of metal ions is 2.5 mol/L; adding a certain amount of citric acid into the solution A, wherein the molar ratio of the citric acid to La, Sr, Fe and Mn is 2.4, stirring, and fully dissolving to obtain a solution B; putting the solution B in an oven, drying for 12h at 115 ℃, and evaporating excessive water to obtain gel A; placing the gel A in a muffle furnace to be roasted for 1h at 900 ℃ to obtain the perovskite La0.7Sr0.3Fe0.3Mn0.7O3。
2) Shaping of composite carriers
140gLa0.7Sr0.3Fe0.3Mn0.7O375g of amorphous silicon-aluminum, 75g of ZSM-5 molecular sieve, 30g of pectin and 10g of pseudo-boehmite; adding 80g of deionized water and 6g of nitric acid into the mixture dry material, fully kneading, and extruding into strips by using a strip extruding machine to obtain a formed object A; and drying the formed product A at 170 ℃ for 1h, and roasting at 450 ℃ for 6h to obtain the composite carrier.
3) Loading of active ingredients
Preparing cobalt nitrate, nickel acetate, ammonium molybdate, ammonium tungstate and deionized water into an aqueous solution C, wherein the ratio of Co: ni: mo: the molar weight ratio of W is 3:1:2:4, and the total molar weight concentration of metal ions is 1.5 mol/L; adding the solution C into the composite carrier according to the loading of active components of cobalt, nickel, molybdenum and tungsten oxide of 3.0% and the mass of the composite carrier of 100g, stirring, and fully soaking to obtain a soaking material A; placing the impregnating material A in an oven to be dried for 2h at the temperature of 130 ℃; and (3) placing the dried impregnating compound A in a muffle furnace to roast for 3h at the temperature of 600 ℃ to obtain the catalyst with the loading of 3.0%.
Example 18
1) Preparation of perovskites
Lanthanum acetate, calcium acetate, copper acetate and manganese acetate are prepared into a precursor aqueous solution A of a perovskite type active component, wherein the molar ratio of metal ions La: ca: cu: the molar weight ratio of Mn is 7:3:3:7, and the total molar weight concentration of metal ions is 2.5 mol/L; adding a certain amount of citric acid into the solution A, wherein the molar ratio of the citric acid to La, Ca, Cu and Mn is 2.4, stirring, and fully dissolving to obtain a solution B; drying the solution B in an oven at 115 ℃ for 12h, evaporating off excessive water to obtainGel A; placing the gel A in a muffle furnace to be roasted for 1h at 900 ℃ to obtain the perovskite La0.7Ca0.3Cu0.3Mn0.7O3。
2) Shaping of composite carriers
140gLa0.7Ca0.3Cu0.3Mn0.7O375g of amorphous silicon-aluminum, 75g of ZSM-5 molecular sieve, 30g of pectin and 10g of pseudo-boehmite; adding 80g of deionized water and 6g of nitric acid into the mixture dry material, fully kneading, and extruding into strips by using a strip extruding machine to obtain a formed object A; and drying the formed product A at 115 ℃ for 12h, and roasting at 500 ℃ for 6h to obtain the composite carrier.
3) Loading of active ingredients
Preparing cobalt nitrate, nickel acetate, ammonium molybdate, ammonium tungstate and deionized water into an aqueous solution C, wherein the ratio of Co: ni: mo: the molar weight ratio of W is 3:1:2:4, and the total molar weight concentration of metal ions is 1.5 mol/L; adding the solution C into the composite carrier according to the loading of the active components of cobalt, nickel, molybdenum and tungsten oxide of 28.0% and the mass of the composite carrier of 100g, stirring, and fully soaking to obtain a soaking material A; placing the impregnating material A in an oven to be dried for 1h at the temperature of 170 ℃; and (3) placing the dried impregnating compound A in a muffle furnace to roast for 3h at 670 ℃, thus obtaining the catalyst with the load of 28.0%.
Example 19
1) Preparation of perovskites
Lanthanum acetate, strontium acetate, copper acetate and manganese acetate are prepared into a precursor aqueous solution A of a perovskite type active component, wherein the molar ratio of metal ions La: sr: cu: the molar weight ratio of Mn is 7:3:3:7, and the total molar weight concentration of metal ions is 2.5 mol/L; adding a certain amount of citric acid into the solution A, wherein the molar ratio of the citric acid to La, Sr, Cu and Mn is 2.4, stirring, and fully dissolving to obtain a solution B; putting the solution B in an oven, drying for 12h at 115 ℃, and evaporating excessive water to obtain gel A; placing the gel A in a muffle furnace to be roasted for 1h at 900 ℃ to obtain the perovskite La0.7Sr0.3Cu0.3Mn0.7O3。
2) Shaping of the support
140gLa0.7Sr0.3Cu0.3Mn0.7O375g of amorphous silicon-aluminum, 75g of ZSM-5 molecular sieve, 30g of pectin and 10g of pseudo-boehmite; adding 80g of deionized water and 6g of nitric acid into the dry mixture, fully kneading, and uniformly stirring the acidic carrier, the organic binder and the inorganic binder to prepare a mixture; (2) extruding and forming by a strip extruding machine to obtain a forming object A; and drying the formed product A at 90 ℃ for 14h, and roasting at 680 ℃ for 4h to obtain the carrier.
