CN116651476A - Zirconium phosphate grease hydrodeoxygenation catalyst loaded with transition metal - Google Patents
Zirconium phosphate grease hydrodeoxygenation catalyst loaded with transition metal Download PDFInfo
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- CN116651476A CN116651476A CN202310854691.0A CN202310854691A CN116651476A CN 116651476 A CN116651476 A CN 116651476A CN 202310854691 A CN202310854691 A CN 202310854691A CN 116651476 A CN116651476 A CN 116651476A
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- transition metal
- zirconium phosphate
- grease
- hydrodeoxygenation
- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 239000004519 grease Substances 0.000 title claims abstract description 43
- 229910000166 zirconium phosphate Inorganic materials 0.000 title claims abstract description 41
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 title claims abstract description 41
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 37
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- -1 transition metal salt Chemical class 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims description 45
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000007873 sieving Methods 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000002028 Biomass Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000011973 solid acid Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- VQYKQHDWCVUGBB-UHFFFAOYSA-N phosphanylidynezirconium Chemical compound [Zr]#P VQYKQHDWCVUGBB-UHFFFAOYSA-N 0.000 claims description 2
- 150000003754 zirconium Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 2
- 238000010025 steaming Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 10
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 3
- 239000012075 bio-oil Substances 0.000 abstract description 3
- 229930195733 hydrocarbon Natural products 0.000 abstract description 3
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 3
- 235000019482 Palm oil Nutrition 0.000 abstract 1
- 239000002540 palm oil Substances 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000002161 passivation Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- FLIACVVOZYBSBS-UHFFFAOYSA-N Methyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC FLIACVVOZYBSBS-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 6
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000003225 biodiesel Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/082—Decomposition and pyrolysis
-
- 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
-
- 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
-
- 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
- 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
- C10G2300/1011—Biomass
-
- 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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
-
- 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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
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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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- 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)
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Abstract
The invention discloses a transition metal-loaded zirconium phosphate grease hydrodeoxygenation catalyst and a preparation method and application thereof, and belongs to the technical field of bio-oil hydrodeoxygenation catalysts. Zirconium phosphate and transition metal salt are used as raw materials, and the transition metal supported zirconium phosphate catalyst is impregnated by incipient wetness. The transition metal-loaded zirconium phosphate grease hydrodeoxygenation catalyst has the biological grease conversion rate of more than 95 percent and the hydrocarbon selectivity of more than 90 percent, realizes the hydrodeoxygenation process of palm oil, waste grease and other biological grease under mild conditions, and has good dispersity and repeated cycle performance of active components and wide application prospect.
Description
Technical Field
The invention belongs to the technical field of bio-oil hydrodeoxygenation catalysts, and particularly relates to a transition metal-loaded zirconium phosphate grease hydrodeoxygenation catalyst, and a preparation method and application thereof.
Background
With the rapid development of economy, the global consumption and demand for energy have increased. Currently, the world's most dominant energy resources are still fossil resources such as coal, natural gas and petroleum. Fossil resources are considered as non-renewable resources because of extremely long formation cycles and extremely severe formation conditions. Meanwhile, the development of human society is seriously affected by the energy shortage problem caused by excessive consumption of fossil resources and the environmental problem caused by the greenhouse gases discharged by combustion. In order to solve the current energy crisis problem, the exploration of renewable energy sources such as nuclear energy, solar energy, wind energy, tidal energy, geothermal energy and the like is greatly increased in the world.
Biomass has received attention as a renewable organic carbon source, in which bio-oil has a carbon chain structure similar to that of petroleum diesel, and the oil has low cost, good renewable properties, and good environmental friendliness without nitrogen/sulfur. However, the grease contains a large amount of ester groups, carboxyl groups and unsaturated bonds, and the direct use as fuel has problems of low calorific value, high viscosity, poor stability, poor fluidity, low energy density and the like, so that it is required to upgrade the grease to improve the quality thereof. The second generation biodiesel produced by using the biological grease as a raw material through the hydrodeoxygenation technology has high heat value and good fluidity, can be mixed with petrochemical diesel in any proportion, and is an ideal liquid fuel. The core of the second generation biodiesel is the development and development of the high-efficiency hydrodeoxygenation catalyst.
