CN118002194A - Biological aviation kerosene catalyst with core-shell structure and application thereof - Google Patents
Biological aviation kerosene catalyst with core-shell structure and application thereof Download PDFInfo
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- CN118002194A CN118002194A CN202410147759.6A CN202410147759A CN118002194A CN 118002194 A CN118002194 A CN 118002194A CN 202410147759 A CN202410147759 A CN 202410147759A CN 118002194 A CN118002194 A CN 118002194A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 239000003350 kerosene Substances 0.000 title claims abstract description 35
- 239000011258 core-shell material Substances 0.000 title claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 239000002184 metal Substances 0.000 claims abstract description 40
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002808 molecular sieve Substances 0.000 claims abstract description 37
- 239000000243 solution Substances 0.000 claims abstract description 25
- 239000011148 porous material Substances 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 239000002028 Biomass Substances 0.000 claims description 6
- 230000008014 freezing Effects 0.000 claims description 6
- 238000007710 freezing Methods 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 239000003225 biodiesel Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 2
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 1
- 238000004806 packaging method and process Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 229910016551 CuPt Inorganic materials 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/62—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing platinum group 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
-
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
- C10G2300/1037—Hydrocarbon fractions
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a biological aviation kerosene catalyst with a core-shell structure and application thereof, and relates to the technical field of green energy, and the technical scheme is characterized in that the biological aviation kerosene catalyst with the core-shell structure is prepared by impregnating a first molecular sieve carrier into a metal precursor solution to prepare an inner core, and then packaging the inner core into a second molecular sieve; the pore diameter of the second molecular sieve is larger than that of the first molecular sieve; the metal precursor solution is a mixed solution of Pt and divalent metal.
Description
Technical Field
The invention relates to the technical field of green energy, in particular to a biological aviation kerosene catalyst with a core-shell structure and application thereof.
Background
The traditional aviation kerosene is prepared by taking petrochemical energy as a raw material, mainly rectifying petroleum, taking hydrocarbon components with chain length of C9-C16, and also can be prepared by a coal liquefaction process and natural gas liquefaction, wherein the petroleum, the coal and the natural gas are non-renewable energy sources, the raw material sources of the aviation kerosene are also reduced sharply along with the exhaustion of resources, and the combustion release of the aviation kerosene is an important source of greenhouse gases, so that the aviation kerosene has serious pollution to the atmosphere. Therefore, there is an urgent need for renewable energy sources that can replace energy sources such as petrochemical industry to produce aviation kerosene. The biological aviation kerosene is clean renewable green energy, and the emission reduction of carbon dioxide reaches more than 80% when the biological aviation kerosene is produced by using waste grease as a raw material.
The biomass raw material has the characteristics of high viscosity, high oxygen content, unstable combustion, low heat value and the like, cannot be directly used as a substitute for petroleum fuel, and needs hydrodeoxygenation treatment before use. The production process of the second-generation biodiesel is mainly a fixed bed hydrogenation process, and the waste grease raw material has the defects of high acid value and excessively high contents of Fe, na, ca metal elements, O, N, P and other elements, and is easy to deposit on a catalyst in the hydrogenation reaction process so as to reduce the activity of the catalyst.
At present, in the production process of biological aviation kerosene, the product of hydrodeoxygenation of the biological raw material is mainly normal alkane with the carbon number of C15-C18, and the normal alkane with the carbon number of C9-C15 is prepared by isomerization and cracking reaction. The catalyst used in hydroisomerization is mainly a molecular sieve supported catalyst, and active metal is supported on the molecular sieve, so that the catalyst has good activity and selectivity. However, the framework of the carrier of the supported catalyst is easy to collapse in application, so that the activity of the catalyst is reduced and the selectivity is poor; the supported catalyst has small active component load, is easy to be aggregated into large particles, and has high noble metal cost.
Disclosure of Invention
Aiming at the defects existing in the prior art, the first aim of the invention is to provide a biological aviation kerosene catalyst with a core-shell structure, which has the advantages of stable structure and high catalytic efficiency; the second aim of the invention is to provide an application of the catalyst with the core-shell structure in preparation of biological aviation kerosene.
In order to achieve the first object, the present invention provides the following technical solutions: a biological aviation kerosene catalyst with a core-shell structure is prepared by impregnating a first molecular sieve carrier into a metal precursor solution to prepare a core, and then packaging the core into a second molecular sieve;
the pore diameter of the second molecular sieve is larger than that of the first molecular sieve;
The metal precursor solution is a mixed solution of Pt and divalent metal.
Further, the content of the active metal is 0.1-5% of the divalent metal, 0.05-3% of Pt, and the metal content ratio of the divalent metal to Pt is 20:1-1:10 based on the total catalyst amount.
Further, the divalent metal is any one of copper, iron and magnesium salt, and the Pt precursor solution is at least one of H2PtCl6、(NH4)2PtCl6、Pt(NH3)2Cl2、Pt(NH3)4(CH3COO)2、PdCl2.
Further, the pore diameter of the first molecular sieve carrier is smaller than 0.5nm, and the mesoporous area is 50-250m 2/g.
Further, the pore size of the second molecular sieve support is greater than 0.6nm.
