CN110465314B - Hydrodeoxygenation catalyst and preparation method and application thereof - Google Patents
Hydrodeoxygenation catalyst and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
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- 239000002184 metal Substances 0.000 claims abstract description 21
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- 238000006243 chemical reaction Methods 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 21
- 241000219782 Sesbania Species 0.000 claims description 16
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
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- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 7
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
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- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 claims description 6
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical group N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims description 6
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- 238000007599 discharging Methods 0.000 claims description 2
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- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
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- 238000010438 heat treatment Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
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- 238000012512 characterization method Methods 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- 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
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- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a hydrodeoxygenation catalyst and a preparation method thereofA preparation method and application thereof, and the hydrodeoxygenation catalyst comprisesγ‑Al 2 O 3 Carrier and carrier supported onγ‑Al 2 O 3 Bimetallic phosphide PdMoP on a carrier; in the double-metal phosphide PdMoP, the mass of the metal element Pd is as followsγ‑Al 2 O 3 0.2-0.8% of the mass of the carrier, and the mass of the metal element Mo is calculated asγ‑Al 2 O 3 5.0-10.0% of the mass of the carrier, and the mass of the non-metallic element P is calculated asγ‑Al 2 O 3 1.0-5.0% of the carrier mass. The preparation method of the hydrodeoxygenation catalyst is simple, and the prepared hydrodeoxygenation catalyst has high hydrodeoxygenation activity and can keep high catalytic activity for a long time. The catalyst of the invention has the advantages of high catalytic activity, high selectivity, high durability and the like and good comprehensive performance.
Description
Technical Field
The invention relates to a hydrodeoxygenation catalyst, a preparation method and application thereof.
Background
With the rapid development of economy, the demand for energy in countries around the world has also increased year by year. The petroleum reserve of China is limited, and the demand for imported petroleum is continuously increased; meanwhile, the combustion of fossil fuels can generate various greenhouse gases such as nitrogen oxides, carbon oxides and the like, and serious influence is caused on the living environment of people. The research on renewable, economically feasible and sustainably produced clean energy is a very important topic. Biomass can store solar energy in the form of chemical energy and is the only renewable carbon source. Among them, biodiesel has become one of the research hotspots because of its advantages of environmental friendliness, renewability, etc. However, biodiesel has significant disadvantages compared to conventional fossil fuels, such as its relatively high freezing and cloud points, poor chemical stability, high viscosity, incomplete compatibility with conventional fossil fuels, and the like. In order to overcome these problems, researchers have studied catalytic hydrodeoxygenation technologies for triglycerides, fatty acid methyl esters, fatty acids, and the like, and developed various catalysts to obtain hydrocarbon biodiesel, also referred to as second generation biodiesel, which is similar to conventional fossil fuel components and has good compatibility with conventional fossil fuel components.
At present, the vulcanization catalyst is generally adopted in the industry, has the advantages of good catalytic effect and high efficiency, but also has the problems of sulfur loss in the production process, sulfur pollution to hydrocarbon products and the like; noble metal catalysts also have very high catalytic activity in the hydrodeoxygenation reaction of methyl esters, but the industrial application of the noble metal catalysts is limited due to the high price of the noble metal catalysts. Therefore, the development of a novel catalyst with good catalytic effect, high stability, no pollution and low price has received much attention.
Two major factors affecting the hydrodeoxygenation activity of supported catalysts are the proper pore size and the proper acidity of the catalyst. The small pore diameter of the catalyst can prevent the contact of the active center and the reactant, and the diffusion resistance of the reactant, the added product and the product can be increased, so that the catalytic activity of the supported catalyst is reduced; with larger pore sizes, the residence time of the reactants in the channels may be reduced, which may reduce the conversion of the reactants and the selectivity to the desired product. The acidity of the catalyst is too low, which directly results in the reduction of the conversion rate of reactants; too strong acidity can lead to reactant cleavage. Therefore, adjusting the pore and acidity of the carrier becomes an important direction and research hotspot in research. Patent CN107913715A discloses a NiMo/gamma-Al 2 O 3 The hydrodeoxygenation catalyst has large metal loading and long preparation time. Patent CN109675589A discloses a composite material composed of metal and MoS 2-x The composition of the hydrodeoxygenation catalyst contains sulfur, which may cause sulfur pollution to the product. Patent CN109745993A discloses a mesoporous Mo-Ni hydrodeoxygenation catalyst, and the process involved in the preparation process is relatively complex.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a hydrodeoxygenation catalyst, and a preparation method and application thereof. The preparation method of the hydrodeoxygenation catalyst is simple, and the prepared hydrodeoxygenation catalyst has high hydrodeoxygenation activity and can keep high catalytic activity for a long time. The catalyst of the invention has the advantages of high catalytic activity, high selectivity, high durability and the like and good comprehensive performance.
