CN117839735A - Multifunctional catalyst for preparing biological aviation kerosene by hydroisomerization of grease and preparation method thereof - Google Patents

Multifunctional catalyst for preparing biological aviation kerosene by hydroisomerization of grease and preparation method thereof Download PDF

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CN117839735A
CN117839735A CN202410004667.2A CN202410004667A CN117839735A CN 117839735 A CN117839735 A CN 117839735A CN 202410004667 A CN202410004667 A CN 202410004667A CN 117839735 A CN117839735 A CN 117839735A
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catalyst
equal
hydroisomerization
grease
salt
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殷长龙
郭永强
刘晨光
闫瑜
韩沂杭
李新月
李振京
哈力米热卡热木拉提
赵会吉
刘宾
刘�东
柴永明
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China University of Petroleum East China
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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
    • 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
    • C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
    • C10G3/46—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof in combination with chromium, molybdenum, tungsten metals or compounds thereof
    • 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
    • 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
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a multifunctional catalyst for preparing biological aviation kerosene by hydroisomerization of grease and a preparation method thereof, belonging to the field of preparing biodiesel or biological aviation kerosene by hydrogenating biological grease and biomass. The catalyst of the invention is non-supported Mo 2 NiP x W y M z Wherein x is more than or equal to 0.6 and less than or equal to 1.2, y is more than or equal to 0 and less than or equal to 2.0, z is more than or equal to 0 and less than or equal to 1.0, and y+z is more than or equal to 0.1, and the metal M is one of Nb, la and Ce. AddingAdding an aqueous solution of a soluble solid compound containing a metal such as W, nb; and cooling, adding a pore-expanding agent and a binder, continuously stirring to form a paste, drying, extruding, forming, drying and calcining to obtain the multifunctional non-supported oil hydroisomerization catalyst. The method disclosed by the invention is simple in preparation process, environment-friendly, pollution-free, mild in preparation condition, good in hydrodeoxygenation activity, strong in acidity, high in isoparaffin selectivity, low in price, free of noble metals and capable of meeting the production requirements of low-condensation-point biological aviation kerosene and biodiesel.

Description

Multifunctional catalyst for preparing biological aviation kerosene by hydroisomerization of grease and preparation method thereof
Technical Field
The invention belongs to the field of biodiesel or biological aviation kerosene prepared by hydrogenating biological grease and biomass, and particularly relates to a method for preparing multifunctional non-supported catalyst with hydrodeoxygenation, isomerization and aromatization simultaneously and preparing biological aviation kerosene by using the multifunctional non-supported catalyst for hydroisomerization of the grease.
Background
With the increasing exhaustion of global reserves of petroleum in recent years, we are pressing to find a substitute for fossil fuels. Biological grease is always considered as an environment-friendly renewable resource, has low nitrogen, sulfur and aromatic hydrocarbon content and high fuel performance, and is an ideal petroleum substitute. However, because of the high oxygen content and high unsaturation in oils and fats, hydrodeoxygenation (HDO) is required to improve the oxidative stability and oil quality. The isoparaffin is a product obtained after the isomerization reaction of normal paraffins, is an important component of gasoline, diesel oil or aviation kerosene, greatly reduces the low-temperature fluidity of the three components, can be mixed with petroleum-based oil in any proportion in a low-temperature environment, and is a key for producing low-condensation-point oil. When the catalyst is more acidic, the cyclic alkane may undergo a cyclic alkylation and aromatization reaction at the acidic site to produce cycloalkane and aromatic hydrocarbon, wherein the aromatic hydrocarbon is one of substances necessary for increasing the lubricity of the oil, and thus the production of high-stability bio-oil with high content of isoparaffin and aromatic hydrocarbon becomes a research hotspot.