Disclosure of Invention
The invention aims to provide a biological grease hydrodeoxygenation catalyst, which aims to solve the problems of low activity, poor stability and higher cost of a noble metal catalyst of the conventional biological grease hydrodeoxygenation catalyst. The invention takes zirconium phosphate as a carrier to load the transition metal synthetic grease hydrodeoxygenation catalyst, the conversion rate of biological grease exceeds 95 percent, and the hydrocarbon selectivity is as high as more than 90 percent.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a transition metal-loaded zirconium phosphate grease hydrodeoxygenation catalyst is prepared from zirconium phosphate and transition metal salt as raw materials through a primary wet impregnation method.
The zirconium phosphate has a zirconium-phosphorus ratio of 0.25-2.00.
The transition metal salt is one of Fe, co, ni, cu acetate.
The preparation method of the transition metal-loaded zirconium phosphate grease hydrodeoxygenation catalyst comprises the following steps of:
1) Respectively dissolving zirconium salt and ammonium salt in deionized water, and carrying out mixed reaction in a beaker after constant volume to obtain a solid acid suspension;
2) Filtering the suspension, and putting filter residues into a baking oven for baking to obtain white solid;
3) Grinding and sieving the obtained solid;
4) Placing the sieved solid in a muffle furnace for roasting;
5) Stirring the roasted solid and transition metal salt in deionized water;
6) The resulting mixture was subjected to rotary evaporation to remove the solvent, followed by drying, and a solid was obtained.
7) The obtained solid is put into a muffle furnace for roasting.
8) The obtained solid is put into a tube chamber furnace for reduction and passivation. The solid obtained after passivation is the transition metal loaded zirconium phosphate grease hydrodeoxygenation catalyst.
Wherein the load of the transition metal is 5-20%.
The application of the transition metal-loaded zirconium phosphate grease hydrodeoxygenation catalyst in the hydrodeoxygenation reaction of biological grease is as follows: the amount of the zirconium phosphate grease hydrodeoxygenation catalyst loaded with the transition metal is 1-10% of the weight of the biomass oil to be treated, the reaction temperature for hydrodeoxygenation is 280-400 ℃, the hydrogen pressure is 2-6 MPa, and the reaction time is 2-10 h.
The invention has the beneficial effects that:
(1) The acid strength of the transition metal-loaded zirconium phosphate grease hydrodeoxygenation catalyst prepared by the invention is easy to regulate, namely, by regulating the Zr/P ratio, the strong ester cracking reaction caused by excessive acidity can be avoided being a small molecule by-product.
(2) The zirconium phosphate solid acid prepared by the invention is a multi-metal oxide formed by bridging a Zr central atom and a P coordination atom through an oxygen atom, and has acidity and redox. The supported transition metal is used as the hydrogenation active component, and the acidity of zirconium phosphate is mainly used for improving the deoxidizing performance of the catalyst.
(3) The preparation method is simple, does not involve noble metal, has relatively low cost, and shows higher activity and alkane selectivity in the hydrodeoxygenation of the biological grease, wherein the total selectivity of pentadecyl alkane/hexadecane is as high as 90%.
Drawings
FIG. 1 is an XRD spectrum of a transition metal-supported zirconium phosphate grease hydrodeoxygenation catalyst obtained in examples 1 to 3.
Detailed Description
In order that the manner in which the above recited invention is attained and can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to the appended drawings and detailed description thereof, which follow.
Example 1
The preparation method of the transition metal-loaded zirconium phosphate grease hydrodeoxygenation catalyst comprises the following steps:
(1) Weigh 1 mol NH 4 H 2 PO 4 In a beaker, deionized water is used for fixing the volume to 4 mol/L, and the solution is marked as solution A; 1 mol ZrOCl is weighed 2 ·8H 2 O was placed in a beaker and was fixed to a volume of 4 mol/L with deionized water, designated as solution B.
(2) Equal volumes of solutions A and B from step (1) were added to the beaker and stirred at room temperature for 1 h, at 80℃for 3 h.
(3) Filtering and washing the suspension in the step (2).
(4) The solid filtered in the step (3) is placed in a 100 ℃ oven to be dried for 12 h. Grinding and sieving the dried solid.
(5) Placing the solid after sieving in the step (4) in a muffle furnace, heating to 550 ℃ at 5 ℃/min, and roasting 12 h, wherein the obtained solid is named ZrPO x (1)。
(6) The solid (1.90 g) obtained by roasting in the step (5) and 0.43 g nickel acetate tetrahydrate are placed in a flask and stirred for 12 h.