3) Loading of active ingredients
Preparing cobalt nitrate, nickel acetate, ammonium molybdate, ammonium tungstate and deionized water into an aqueous solution C, wherein the ratio of Co: ni: mo: the molar weight ratio of W is 3:1:2:4, and the total molar weight concentration of metal ions is 1.5 mol/L; adding the solution C into a carrier according to the loading of the active components of cobalt, nickel, molybdenum and tungsten oxide of 18.0 percent and the mass of the composite carrier of 100g, stirring and fully soaking to obtain a soaking material A; placing the impregnating material A in an oven to be dried for 24 hours at 50 ℃; and (3) placing the dried impregnating compound A in a muffle furnace to roast for 6h at the temperature of 450 ℃, thus obtaining the catalyst with the loading of 18.0%.
Comparative example 1
Preparing cobalt acetate, nickel acetate, ammonium molybdate, ammonium tungstate and deionized water into an aqueous solution, wherein the ratio of Co: ni: mo: the molar weight ratio of W is 1:1:1:1, and the total molar weight concentration of metal ions is 2.5 mol/L; adding the solution into gamma-Al2O3Stirring and fully soaking to obtain a soaking material; placing the impregnated material in a drying oven to be dried for 10 hours at the temperature of 130 ℃; and (3) placing the dried impregnated material in a muffle furnace, and roasting at 550 ℃ for 5 hours to obtain the catalyst with the load of 12.5%.
Comparative example 2
Preparing cobalt acetate, nickel acetate, ammonium molybdate, ammonium tungstate and deionized water into an aqueous solution, wherein the ratio of Co: ni: mo: the molar weight ratio of W is 1:1:1:1, and the total molar weight concentration of metal ions is 2.5 mol/L; adding the solution into ZSM-5, stirring, and fully impregnating to obtain an impregnating material; placing the impregnated material in a drying oven to be dried for 10 hours at the temperature of 130 ℃; and (3) placing the dried impregnated material in a muffle furnace, and roasting at 550 ℃ for 5 hours to obtain the catalyst with the load of 12.5%.
Comparative example 3
1) Shaping of the support
100g of gamma-Al2O3100g of amorphous silicon aluminum, 5g of guar gum and 50g of pseudo-boehmite are fully mixed; adding 120g of deionized water and 12g of acetic acid into the dry mixture, fully kneading, and extruding and molding by using a bar extruding machine to obtain a molding A; and drying the formed product A at 135 ℃ for 8h, and roasting at 650 ℃ for 4h to obtain the carrier.
2) Loading of active ingredients
Preparing cobalt acetate, nickel acetate, ammonium molybdate, ammonium tungstate and deionized water into an aqueous solution, wherein the ratio of Co: ni: mo: the molar weight ratio of W is 1:1:1:1, and the total molar weight concentration of metal ions is 2.5 mol/L; adding the solution into a carrier, stirring, and fully soaking to obtain a soaking material; placing the impregnated material in a drying oven to be dried for 10 hours at the temperature of 130 ℃; and (3) placing the dried impregnated material in a muffle furnace, and roasting at 550 ℃ for 5 hours to obtain the catalyst with the load of 12.5%.
Comparative example 4
1) Shaping of the support
100g of gamma-Al2O3100g of SAPO-11, 5g of sesbania powder and 50g of pseudo-boehmite are fully mixed; adding 120g of deionized water and 6g of concentrated nitric acid into the dry mixture, fully kneading, and uniformly stirring the acidic carrier, the organic binder and the inorganic binder to prepare a mixture; (2) extruding and forming by a strip extruding machine to obtain a forming object A; and drying the formed product A at 120 ℃ for 8h, and roasting at 650 ℃ for 4h to obtain the carrier.
2) Loading of active ingredients
Preparing cobalt acetate, nickel acetate, ammonium molybdate, ammonium tungstate and deionized water into an aqueous solution, wherein the ratio of Co: ni: mo: the molar weight ratio of W is 1:1:1:1, and the total molar weight concentration of metal ions is 2.5 mol/L; adding the solution into a carrier, stirring, and fully soaking to obtain a soaking material; placing the impregnated material in a drying oven to be dried for 10 hours at the temperature of 130 ℃; and (3) placing the dried impregnated material in a muffle furnace, and roasting at 550 ℃ for 5 hours to obtain the catalyst with the load of 12.5%.
Test examples
The activity of the catalysts prepared in the examples and comparative examples was evaluated. The specific evaluation implementation steps comprise:
1) catalyst loading
20ml of catalyst is filled into a reactor, an inlet flange and an outlet flange of the reactor are connected, the airtightness of the device is firstly detected under the hydrogen atmosphere and the pressure of 8.0MPa, and the airtightness is qualified when the pressure drop in the period is less than 0.01 MPa/h.