The hydrodeoxygenation catalyst is characterized by comprisingγ-Al 2 O 3 Carrier and carrier supported onγ-Al 2 O 3 Bimetallic phosphide PdMoP on a carrier; in the double metal phosphide PdMoP, the mass of a metal element Pd is as followsγ-Al 2 O 3 0.2-0.8% of the mass of the carrier, and the mass of the metal element Mo is calculated asγ-Al 2 O 3 5.0-10.0% of the mass of the carrier, and the mass of the non-metal element P is calculated asγ-Al 2 O 3 1.0-5.0% of the carrier mass.
The preparation method of the hydrodeoxygenation catalyst is characterized by comprising the following steps of:
1) Preparing a catalyst carrier: mixing pseudoboehmite powder and sesbania powder uniformly, adding a small amount of deionized water, and then dropwise adding a small amount of 93-98% concentrated HNO 3 Adding deionized water until the powder is full of viscosity to obtain Gaohuang mixture; kneading the obtained Gaohuang mixture into a dough, extruding the dough into thin strips, drying the strips, and then placing the strips in a muffle furnace to be roasted for 3 to 5h under the air atmosphere at the temperature of 500 to 750 ℃ to obtain a catalyst carrierγ-Al 2 O 3 ；
2) Preparing a catalyst precursor: the catalyst carrier obtained in the step 1)γ-Al 2 O 3 Soaking the catalyst in a mixed aqueous solution of a palladium source, a molybdenum source and a phosphorus source for 6 to 24 hours at room temperature by an isometric soaking method to load the palladium source, the molybdenum source and the phosphorus source on a catalyst carrierγ-Al 2 O 3 Drying at 60-120 ℃ until the water is completely volatilized, and then roasting at 400-700 ℃ for 3-6 h in an air atmosphere to prepare a catalyst precursor;
3) Preparation of catalyst product: and (3) placing the catalyst precursor obtained in the step 2) in a tubular furnace, and calcining and reducing the catalyst precursor in a hydrogen atmosphere at the temperature of 350-400 ℃ for 2-5 h under the hydrogen pressure of 0.5-2.5 MPa to finally obtain the hydrodeoxygenation catalyst.
The preparation method of the hydrodeoxygenation catalyst is characterized in that in the step 1), the mass ratio of the pseudoboehmite powder to the sesbania powder is 15-25: 1, and the sesbania powder and the concentrated HNO are mixed 3 The mass ratio of the solution is 5-20: 1.
The preparation method of the hydrodeoxygenation catalyst is characterized in that in the step 2), a palladium source is palladium chloride or palladium nitrate, a molybdenum source is ammonium molybdate tetrahydrate, and a phosphorus source is diammonium hydrogen phosphate.
The application of the hydrodeoxygenation catalyst is characterized in that the hydrodeoxygenation catalyst is used for catalyzing fatty acid methyl ester to prepare aliphatic hydrocarbon.
The application of the hydrodeoxygenation catalyst is characterized in that the hydrodeoxygenation catalyst is used for catalyzing fatty acid methyl ester to prepare long-chain n-alkane, and comprises the following steps: filling the hydrodeoxygenation catalyst into a fixed bed reactor, inputting a fatty acid methyl ester raw material and hydrogen into the fixed bed reactor at a reaction temperature to carry out hydrodeoxygenation reaction, wherein the length of a carbon chain at a fatty acid part of the fatty acid methyl ester is 16-18, and discharging a long-chain n-alkane product from the fixed bed reactor.
The application of the hydrodeoxygenation catalyst is characterized in that the reaction temperature is 315 to 375 ℃, the pressure of hydrogen input into a fixed bed reactor is 1.0 to 2.5 MPa, and the volume ratio of hydrogen to oil is 400 to 1900.