There are many kinds of biological grease hydrodeoxygenation and isomerization catalysts, and at this time, the catalysts are required to have excellent hydrogenation activity and sufficient number of strong acid sites capable of ensuring isomerization reaction. The hydrogenation activity of the noble metal catalyst is high naturally, but the wide application of the noble metal catalyst is limited due to the expensive price and the scarcity of resources, so that the industrialization process of the noble metal catalyst is restrained; the deoxidization activity of the sulfide catalyst is excellent, but the activity of the catalyst is gradually reduced in the reaction process, and the catalyst activity is maintained by additionally supplementing a vulcanizing agent, so that certain sulfur pollution to the biological oil is unavoidable; the disadvantages of high synthesis cost, easy loss of active sites, many defects of pore structure properties, insufficient deoxidizing activity and the like of the metal carbide or nitride catalyst prevent industrial application. Some catalysts have better catalytic activity at temperatures above 500 ℃, but have high energy consumption at high temperatures, and the sintering of the catalyst surface is easy to cause the coverage of active sites, so that the catalytic activity is reduced, and the hydrodeoxygenation and isomerization rate are reduced.
Chinese patent CN109833906B discloses Pd-Ni with hierarchical porous nano SAPO-31 molecular sieve as carrier 2 The P hydroisomerization bifunctional catalyst is used for hydroisomerizing vegetable oil hydrodeoxygenation oil to prepare low-condensation-point biodiesel, the catalyst has high reaction activity and isomerization selectivity, and the biodiesel yield is good, but the introduction of noble metal Pd can limit industrialized application, and the load capacity of the supported catalyst is not well controlled and is limited. Chinese patent CN116328830A discloses a sulfurized hydroisomerization catalyst prepared from Mo source and molecular sieve through in-situ sulfurizing, and preparing fatty acid and its fatty acidThe methyl ester oil product is subjected to hydrodeoxygenation isomerization. The catalyst prepared by the method has mild acidity and low cracking rate, but the catalyst has higher selectivity to straight-chain alkane and lower selectivity to isoparaffin, which is about 30% at most, and the catalyst still needs to be lifted; in addition, sulfur powder is required to be continuously added in the reaction process of the catalyst to maintain the sulfur-containing environment and the activity of the catalyst, so that sulfur pollution of different degrees can be caused to the obtained oil product. Chinese patent CN110871083a discloses a method of using non-loaded Ni x Nb y O z As a catalyst, oleic acid and stearic acid are subjected to hydrodeoxygenation treatment and show good catalytic performance. This reflects that hydrodeoxygenation of fats and oils with unsupported catalysts is feasible and avoids the limitation of carriers on active components, with simple operation. Therefore, it is important to develop a sulfur-free catalyst with simple preparation method, low cost, green pollution-free, good hydrogenation activity and high isoparaffin selectivity.
Disclosure of Invention
The invention aims to provide a preparation method of a multifunctional catalyst for preparing biological aviation kerosene by oil hydroisomerization, which has the advantages of good hydrodeoxygenation activity, high isoparaffin selectivity, strong acidity, low price, no need of noble metal and the like, and the preparation method is simple in preparation process, environment-friendly, pollution-free and mild in preparation condition, and the obtained catalyst can meet the production requirement of low-condensation-point oil products.
The technical scheme of the catalyst is as follows:
(1) Mixing molybdenum trioxide (ammonium molybdate or phosphomolybdic acid), basic nickel carbonate (nickel acetate or nickel nitrate) and phosphoric acid in an autoclave according to the mol ratio of MoNiP of 2:1:0.6-1.2, and the mass m Molybdenum-containing compound :m Deionized water Deionized water is added in a ratio of (0.3:1), and the mixture is continuously stirred for 1.5 to 2.5 hours at the temperature of 60 to 150 ℃ to obtain a green transparent MoNiP solution;
(2) Sequentially adding ammonium meta-tungstate (ammonium tungstate or phosphotungstic acid) and aqueous solution of hydrated niobium oxalate (ammonium niobate oxalate hydrate) or lanthanum acetate (lanthanum chloride or lanthanum nitrate) or cerium acetate (cerium nitrate or cerium ammonium nitrate) into the green transparent solution obtained in the step (1) according to the molar ratio of MoNiPWM of 2:1:0.6-1.2:0-2.0:0-1.0, adding the aqueous solution for 0.5-1 h at intervals of 0.5-150 ℃ for two times, and continuously stirring for 0.5-1 h to obtain MoNiPWM mixed solution;
(3) Cooling the mixed solution obtained in the step (2) to room temperature, and sequentially adding 1-5 wt% of methyl cellulose and 0-30 wt% of pseudo-boehmite, wherein the interval between the two adding steps is 0.5-1 h; stirring for 0.5-1 h at room temperature to obtain MoNiPWM paste;
(4) Slightly drying the paste, extruding to form strips, and transferring to an oven at 80-120 ℃ for drying for 8-12 h; and then transferring the catalyst into a muffle furnace, calcining the catalyst for 2 to 6 hours at the temperature of 450 to 550 ℃, and cooling to obtain the multifunctional non-supported oil hydroisomerization catalyst.