2) Presulfiding of catalysts
The catalyst is pre-vulcanized by a wet vulcanization mode, and the vulcanized oil is a mixed solution of cyclohexane with the concentration of 4% and DMDS (dimethyl disulfide); increasing the temperature of the catalyst bed to 150 ℃ at the speed of 25 ℃/h in the hydrogen atmosphere; at 1.0h-1Injecting the sulfurized oil at the airspeed of (1); heating to 320 ℃ at the speed of 10 ℃/h, and keeping the temperature of 320 ℃ for 4 h; then heating to 350 ℃ at the speed of 10 ℃/h, and keeping the temperature at 350 ℃ for 12 h; the sulfurized oil was replaced with cyclohexane without DMDS for 1.0h-1Starts to lower the reaction temperature to 320 c at a rate of 10 c/h. About 200ml of n-hexane is consumed in the process;
3) evaluation of catalyst Activity
When the catalyst bed layer reaches 320 ℃, the cyclohexane is completely replaced by normal raw oil, the physicochemical properties of the raw oil are shown in table 1, the catalyst bed layer is at 6.0MPa and the space velocity is 1.0h-1The activity evaluation was carried out under the condition of a hydrogen-oil volume ratio of 800, the catalyst activity evaluation conditions are shown in Table 2, and the physicochemical properties of the finally obtained product are shown in Table 3.
TABLE 1 physicochemical Properties of vegetable oil feedstock
Item Content (wt.)
Fatty acid glyceride composition C14-C18Fatty acid glycerides
Iodine number 45.8gI2/100g
Oxygen content 9.2wt％
Freezing point 18℃
TABLE 2 catalyst evaluation conditions
Item Evaluation conditions
Catalyst loading 20ml
Reaction temperature 320℃
Reaction pressure 6.0MPa
LHSV 1.0h-1
H2Oil ratio 800
TABLE 3 physicochemical Properties of the products
Figure BDA0002000170300000271
Figure BDA0002000170300000281
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (15)

1. A catalyst for preparing hydrocarbon fuel by hydrodeoxygenation of animal and vegetable oil is characterized by comprising the following components:
the active component comprises at least one metal element in VIB group and at least one metal element in VIII group;
perovskite of the formula A1-xA'xB1-yB'yO3In the formula, A is a rare earth metal element, A 'is an alkaline earth metal element, B and B' are transition metal elements, x is more than or equal to 0.1 and less than or equal to 0.9, and y is more than or equal to 0.1 and less than or equal to 0.9;
acidic carrier comprising gamma-Al2O3Or at least one of amorphous silicon aluminum and a molecular sieve;
the preparation method of the catalyst comprises the following steps: the active component is loaded on a composite carrier prepared from perovskite and an acidic carrier.
2. The catalyst according to claim 1, wherein the group VIB element is Mo and/or W, and the group VIII metal element is Co and/or Ni.
3. The catalyst according to any one of claims 1 or 2, wherein the oxide containing the active component is present in the catalyst in an amount of 5 to 25 wt%.
4. The catalyst according to claim 1, wherein the rare earth metal element is La, the alkaline earth metal element is Ca or Sr, and the transition metal element is Fe and Mn, or Cu and Mn.
5. A catalyst as claimed in any one of claims 1 or 4, wherein the perovskite comprises from 15 to 50 wt% of the catalyst.
6. The catalyst of claim 1, wherein the acidic support further comprises amorphous silica-alumina.
7. The catalyst of claim 1, wherein the molecular sieve is at least one of ZSM-5, ZSM-22, ZSM-23, SAPO-11, SAPO-31, SAPO-41.
8. A catalyst according to any one of claims 1 or 6 to 7, characterized in that the acidic support constitutes 45-65 wt% of the catalyst.
9. The catalyst according to claim 1, characterized in that the preparation of the composite support comprises in particular the following steps:
and adding a binder into the perovskite and the acidic carrier to prepare a mixture, then adding a peptizing agent and water into the mixture, kneading and molding after mixing, and drying and roasting the molded product to obtain the composite carrier.
10. The catalyst of claim 9, wherein the binder comprises an organic binder and an inorganic binder, the organic binder is at least one of sesbania gum, guar gum, carboxymethyl cellulose, gum, and pectin, and the inorganic binder is pseudo-boehmite.
11. The catalyst of claim 10 wherein the organic binder comprises 2 to 10 wt% of the mixture and the inorganic binder comprises 2 to 10 wt% of the mixture.
12. The catalyst of any of claim 9, wherein the peptizing agent is at least one of acetic acid, oxalic acid, nitric acid.
13. The catalyst as claimed in any one of claims 9 to 12, wherein the drying temperature of the shaped product is 100-150 ℃ and the drying time is 4-24 h; the roasting temperature is 500-650 ℃, and the roasting time is 3-6 h.
14. The catalyst according to claim 1, characterized in that the loading step comprises in particular the operations of: and preparing soluble salt of the active component into aqueous solution, adding the aqueous solution into the composite carrier for impregnation to obtain an impregnation material, and finally drying and roasting the impregnation material to obtain the catalyst loaded with the active component.
15. The catalyst as claimed in claim 14, wherein the drying temperature of the impregnant is 60-150 ℃, the drying time is 3-24h, the calcination temperature is 500-650 ℃, and the calcination time is 3-6 h.
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