Compared with the prior art, the invention has the beneficial effects that:
(1) PdMoP-γ-Al 2 O 3 In the hydrodeoxygenation catalyst, the introduction of the P element regulates the acidity of the catalyst, so that the strong acid acidity of the catalyst is increased in a proper amount; the double metal phosphide PdMoP is used as an active component of the catalyst, so that the yield of C15-18 alkane in the product of the hydrodeoxygenation reaction is higher than that of C15-18 alkaneThe content of the C18 alkane in the C15-18 alkane liquid product is high (the additional value of the C18 alkane is higher than that of the C15-17 alkane). The catalyst has higher hydrodeoxygenation catalytic activity when preparing the second-generation biodiesel, can keep stable activity in longer reaction time, and has great significance for improving the quality of the second-generation biodiesel.
(2) The preparation method provided by the invention is simple, the preparation steps are simplified, and the preparation cost is reduced; in the preparation process of the catalyst carrier, the pseudoboehmite powder is roasted at high temperature to form gamma-Al 2 O 3 (ii) a The sesbania powder is added as an adhesive to adhere the pseudo-boehmite powder together so as to facilitate the carrier molding; concentrated nitric acid is added dropwise as a peptizing agent to convert the mixture into a substance with rheological property. Gamma-Al prepared by the invention 2 O 3 The carrier has high specific surface area and proper pore diameter, gamma-Al 2 O 3 The pore diameter of the porous material is mainly concentrated in 3 to 15 nm. The preparation process of the carrier has the advantages of simple operation and low cost.
Drawings
FIG. 1 shows N of the catalyst precursor prepared in example 1 of the present invention 2 An adsorption-desorption isotherm result graph;
FIG. 2 is a calculated pore size distribution graph by BJH method for the catalyst precursor prepared in example 1 of the present invention;
FIG. 3 shows NH of catalyst precursors in example 1, comparative example 1 and comparative example 2 3 -TPD spectrogram comparison;
FIG. 4 is an XRD spectrum of the catalyst precursor prepared in example 1 of the present invention;
FIG. 5 is a GC analysis spectrum of the hydrodeoxygenated liquid product of example 1 of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1:
1) Preparing a catalyst carrier: weighing 20.0 g of pseudoboehmite powder and 1.0 g of fieldAdding 5 mL of deionized water after uniformly mixing the components, and then dropwise adding two drops of 98% HNO 3 The solution (about 0.1 mL) was then added with deionized water until the mixed powder of pseudo-boehmite powder and sesbania powder was filled with a viscous substance, and then kneaded into a dough, extruded into a thin strip (diameter 2 mm) with a plodder, and placed in a forced-air oven set to 105 ℃ for 4 hours for drying. And taking out the dried thin strips, and roasting for 4 hours in a muffle furnace at 500 ℃. And cutting the thin strips into small strips with the length of 3-5 mm after fully cooling. The small strips are catalyst carriersγ-Al 2 O 3 To the obtained catalyst carrierγ-Al 2 O 3 BET characterization was performed, which is gamma-Al 2 O 3 The carrier has high specific surface area and pore volume of 325 m respectively 2 /g、1.02 cm 3 The pore diameter is mainly concentrated in 3 to 15 nm per gram.
2) Preparing a catalyst precursor: dissolving palladium chloride, ammonium molybdate tetrahydrate and diammonium hydrogen phosphate in deionized water to prepare a precursor solution; the catalyst carrier obtained in the step 1) is usedγ-Al 2 O 3 Soaking the precursor solution in an isometric soaking method for 12 hours at room temperature, drying at 105 ℃ to evaporate water, and roasting at 500 ℃ in an air atmosphere for 4 hours to prepare the catalyst precursor.
EDS energy spectrum analysis is carried out on the catalyst precursor obtained in the step 2) to determine the composition content of Pd, mo and P elements in the catalyst precursor. The EDS energy spectrum analysis result is as follows: in the catalyst precursor obtained in the step 2), the mass of the contained metal element Pd is 0.5 percent of the mass of the catalyst carrier, the mass of the metal element Mo is 9.0 percent of the mass of the catalyst carrier, and the mass of the nonmetal element P is 3.0 percent of the mass of the catalyst carrier;
EXAMPLE 1N of catalyst precursor obtained in step 2) 2 The results of the adsorption-desorption isotherm characterization are shown in fig. 1, and the results of the pore size distribution calculated by the BJH method based on the results in fig. 1 are shown in fig. 2. As can be seen from fig. 1, the catalyst precursor has a significant mesoporous structure; as can be seen from FIG. 2, the pore diameter of the catalyst precursor is mainly concentrated around 3-6 nm.