(5) Before the multifunctional non-load grease hydroisomerization catalyst is used, the multifunctional non-load grease hydroisomerization catalyst is activated for 8 to 12 hours under the conditions of the temperature of 400 to 500 ℃ and the hydrogen pressure of 1 to 4 MPa.
Drawings
FIGS. 1 a and b are respectively the Mo in comparative example 1 2 NiP 0.8 Catalyst and Mo in example 4 2 NiP 0.8 W 0.5 Nb 0.5 Partial product liquid chromatogram of hydroisomerization reaction of methyl stearate under the catalysis of catalyst.
The process according to the invention is described in further detail below by way of comparative examples and examples: :
comparative example
11.52g of molybdenum trioxide, 5.02g of basic nickel carbonate and 3.14g of phosphoric acid are mixed in an autoclave, 38mL of deionized water is added and stirring is continued for 2 hours at 90 ℃ to obtain a green transparent MoNiP solution; after the obtained green transparent solution is cooled to room temperature, 0.74g of methyl cellulose and 10.31g of pseudo-boehmite are sequentially and respectively added under the stirring condition, and the intervals of the two are 30 minutes; stirring at room temperature for 30min to obtain paste. Slightly drying the paste, extruding to form strips, and transferring to an 80 ℃ oven for drying for 12 hours; then transferring the catalyst into a muffle furnace, calcining for 4 hours at 500 ℃, and cooling to obtain the catalyst Mo 2 NiP 0.8 This was designated Cat-0.
Example 1
In an autoclave, 11.52g of molybdenum trioxide, 5.02g of basic nickel carbonate and 3.14g of phosphoric acid were mixed and 38mL of deionized water was addedContinuously stirring the child water at 90 ℃ for 2 hours to obtain a green transparent MoNiP solution; adding 0.99g of ammonium metatungstate dissolved to prepare an aqueous solution into the obtained MoNiP solution, and stirring for 30min at 90 ℃ to obtain a MoNiPW mixed solution; after the obtained mixed solution is cooled to room temperature, 0.79g of methylcellulose and 10.88g of pseudo-boehmite are sequentially and respectively added under the stirring condition, and the intervals are 30 minutes; stirring at room temperature for 30min to obtain paste. Slightly drying the paste, extruding to form strips, and transferring to an 80 ℃ oven for drying for 12 hours; then transferring the catalyst into a muffle furnace, calcining for 4 hours at 500 ℃, and cooling to obtain the catalyst Mo 2 NiP 0.8 W 0.1 This was designated Cat-1.
Example 2
11.52g of molybdenum trioxide, 5.02g of basic nickel carbonate and 3.14g of phosphoric acid are mixed in an autoclave, 38mL of deionized water is added and stirring is continued for 2 hours at 90 ℃ to obtain a green transparent MoNiP solution; adding 4.93g of ammonium metatungstate dissolved to prepare an aqueous solution into the obtained MoNiP solution, and stirring for 30min at 90 ℃ to obtain a MoNiPW mixed solution; after the obtained mixed solution is cooled to room temperature, 0.95g of methylcellulose and 13.15g of pseudo-boehmite are sequentially and respectively added under the stirring condition, and the intervals are 30 minutes; stirring at room temperature for 30min to obtain paste. Slightly drying the paste, extruding to form strips, and transferring to an 80 ℃ oven for drying for 12 hours; then transferring the catalyst into a muffle furnace, calcining for 4 hours at 500 ℃, and cooling to obtain the catalyst Mo 2 NiP 0.8 W 0.5 This was designated Cat-2.