(7) Placing the mixed solution obtained in the step (6) in a rotary evaporator at 80 ℃ to remove the solvent;
(8) And (3) placing the solid obtained in the step (7) in a muffle furnace, and roasting at a speed of 5 ℃/min to 450 ℃ for 3 h.
(9) Placing the sample obtained in the step (8) in a tube furnace at 10 vol% of H 2 Reducing 3 h at 550 ℃ at 5 ℃/min in an Ar atmosphere and at 2 vol% O 2 He normal temperature passivation 12 h. The nickel-supported zirconium phosphate catalyst, designated 5Ni/ZrPO, was obtained x (1)。
Example 2
The preparation method of the transition metal-loaded zirconium phosphate grease hydrodeoxygenation catalyst comprises the following steps:
(1) Weigh 1 mol NH 4 H 2 PO 4 In a beaker, deionized water is used for fixing the volume to 4 mol/L, and the solution is marked as solution A; 1 mol ZrOCl is weighed 2 ·8H 2 O was placed in a beaker and was fixed to a volume of 4 mol/L with deionized water, designated as solution B.
(2) Equal volumes of solutions A and B from step (1) were added to the beaker and stirred at room temperature for 1 h, at 80℃for 3 h.
(3) Filtering and washing the suspension in the step (2).
(4) The solid filtered in the step (3) is placed in a 100 ℃ oven to be dried for 12 h. Grinding and sieving the dried solid.
(5) Placing the solid after sieving in the step (4) in a muffle furnace, heating to 550 ℃ at 5 ℃/min, and roasting 12 h, wherein the obtained solid is named ZrPO x (1)。
(6) The solid (1.80, g) obtained by roasting in the step (5) and 0.86, g nickel acetate tetrahydrate are placed in a flask and stirred for 12, h.
(7) Placing the mixed solution obtained in the step (6) in a rotary evaporator at 80 ℃ to remove the solvent;
(8) And (3) placing the solid obtained in the step (7) in a muffle furnace, and roasting at a speed of 5 ℃/min to 450 ℃ for 3 h.
(9) Placing the sample obtained in the step (8) in a tube furnace at 10 vol% of H 2 Reducing 3 h at 550 ℃ at 5 ℃/min in an Ar atmosphere and at 2 vol% O 2 He normal temperature passivation 12 h. The nickel-supported zirconium phosphate catalyst was obtained and was designated as 10Ni/ZrPO x (1)。
Example 3
The preparation method of the transition metal-loaded zirconium phosphate grease hydrodeoxygenation catalyst comprises the following steps:
(1) Weigh 1 mol NH 4 H 2 PO 4 In a beaker, deionized water is used for fixing the volume to 4 mol/L, and the solution is marked as solution A; 1 mol ZrOCl is weighed 2 ·8H 2 O was placed in a beaker and was fixed to a volume of 4 mol/L with deionized water, designated as solution B.
(2) Equal volumes of solutions A and B from step (1) were added to the beaker and stirred at room temperature for 1 h, at 80℃for 3 h.
(3) Filtering and washing the suspension in the step (2).
(4) The solid filtered in the step (3) is placed in a 100 ℃ oven to be dried for 12 h. Grinding and sieving the dried solid.
(5) Placing the solid after sieving in the step (4) in a muffle furnace, heating to 550 ℃ at 5 ℃/min, and roasting 12 h, wherein the obtained solid is named ZrPO x (1)。
(6) The solid (1.60, g) obtained by roasting in the step (5) and 1.72, g of nickel acetate tetrahydrate are placed in a flask and stirred for 12, h.
(7) Placing the mixed solution obtained in the step (6) in a rotary evaporator at 80 ℃ to remove the solvent;
(8) And (3) placing the solid obtained in the step (7) in a muffle furnace, and roasting at a speed of 5 ℃/min to 450 ℃ for 3 h.
(9) Placing the sample obtained in the step (8) in a tube furnace at 10 vol% of H 2 Reducing 3 h at 550 ℃ at 5 ℃/min in an Ar atmosphere and at 2 vol% O 2 He normal temperature passivation 12 h. The nickel-supported zirconium phosphate catalyst was obtained and was designated 20Ni/ZrPO x (1)。
Example 4
The preparation method of the transition metal-loaded zirconium phosphate grease hydrodeoxygenation catalyst comprises the following steps:
(1) Weigh 2 mol NH 4 H 2 PO 4 In a beaker, deionized water is used for fixing the volume to 8 mol/L, and the solution is marked as solution A; 1 mol ZrOCl is weighed 2 ·8H 2 O was placed in a beaker and was fixed to a volume of 4 mol/L with deionized water, designated as solution B.