Practice ofExample 1 NH of catalyst precursor obtained in step 2) 3 The TPD spectrum is shown by the solid curve in FIG. 3. As can be seen from the solid-line curve in fig. 3, the catalyst precursor prepared in this example has a strong weak acid acidity and a relatively low strong acid acidity.
The XRD pattern of the catalyst precursor obtained in step 2) of example 1 is shown in FIG. 4, and it can be seen from FIG. 4 that the catalyst precursor has a large amount of impuritiesγ-Al 2 O 3 (carrier) and an oxide of the active component Pd.
3) Putting the catalyst precursor in the step 2) into a fixed bed reactor, and introducing H with the flow rate of 0.03L/min into the fixed bed reactor 2 Heating the fixed bed reactor to 380 ℃ for roasting reduction for 3 h 2 The pressure was 1.0 MPa. The catalyst precursor is reduced to obtain PdMoP-γ-Al 2 O 3 A hydrodeoxygenation catalyst.
4) PdMoPγ-Al 2 O 3 The hydrodeoxygenation catalyst is filled into a fixed bed catalyst. The method comprises the steps of taking soybean oil methyl ester as a raw material, and injecting the soybean oil methyl ester raw material into a fixed bed reactor by using a high-pressure plunger pump for carrying out hydrodeoxygenation reaction. Under the hydrogen pressure of 1.5 MPa, the volume ratio of hydrogen to oil is 1100, the reaction temperature is 315 ℃, and the mass space velocity of the soybean oil methyl ester is 0.5 h -1 In PdMoP-γ-Al 2 O 3 Carrying out hydrodeoxygenation reaction under the action of the hydrodeoxygenation catalyst to obtain a liquid product at room temperature, continuously reacting for 40h, sampling and analyzing, carrying out GC analysis on the obtained liquid product as shown in figure 5, and showing that the liquid product is basically C from figure 5 15-18 Alkanes, with minor amounts of C16:0 methyl esters and C18:0 methyl esters. Calculating according to the GC spectrogram result: conversion rate of soybean oil methyl ester is 98.4%, C 15-18 The yield of alkane reaches 91.5 percent, C 15~18 The alkane yields were 1.11%, 10.87%, 2.08% and 77.41%, respectively.
Example 2:
1) Preparing a catalyst carrier: weighing 20.0 g of pseudo-boehmite powder and 1.0 g of sesbania powder, uniformly mixing, adding 5 mL of deionized water, and dropwise adding two drops of 98% HNO 3 Solution and then adding continuouslyDeionized water until the mixed powder of pseudo-boehmite powder and sesbania powder is full of viscosity, kneading into a dough, extruding into fine strips (diameter 2 mm) by a strip extruder, and drying at 105 deg.C for 4 h in a blast-type oven. And taking out the dried strips, and roasting for 4 hours in a muffle furnace at 500 ℃. And cutting the thin strips into small strips with the length of 3-5 mm after fully cooling. The small strips are catalyst carriersγ-Al 2 O 3 。
2) Preparing a catalyst precursor: dissolving palladium chloride, ammonium molybdate tetrahydrate and diammonium hydrogen phosphate in water to prepare a precursor solution; the catalyst carrier obtained in the step 1)γ-Al 2 O 3 Soaking the precursor solution in an isometric soaking method for 12 hours at room temperature, drying at 105 ℃ to evaporate water, and roasting at 500 ℃ in an air atmosphere for 4 hours to obtain the catalyst precursor.