Example 3
11.52g of molybdenum trioxide, 5.02g of basic nickel carbonate and 3.14g of phosphoric acid are mixed in an autoclave, 38mL of deionized water is added and stirring is continued for 2 hours at 90 ℃ to obtain a green transparent MoNiP solution; 9.85g of ammonium metatungstate is dissolved to prepare an aqueous solution, and the aqueous solution is added into the obtained MoNiP solution and stirred for 30min at 90 ℃ to obtain a MoNiPW mixed solution; after the obtained mixed solution is cooled to room temperature, 1.15g of methylcellulose and 15.99g of pseudo-boehmite are sequentially and respectively added under the stirring condition, and the intervals are 30 minutes; stirring at room temperature for 30min to obtain paste. Slightly drying the paste, extruding to form strips, and transferring to an 80 ℃ oven for drying for 12 hours; it was then transferred to a muffle furnace for calcination at 500 c for 4 hours,cooling to obtain the catalyst Mo 2 NiP 0.8 W 1.0 This was designated Cat-3.
Example 4
11.52g of molybdenum trioxide, 5.02g of basic nickel carbonate and 3.14g of phosphoric acid are mixed in an autoclave, 38mL of deionized water is added and stirring is continued for 2 hours at 90 ℃ to obtain a green transparent MoNiP solution; respectively dissolving 4.93g of ammonium metatungstate and 10.76g of hydrated niobium oxalate to prepare aqueous solutions, sequentially adding the aqueous solutions into the obtained MoNiP solution, and continuously stirring at 90 ℃ at intervals of 30min; and (3) reacting for 1h to obtain the MoNiPWNb mixed solution. After the obtained mixed solution is cooled to room temperature, 1.07g of methylcellulose and 14.78g of pseudo-boehmite are sequentially and respectively added under the stirring condition, and the intervals are 30 minutes; stirring at room temperature for 30min to obtain paste. Slightly drying the paste, extruding to form strips, and transferring to an 80 ℃ oven for drying for 12 hours; then transferring the catalyst into a muffle furnace, calcining for 4 hours at 500 ℃, and cooling to obtain the catalyst Mo 2 NiP 0.8 W 0.5 Nb 0.5 This was designated Cat-4.
Example 5
11.52g of molybdenum trioxide, 5.02g of basic nickel carbonate and 3.14g of phosphoric acid are mixed in an autoclave, 38mL of deionized water is added and stirring is continued for 2 hours at 90 ℃ to obtain a green transparent MoNiP solution; respectively dissolving 4.93g of ammonium metatungstate and 6.32g of lanthanum acetate to prepare aqueous solutions, sequentially adding the aqueous solutions into the obtained MoNiP solution, and continuously stirring at 90 ℃ at intervals of 30min; and (3) reacting for 1h to obtain the MoNiPWA mixed solution. After the obtained mixed solution is cooled to room temperature, 1.09g of methylcellulose and 15.15g of pseudo-boehmite are sequentially and respectively added under the stirring condition, and the intervals are 30 minutes; stirring at room temperature for 30min to obtain paste. Slightly drying the paste, extruding to form strips, and transferring to an 80 ℃ oven for drying for 12 hours; then transferring the catalyst into a muffle furnace, calcining for 4 hours at 500 ℃, and cooling to obtain the catalyst Mo 2 NiP 0.8 W 0.5 La 0.5 This was designated Cat-5.