(2) Equal volumes of solutions A and B from step (1) were added to the beaker and stirred at room temperature for 1 h, at 80℃for 3 h.
(3) Filtering and washing the suspension in the step (2).
(4) The solid filtered in the step (3) is placed in a 100 ℃ oven to be dried for 12 h. Grinding and sieving the dried solid.
(5) Placing the solid after sieving in the step (4) in a muffle furnace, heating to 550 ℃ at 5 ℃/min, and roasting 12 h, wherein the obtained solid is named ZrPO x (0.5)。
(6) The solid (1.80, g) obtained by roasting in the step (5) and 0.86, g nickel acetate tetrahydrate are placed in a flask and stirred for 12, h.
(7) Placing the mixed solution obtained in the step (6) in a rotary evaporator at 80 ℃ to remove the solvent;
(8) And (3) placing the solid obtained in the step (7) in a muffle furnace, and roasting at a speed of 5 ℃/min to 450 ℃ for 3 h.
(9) Placing the sample obtained in the step (8) in a tube furnace at 10 vol% of H 2 Reducing 3 h at 550 ℃ at 5 ℃/min in an Ar atmosphere and at 2 vol% O 2 He normal temperature passivation 12 h. The nickel-supported zirconium phosphate catalyst was obtained and was designated as 10Ni/ZrPO x (0.5)。
Example 5
The preparation method of the transition metal-loaded zirconium phosphate grease hydrodeoxygenation catalyst comprises the following steps:
(1) Weigh 1 mol NH 4 H 2 PO 4 In a beaker, deionized water is used for fixing the volume to 4 mol/L, and the solution is marked as solution A; weigh 2 mol ZrOCl 2 ·8H 2 O was placed in a beaker and was fixed to a volume of 8 mol/L with deionized water, designated as solution B.
(2) Equal volumes of solutions A and B from step (1) were added to the beaker and stirred at room temperature for 1 h, at 80℃for 3 h.
(3) Filtering and washing the suspension in the step (2).
(4) The solid filtered in the step (3) is placed in a 100 ℃ oven to be dried for 12 h. Grinding and sieving the dried solid.
(5) Placing the solid after sieving in the step (4) in a muffle furnace, heating to 550 ℃ at 5 ℃/min, and roasting 12 h, wherein the obtained solid is named ZrPO x (2)。
(6) The solid (1.80, g) obtained by roasting in the step (5) and 0.86, g nickel acetate tetrahydrate are placed in a flask and stirred for 12, h.
(7) Placing the mixed solution obtained in the step (6) in a rotary evaporator at 80 ℃ to remove the solvent;
(8) And (3) placing the solid obtained in the step (7) in a muffle furnace, and roasting at a speed of 5 ℃/min to 450 ℃ for 3 h.
(9) Placing the sample obtained in the step (8) in a tube furnace at 10 vol% of H 2 Reducing 3 h at 550 ℃ at 5 ℃/min in an Ar atmosphere and at 2 vol% O 2 He normal temperature passivation 12 h. The nickel-supported zirconium phosphate catalyst was obtained and was designated as 10Ni/ZrPO x (2)。
Example 6
The preparation method of the transition metal-loaded zirconium phosphate grease hydrodeoxygenation catalyst comprises the following steps:
(1) Weigh 1 mol NH 4 H 2 PO 4 In a beaker, deionized water was used to determine the volume to 4 mol/L, noted as dissolvedA liquid A; weighing 4 mol ZrOCl 2 ·8H 2 O was placed in a beaker and was fixed to a volume of 16 mol/L with deionized water and designated as solution B.
(2) Equal volumes of solutions A and B from step (1) were added to the beaker and stirred at room temperature for 1 h, at 80℃for 3 h.
(3) Filtering and washing the suspension in the step (2).
(4) The solid filtered in the step (3) is placed in a 100 ℃ oven to be dried for 12 h. Grinding and sieving the dried solid.