EDS energy spectrum analysis is carried out on the catalyst precursor obtained in the step 2) to determine the composition content of Pd, mo and P elements in the catalyst precursor. The EDS energy spectrum analysis result is as follows: in the obtained catalyst precursor, the mass of the metal element Pd is 0.5 percent of the mass of the catalyst carrier, the mass of the metal element Mo is 9.0 percent of the mass of the catalyst carrier, and the mass of the nonmetal element P is 1.6 percent of the mass of the catalyst carrier;
3) Putting the catalyst precursor in the step 2) into a fixed bed reactor, and introducing H with the flow rate of 0.05L/min into the fixed bed reactor 2 Heating the fixed bed reactor to 380 ℃ for roasting reduction for 3 h 2 The pressure was 1.0 MPa. The catalyst precursor is reduced to obtain PdMoP-γ-Al 2 O 3 A hydrodeoxygenation catalyst.
4) PdMoPγ-Al 2 O 3 The hydrodeoxygenation catalyst is filled into a fixed bed catalyst. The method comprises the steps of taking soybean oil methyl ester as a raw material, and injecting the soybean oil methyl ester raw material into a fixed bed reactor by using a high-pressure plunger pump for carrying out hydrodeoxygenation reaction. Under the hydrogen pressure of 1.5 MPa, the volume ratio of hydrogen to oil is 1100, the reaction temperature is 335 ℃, and the mass space velocity of the soybean oil methyl ester is 0.5 h -1 In PdMoP-γ-Al 2 O 3 Under the action of the hydrodeoxygenation catalyst, carrying out hydrodeoxygenation reaction to obtain C 15-18 The alkane liquid product is continuously reacted for 40 hours, sampled and analyzed, the conversion rate of the soybean oil methyl ester is 100.0 percent, and C is 15-18 The yield of alkane reaches 95.3 percent, C 15~18 The alkane yields were 1.01%, 10.26%, 5.00%, and 79.07%, respectively.
Example 3:
1) Preparing a catalyst carrier: weighing 20.0 g of pseudo-boehmite powder and 1.0 g of sesbania powder, uniformly mixing, adding 5 mL of deionized water, and dropwise adding two drops of 98% HNO 3 And adding deionized water into the solution continuously until the mixed powder of the pseudo-boehmite powder and the sesbania powder is full of viscosity, kneading the mixture into a cluster, extruding the cluster into thin strips (the diameter is 2 mm) by using a strip extruding machine, placing the strips into a blast type oven, and drying the strips for 4 hours at the temperature of 105 ℃. And taking out the dried strips, and roasting for 4 hours in a muffle furnace at 500 ℃. And cutting the thin strips into small strips with the length of 3-5 mm after fully cooling. The small strips are catalyst carriersγ-Al 2 O 3 。
2) Preparing a catalyst precursor: dissolving palladium chloride, ammonium molybdate tetrahydrate and diammonium hydrogen phosphate in water to prepare a precursor solution; the catalyst carrier gamma-Al obtained in the step 1) 2 O 3 Soaking the precursor solution in an isometric soaking method for 12 hours at room temperature, drying at 105 ℃ to evaporate water, and roasting at 500 ℃ in an air atmosphere for 4 hours to obtain the catalyst precursor.
EDS energy spectrum analysis is carried out on the catalyst precursor obtained in the step 2) to determine the composition content of Pd, mo and P elements in the catalyst precursor. The EDS energy spectrum analysis result is as follows: in the obtained catalyst precursor, the mass of the metal element Pd was 0.5% of the mass of the catalyst carrier, the mass of the metal element Mo was 9.0% of the mass of the catalyst carrier, and the mass of the nonmetal element P was 4.3% of the mass of the catalyst carrier.
3) Putting the catalyst precursor in the step 2) into a fixed bed reactor, and introducing H with the flow rate of 0.05L/min into the fixed bed reactor 2 Heating the fixed bed reactor to 380 deg.C for bakingThe reduction time is 3 h 2 The pressure was 1.0 MPa. The catalyst precursor is reduced to obtain PdMoP-γ-Al 2 O 3 A hydrodeoxygenation catalyst.