Example 6
11.52g of molybdenum trioxide, 5.02g of basic nickel carbonate and 3.14g of phosphoric acid were mixed in an autoclave, 38mL of deionized water was added and stirring was continued at 90℃for 2 hours to give a green colorTransparent MoNiP solution; respectively dissolving 4.93g of ammonium metatungstate and 6.35g of cerium acetate to prepare aqueous solutions, sequentially adding the aqueous solutions into the obtained MoNiP solution, and continuously stirring at 90 ℃ at intervals of 30min; and (3) reacting for 1h to obtain the MoNiPWCe mixed solution. After the obtained mixed solution is cooled to room temperature, 1.10g of methylcellulose and 15.26g of pseudo-boehmite are sequentially and respectively added under the stirring condition, and the intervals are 30 minutes; stirring at room temperature for 30min to obtain paste. Slightly drying the paste, extruding to form strips, and transferring to an 80 ℃ oven for drying for 12 hours; then transferring the catalyst into a muffle furnace, calcining for 4 hours at 500 ℃, and cooling to obtain the catalyst Mo 2 NiP 0.8 W 0.5 Ce 0.5 This was designated Cat-6.
Example 7
This example illustrates a method for evaluating catalyst activity.
2mL of the catalyst was activated and reduced in a fixed bed apparatus at 380℃under a hydrogen pressure of 3MPa and a hydrogen flow rate of 30mL/min for 8 hours. Then at 360 ℃ under 3MPa of hydrogen pressure and 3h of liquid hourly space velocity -1 And a hydrogen-to-oil ratio of 300:1, which was hydroisomerized using 10wt% methyl stearate/cyclohexane as a feedstock.
The following table shows the distribution results of the catalyst of the present invention on the product of the hydroisomerization reaction of methyl stearate. Wherein n-C 5～18 i-C is the content of n-alkane with 5-18 carbon atoms in the product 5～18 The different proportion is i-C, the content of isoparaffin with 5-18 carbon numbers in the product 5～18 /n-C 5～18 The value of C 9～14 The content of alkane (normal structure and isomerization) with the carbon number of 9-14 in the product is the content of alkane in the range of aviation kerosene fraction.
TABLE 1 distribution table of the catalyst of the invention for the hydroisomerization reaction products of methyl stearate
Table 1 above lists the product distributions of the hydroisomerization reactions of methyl stearate over different catalysts. From the data, it can be seen that the grease prepared by the method of the inventionUnder the catalysis of the hydroisomerization catalyst, the content of isoparaffin is greatly improved. Mo in example 4 2 NiP 0.8 W 0.5 Nb 0.5 C in the reaction product of the catalyst 5～18 The content of isoparaffin is highest and can reach 66.76%, the isoparaffin content in the products of other catalysts is 3.60% or more, which indicates that the catalyst prepared by the method has higher isoparaffin selectivity, can increase the low-temperature fluidity of oil products and meets the production requirement of aviation kerosene with low condensation point; in addition, the contents of aromatic hydrocarbons and naphthenes in the reaction products of the catalysts prepared by the process of the present invention are increased to various extents, wherein both of them are Mo in example 4 2 NiP 0.8 W 0.5 Nb 0.5 The highest content of the reaction products of the catalyst respectively contains 9.57 percent of aromatic hydrocarbon and 4.41 percent of naphthene, which shows that the acidity of the catalyst prepared by the method is improved, so that partial alkane is subjected to aromatization and naphthenation reactions, and the aromatic hydrocarbon is required for increasing the lubricity of aviation kerosene; finally, it can also be seen from the table that the alkane component content in the aviation kerosene fraction range of the catalyst prepared is also greatly increased, wherein Mo in example 4 2 NiP 0.8 W 0.5 Nb 0.5 The alkane component content of the aviation kerosene fraction range of the catalyst is maximum and can reach 54.03 percent. In conclusion, the catalyst prepared by the method has high hydrodeoxygenation and isomerization activity and good selectivity to alkane of aviation kerosene components, and completely meets the production requirements of aviation kerosene with low condensation point and high oxidation stability.