(5) Placing the solid after sieving in the step (4) in a muffle furnace, heating to 550 ℃ at 5 ℃/min, and roasting 12 h, wherein the obtained solid is named ZrPO x (4)。
(6) The solid (1.80, g) obtained by roasting in the step (5) and 0.86, g nickel acetate tetrahydrate are placed in a flask and stirred for 12, h.
(7) Placing the mixed solution obtained in the step (6) in a rotary evaporator at 80 ℃ to remove the solvent;
(8) And (3) placing the solid obtained in the step (7) in a muffle furnace, and roasting at a speed of 5 ℃/min to 450 ℃ for 3 h.
(9) Placing the sample obtained in the step (8) in a tube furnace at 10 vol% of H 2 Reducing 3 h at 550 ℃ at 5 ℃/min in an Ar atmosphere and at 2 vol% O 2 He normal temperature passivation 12 h. The nickel-supported zirconium phosphate catalyst was obtained and was designated as 10Ni/ZrPO x (4)。
As can be seen from the XRD spectrum of fig. 1, the transition metal-loaded zirconium phosphate grease hydrodeoxygenation catalyst sample has a distinct nickel signal peak, and the nickel signal peak becomes more and more distinct as the metal content increases.
Hydrodeoxygenation activity test of suspended bed biological grease
The transition metal-loaded zirconium phosphate grease hydrodeoxygenation catalyst prepared in the example is subjected to a grease hydrodeoxygenation activity test, and the specific operation is as follows: methyl palmitate is taken as a biological grease raw material, the addition amount of the methyl palmitate is 50.0g, the addition amount of the catalyst is 2.0 g (the addition amount is 4 wt%), the initial hydrogen pressure is 6 MPa, and the reaction time is 4 h after the hydrodeoxygenation reaction is carried out by heating to 360 ℃ at the speed of 5 ℃/min. The test results are shown in Table 1.
As can be seen from table 1, the introduction of nickel significantly improved the hydrodeoxygenation properties of the grease. With the increase of the loading, the catalytic activity tends to be improved first and then reduced, and the activity is highest when the loading of nickel is 10%.
As can be seen from Table 2, changing the ratio of zirconium to phosphorus has a large effect on the hydrodeoxygenation performance of the catalyst, and when the ratio of zirconium to phosphorus is 1, the conversion of methyl palmitate is 97.1% and the hydrocarbon selectivity is 95.4%.
While the invention has been described in detail with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes in form and details can be made therein without departing from the scope of the invention encompassed by the appended claims.
Claims (7)
1. A transition metal-loaded zirconium phosphate grease hydrodeoxygenation catalyst is characterized in that: zirconium phosphate and transition metal salt are used as raw materials, and a primary wet impregnation method is adopted to prepare the transition metal-loaded zirconium phosphate grease hydrodeoxygenation catalyst.
2. The catalyst of claim 1, wherein: the zirconium phosphate has a zirconium-phosphorus ratio of 0.25-2.00.
3. The catalyst of claim 1, wherein: the loading of the transition metal in the catalyst is 5-20%.
4. The catalyst of claim 1, wherein: the transition metal salt is one of acetate of Fe, co, ni, cu.
5. A method for preparing the transition metal-loaded zirconium phosphate grease hydrodeoxygenation catalyst according to any one of claims 1-4, which is characterized in that: the method comprises the following steps:
1) Respectively dissolving zirconium salt and ammonium salt in deionized water, and stirring and mixing to obtain a solid acid suspension;
2) Filtering the suspension, drying the filter residue at 100 ℃, grinding, sieving with a 60-mesh sieve, and roasting at 550 ℃;
3) Dissolving the roasted solid and transition metal salt in deionized water, stirring and mixing, removing the solvent by rotary steaming, roasting at 450 ℃, reducing and passivating at 550 ℃ to prepare the transition metal-loaded zirconium phosphate grease hydrodeoxygenation catalyst.
6. Use of the transition metal supported zirconium phosphate grease hydrodeoxygenation catalyst of claim 1 in the hydrodeoxygenation of biological grease.
7. The use according to claim 6, characterized in that: the dosage of the transition metal-loaded zirconium phosphate grease hydrodeoxygenation catalyst is 1-10% of the weight of the biomass oil to be treated, the reaction temperature for hydrodeoxygenation is 280-400 ℃, the hydrogen pressure is 2-6 MPa, and the reaction time is 2-10 h.
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