4) PdMoPγ-Al 2 O 3 The hydrodeoxygenation catalyst is filled into a fixed bed catalyst. The method comprises the steps of taking soybean oil methyl ester as a raw material, and injecting the soybean oil methyl ester raw material into a fixed bed reactor by using a high-pressure plunger pump to carry out hydrodeoxygenation reaction. Under the hydrogen pressure of 1.5 MPa, the volume ratio of hydrogen to oil is 1100, the reaction temperature is 335 ℃, and the mass space velocity of the soybean oil methyl ester is 0.5 h -1 In PdMoPγ-Al 2 O 3 Under the action of the hydrodeoxygenation catalyst, carrying out hydrodeoxygenation reaction to obtain C 15-18 The alkane liquid product is continuously reacted for 40 hours, sampled and analyzed, the conversion rate of the soybean oil methyl ester is 99.1 percent, and C 15-18 The alkane yield reaches 87.1 percent, C 15~18 The alkane yields were 1.12%, 9.95%, 6.35%, and 69.67%, respectively.
In the preparation processes of the catalysts in the embodiments 1 to 3, the amounts of diammonium hydrogen phosphate added are different, so that PdMoP/gamma-Al is finally obtained 2 O 3 Hydrodeoxygenation catalysts have varying phosphorus content and the active components of the catalyst may not have completely formed the bimetallic phosphide either. It can be seen that the liquid product C increases with the increase of the P content while keeping the Pd content and the Mo content constant 15~18 The yield drops slightly, probably because too much P causes the catalyst to be relatively too acidic in strong acid, so that some of the feedstock is cracked.
Comparative example 1:
1) Preparing a catalyst carrier: weighing 20.0 g of pseudo-boehmite powder and 1.0 g of sesbania powder, uniformly mixing, adding 5 mL of deionized water, and dropwise adding two drops of 98% HNO 3 Adding deionized water until the mixed powder of pseudoboehmite powder and sesbania powder is full of viscosity, kneading into dough, extruding into fine strips (diameter 2 mm) with a strip extruder, and oven drying at 105 deg.C for 4 hr in a blast-type oven. And taking out the dried strips, and roasting for 4 hours in a muffle furnace at 500 ℃. And cutting the thin strips into small strips with the length of 3-5 mm after fully cooling. The small strips are catalyst carriersγ-Al 2 O 3 。
2) Preparing a catalyst precursor: dissolving palladium chloride and ammonium molybdate tetrahydrate in water to prepare a precursor solution; the catalyst carrier gamma-Al obtained in the step 1) 2 O 3 Soaking the precursor solution in an isometric soaking method for 12 hours at room temperature, drying at 105 ℃ to evaporate water, and roasting at 500 ℃ in an air atmosphere for 4 hours to obtain the catalyst precursor.
And 3) performing EDS (electron-directed spectroscopy) analysis on the catalyst precursor obtained in the step 2) to determine the composition content of Pd and Mo elements in the catalyst precursor. The EDS energy spectrum analysis result is as follows: in the obtained catalyst precursor, the mass of the metal element Pd was 0.5% of the mass of the catalyst carrier, and the mass of the metal element Mo was 9.0% of the mass of the catalyst carrier.
Comparative example 1 NH of catalyst precursor prepared in step 2) 3 The TPD spectrum is shown by the lower dotted line in fig. 3, and it can be seen that the strong acid acidity of the catalyst precursor is somewhat reduced due to the absence of P element.
3) Putting the catalyst precursor in the step 2) into a fixed bed reactor, and adding H with the flow rate of 0.05L/min 2 In the flow, the reduction of the catalyst precursor is carried out at a temperature of 380 ℃ for 3H, reducing H 2 The pressure was 1.0 MPa. The catalyst precursor is reduced to obtain PdMo-γ-Al 2 O 3 A hydrodeoxygenation catalyst.
4) PdMo is combined with the tissue culture mediumγ-Al 2 O 3 The hydrodeoxygenation catalyst is filled into a fixed bed catalyst. The method comprises the steps of taking soybean oil methyl ester as a raw material, and injecting the soybean oil methyl ester raw material into a fixed bed reactor by using a high-pressure plunger pump to carry out hydrodeoxygenation reaction. Under the hydrogen pressure of 1.5 MPa, the volume ratio of hydrogen to oil is 1100, the reaction temperature is 335 ℃, and the mass space velocity of the soybean oil methyl ester is 0.5 h -1 In PdMo-γ-Al 2 O 3 Under the action of the hydrodeoxygenation catalyst, carrying out hydrodeoxygenation reaction to obtain C 15-18 The alkane liquid product is continuously reacted for 40 hours, sampled and analyzed, the conversion rate of the soybean oil methyl ester is 90.90 percent, and C is 15-18 The alkane yield reaches 76.06%，C 15~18 The yields were 1.54%, 8.50%, 11.66% and 54.37%, respectively. In comparison with example 1, it can be seen that the absence of P element reduces the raw material conversion rate of methyl ester of soybean oil, while C 18 The alkane yield was also reduced, presumably due to lack of acidity of the strong acid due to the deletion of P, in conjunction with fig. 3.