FIGS. 1 a and b are respectively the Mo in comparative example 1 2 NiP 0.8 Catalyst and Mo in example 4 2 NiP 0.8 W 0.5 Nb 0.5 Partial liquid product gas chromatogram of hydroisomerization reaction of methyl stearate under the catalysis of catalyst. It can be seen that the isoparaffin content is greatly increased under the catalysis of the catalyst prepared by the method, and the isoparaffin selectivity is increased, i.e. the catalyst has excellent hydroisomerization performance.
The foregoing description is that of the preferred embodiments of the invention, but is not limited to certain specific details, and certain simple modifications and variations can be made to the technical solution without departing from the scope of the technical idea of the invention, but all such modifications and variations fall within the scope of the invention.

Claims (8)

1. Multifunctional catalyst for preparing biological aviation kerosene by hydroisomerization of grease and bulk active component molar composition of Mo 2 NiP x W y M z Wherein x is more than or equal to 0.6 and less than or equal to 1.2, y is more than or equal to 0 and less than or equal to 2.0, z is more than or equal to 0 and less than or equal to 1.0, and y+z is more than or equal to 0.1, and the metal M is one of Nb, la and Ce, and is characterized in that the preparation of the catalyst comprises the following steps:
(1) Mixing a solid molybdenum-containing compound, a nickel-containing compound and phosphoric acid in an autoclave according to the mol ratio of MoNiP of 2:1:0.6-1.2, and the mass m Molybdenum-containing compound :m Deionized water Deionized water is added in a ratio of (0.3:1), and the mixture is continuously stirred for 1.5 to 2.5 hours at the temperature of 60 to 150 ℃ to obtain green transparent solution;
(2) Sequentially adding water solution of soluble tungsten salt, soluble niobium salt or lanthanum salt or cerium salt into the green transparent solution obtained in the step (1) according to the molar ratio of MoNiPWM of 2:1:0.6-1.2:0-2.0:0-1.0, wherein the adding interval is 0.5-1 h for two times, and then continuously stirring at 60-150 ℃ for 0.5-1 h to obtain MoNiPWM mixed solution;
(3) Cooling the mixed solution obtained in the step (2) to room temperature, sequentially adding 1-5 wt% of methyl cellulose and 0-30 wt% of pseudo-boehmite for 0.5-1 h at intervals, and then continuing stirring at room temperature for 0.5-1 h to obtain MoNiPWM paste;
(4) Slightly drying the paste, extruding to form strips, transferring to an oven at 80-120 ℃ for drying for 8-12 h, transferring to a muffle furnace, calcining at 450-550 ℃ for 2-6 h, and cooling to obtain the multifunctional non-load grease hydroisomerization catalyst;
(5) Before the multifunctional non-load grease hydroisomerization catalyst is used, the multifunctional non-load grease hydroisomerization catalyst is activated for 8 to 12 hours under the conditions of the temperature of 400 to 500 ℃ and the hydrogen pressure of 1 to 4 MPa.
2. The catalyst of claim 1, wherein: the solid molybdenum-containing compound is molybdenum trioxide or ammonium molybdate or phosphomolybdic acid.
3. The catalyst of claim 1, wherein: the solid nickel-containing compound is basic nickel carbonate or nickel acetate or nickel nitrate.
4. The catalyst of claim 1, wherein: the soluble tungsten salt is ammonium metatungstate or phosphotungstic acid or ammonium tungstate.
5. The catalyst of claim 1, wherein: the soluble niobium salt is hydrated niobium oxalate or ammonium niobate oxalate hydrate.
6. The catalyst of claim 1, wherein: the soluble lanthanum salt is lanthanum acetate or lanthanum chloride or lanthanum nitrate.
7. The catalyst of claim 1, wherein: the soluble cerium salt is cerium acetate or cerium nitrate or ammonium cerium nitrate.
8. The use of the catalyst according to claim 1 in the preparation of biodiesel or bio-aviation kerosene by hydrogenation of biological oil and biomass.
CN202410004667.2A 2024-01-03 2024-01-03 Multifunctional catalyst for preparing biological aviation kerosene by hydroisomerization of grease and preparation method thereof Pending CN117839735A (en)

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