Comparative example 2:
1) Preparing a catalyst carrier: weighing 20.0 g of pseudo-boehmite powder and 1.0 g of sesbania powder, uniformly mixing, adding 5 mL of deionized water, and dropwise adding two drops of 98% HNO 3 And adding deionized water into the solution continuously until the mixed powder of the pseudo-boehmite powder and the sesbania powder is full of viscosity, kneading the mixture into a cluster, extruding the cluster into thin strips (the diameter is 2 mm) by using a strip extruding machine, placing the strips into a blast type oven, and drying the strips for 4 hours at the temperature of 105 ℃. And taking out the dried thin strips, and roasting for 4 hours in a muffle furnace at 500 ℃. And cutting the thin strips into small strips with the length of 3-5 mm after fully cooling. The small strips are catalyst carriersγ-Al 2 O 3 。
2) Preparing a catalyst precursor: dissolving palladium chloride and diammonium hydrogen phosphate in water to prepare a precursor solution; the catalyst carrier gamma-Al obtained in the step 1) 2 O 3 Soaking the precursor solution in an isometric soaking method for 12 hours at room temperature, drying at 105 ℃ to evaporate water, and roasting at 500 ℃ in an air atmosphere for 4 hours to obtain the catalyst precursor.
EDS energy spectrum analysis is carried out on the catalyst precursor obtained in the step 2) to determine the composition content of Pd and P elements in the catalyst precursor. The EDS energy spectrum analysis result is as follows: in the obtained catalyst precursor, the mass of the metal element Pd is 0.5 percent of the mass of the catalyst carrier, and the mass of the nonmetal element P is 4.3 percent of the mass of the catalyst carrier;
comparative example 1 NH of catalyst precursor prepared in step 2) 3 The TPD spectrum is shown by the upper dotted line in fig. 3, and it can be seen that the strong acid acidity of the catalyst precursor is greatly increased due to the absence of Mo element. This is probably because the absence of Mo makes P element form a large amount of P-OH components, and further, the P element forms a large amount of P-OH componentsSo that the strong acid acidity of the catalyst precursor is relatively too high.
3) Putting the catalyst precursor in the step 2) into a fixed bed reactor, and adding hydrogen at the flow rate of 0.05L/min 2 The reduction of the catalyst precursor was carried out at a temperature of 380 ℃ in a stream for 3H, reducing H 2 The pressure was 1.0 MPa. The catalyst precursor is reduced to obtain PdP-γ-Al 2 O 3 A hydrodeoxygenation catalyst.
4) PdP is/are combinedγ-Al 2 O 3 The hydrodeoxygenation catalyst is filled into a fixed bed catalyst. The method comprises the steps of taking soybean oil methyl ester as a raw material, and injecting the soybean oil methyl ester raw material into a fixed bed reactor by using a high-pressure plunger pump for carrying out hydrodeoxygenation reaction. Under the hydrogen pressure of 1.5 MPa, the volume ratio of hydrogen to oil is 1100, the reaction temperature is 335 ℃, and the mass space velocity of the soybean oil methyl ester is 0.5 h -1 In PdP-γ-Al 2 O 3 Under the action of the hydrodeoxygenation catalyst, carrying out hydrodeoxygenation reaction to obtain C 15-18 The alkane liquid product is continuously reacted for 40 hours, sampled and analyzed, the conversion rate of the soybean oil methyl ester is 100.00 percent, and C is 15-18 The yield of alkane reaches 98.95 percent, C 15~18 The yields were 5.40%, 4.97%, 52.26% and 36.30%, respectively. It can be seen that the absence of Mo element greatly reduces the C18 yield compared with example 1, probably because the PdP ^ based on comparative example 2γ-Al 2 O 3 The hydrodeoxygenation catalyst has higher strong acid acidity, and the excessive strong acid acidity ensures that the deoxygenation path of the soybean oil methyl ester is mainly deacidification/decarboxylation, thereby greatly reducing the yield of the C18 alkane.
The catalyst adopts PdMoP-γ-Al 2 O 3 The hydrodeoxygenation catalyst has the combined synergistic effect of a high-content weak-acid site and a proper-content strong-acid site, so that the route of the hydrodeoxygenation catalytic reaction of the soybean oil methyl ester is mainly in the deoxygenation form of the generated water, and the reaction product has a high-content C18 alkane product with a high added value.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (5)
1. The application of a hydrodeoxygenation catalyst is characterized in that the hydrodeoxygenation catalyst is used for catalyzing fatty acid methyl ester to prepare long-chain normal paraffin, and comprises the following steps: filling the hydrodeoxygenation catalyst into a fixed bed reactor, inputting a fatty acid methyl ester raw material and hydrogen into the fixed bed reactor at a reaction temperature to carry out hydrodeoxygenation reaction, wherein the length of a carbon chain at a fatty acid part of the fatty acid methyl ester is 16-18, and discharging a long-chain n-alkane product from the fixed bed reactor;
the hydrodeoxygenation catalyst comprisesγ-Al 2 O 3 Carrier and carrier supported onγ-Al 2 O 3 Bimetallic phosphide PdMoP on a carrier; in the double-metal phosphide PdMoP, the mass of the metal element Pd is as followsγ-Al 2 O 3 0.2-0.8% of the mass of the carrier, and the mass of the metal element Mo is calculated asγ-Al 2 O 3 9.0-10.0% of the mass of the carrier, and the mass of the non-metallic element P is calculated asγ-Al 2 O 3 1.6 to 3.0 percent of the mass of the carrier.
2. Use of a hydrodeoxygenation catalyst as claimed in claim 1, characterised in that the preparation process of the hydrodeoxygenation catalyst comprises the following steps:
1) Preparing a catalyst carrier: mixing pseudoboehmite powder and sesbania powder uniformly, adding a small amount of deionized water, and then dropwise adding a small amount of 93-98% concentrated HNO 3 Adding deionized water until the powder is full of viscosity to obtain Gaohuang mixture; kneading the obtained Gaohuang mixture into a dough, extruding the dough into thin strips, drying the strips, and then placing the strips in a muffle furnace to be roasted for 3 to 5h under the air atmosphere at the temperature of 500 to 750 ℃ to obtain a catalyst carrierγ-Al 2 O 3 ；
2) Preparing a catalyst precursor: the catalyst carrier obtained in the step 1)γ-Al 2 O 3 Soaking in mixed aqueous solution of palladium source, molybdenum source and phosphorus source at room temperature by an equal volume soaking methodSoaking for 6 to 24 hours to load a palladium source, a molybdenum source and a phosphorus source on a catalyst carrierγ-Al 2 O 3 Drying at 60-120 ℃ until the water is completely volatilized, and then roasting at 400-700 ℃ for 3-6 h in an air atmosphere to prepare a catalyst precursor;
3) Preparation of catalyst product: and (3) placing the catalyst precursor obtained in the step 2) in a tubular furnace, and calcining and reducing at the temperature of 350-400 ℃ for 2-5 h in a hydrogen atmosphere, wherein the hydrogen pressure for calcining and reducing is 0.5-2.5 MPa, so as to finally obtain the hydrodeoxygenation catalyst.
3. The use of the hydrodeoxygenation catalyst according to claim 2, wherein in the step 1), the mass ratio of the pseudoboehmite powder to the sesbania powder is 15 to 25: 1, and the sesbania powder and the concentrated HNO are mixed 3 The mass ratio of the solution is 5-20: 1.
4. Use of a hydrodeoxygenation catalyst as claimed in claim 2, characterised in that in step 2) the palladium source is palladium chloride or palladium nitrate, the molybdenum source is ammonium molybdate tetrahydrate and the phosphorus source is diammonium hydrogen phosphate.
5. The use of the hydrodeoxygenation catalyst as claimed in claim 1, characterized in that the reaction temperature is 315 to 375 ℃, the pressure of hydrogen input into the fixed bed reactor is 1.0 to 2.5 MPa, and the volume ratio of hydrogen to oil is 400 to 1900.
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