Further, the first molecular sieve is a 4A or 5A molecular sieve.
Further, the second molecular sieve is one of twelve-membered ring large pore zeolite or fourteen-membered ring super large pore zeolite.
Further, the preparation method of the catalyst comprises the following steps:
(1) Preparing an aqueous solution containing a metal precursor to obtain an impregnating solution, impregnating a first molecular sieve carrier in the impregnating solution to carry out metal loading, and then filtering, washing and drying to obtain a first molecular sieve core loaded with divalent metal and Pt;
(2) Mixing the first molecular sieve loaded with metal and Pt, a template agent, a silicon source or a silicon source, an aluminum source and water, performing hydrothermal reaction in a reaction system, filtering, drying and activating to prepare the catalyst with the core-shell structure.
In order to achieve the second object, the present invention provides the following technical solutions:
The application of the catalyst with the core-shell structure in the preparation of the biological aviation kerosene is that the biomass-derived raw oil and the catalyst with the core-shell structure are subjected to hydroisomerization reaction under a reaction system to prepare the biological aviation kerosene, and the freezing point of the biological aviation kerosene is lower than-41 ℃.
Further, the raw oil is biodiesel prepared from biomass sources.
Further, hydroisomerization conditions are: the reaction temperature is 300-400 ℃, and the hydrogen partial pressure is 3-10MPa.
In summary, the invention has the following beneficial effects:
The catalyst disclosed by the invention adopts the common metal and the Pt composite active metal, is uniformly anchored on the surface of the molecular sieve to form a stable structure, and different metals have different activities to generate a synergistic effect, so that the addition cost of noble metals is reduced, and the activity of the catalyst is enhanced; and then the catalyst is packaged in the second molecular sieve or fixed on the surface of the second molecular sieve to form a geometric structure effect, so that the framework of the second molecular sieve is better supported, collapse and inactivation of the framework are avoided, and the stability of the catalyst is enhanced.
Drawings
FIG. 1 is a flow chart of the preparation of the core-shell catalyst of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
(1) Dissolving 0.25g of H 2PtCl6 and 41.8g of CuSO in water to prepare an aqueous solution to obtain an impregnating solution; weighing 15g of ZSM-5, immersing in the immersion liquid for metal loading, filtering, washing, and drying a filter cake for 5 hours to obtain CuPt/ZSM-5;
(2) 2g of CuPt/ZSM-5, 10mL of C 19H42 BrN solution, 6mL of tetraethoxysilane and 18mL of water are mixed, and the mixture is subjected to hydrothermal reaction in a reaction system, filtered, washed by deionized water, dried at 60 ℃ and activated under the condition of hydrogen atmosphere, so that the catalyst with the core-shell structure is prepared.
Example 2
(1) Dissolving PtN 2O6 1.0.0 g and Cu (NO 3)2 5.0.0 g in water to prepare an aqueous solution to obtain an impregnating solution, weighing ZSM-5 18g, impregnating the impregnating solution to carry out metal loading, filtering, washing, and drying a filter cake for 6 hours to obtain CuPt/ZSM-5;
(2) 2g of CuPt/ZSM-5, 10mL of C 12H29 NO solution, 6mL of methyl orthosilicate and 18mL of water are mixed, hydrothermal reaction is carried out in a reaction system, filtration, washing with deionized water, drying at 70 ℃ and activation under the condition of hydrogen atmosphere are carried out, and the catalyst with a core-shell structure is prepared.
Example 3
(1) Dissolving 0.25g of H 2PtCl6 and 41.8g of CuSO in water to prepare an aqueous solution to obtain an impregnating solution; weighing 15g of ZSM-5, immersing in the immersion liquid for metal loading, filtering, washing, and drying a filter cake for 5 hours to obtain CuPt/ZSM-5;
(2) 2g of CuPt/ZSM-5, 10mL of C 12H29 NO solution, 6mL of ethyl orthosilicate and 18mL of water are mixed, hydrothermal reaction is carried out in a reaction system, filtration, washing with deionized water, drying at 70 ℃ and activation are carried out under the condition of hydrogen atmosphere, and the catalyst with the core-shell structure is prepared.
Example 4
(1) Dissolving 0.36g of H 2PtCl6 in water to prepare an aqueous solution to obtain an impregnating solution; weighing 515g of ZSM-515g, immersing in the immersion liquid for metal loading, filtering, washing, and drying a filter cake for 5 hours to obtain Pt/ZSM-5.
(2) 2G of Pt/ZSM-5, 10mL of C 19H42 BrN solution, 6mL of tetraethoxysilane and 18mL of water are mixed, and the mixture is subjected to hydrothermal reaction in a reaction system, filtered, washed by deionized water, dried at 60 ℃ and activated under the condition of hydrogen atmosphere, so that the catalyst with the core-shell structure is prepared.
Example 5
(1) Dissolving CuSO42.5g in water to prepare an aqueous solution to obtain an impregnating solution; weighing 515g of ZSM-515g, immersing in the immersion liquid for metal loading, filtering, washing, and drying a filter cake for 5 hours to obtain Cu/ZSM-5;
(2) 2g of Cu/ZSM-5, 10mL of C 19H42 BrN solution, 6mL of tetraethoxysilane and 18mL of water are mixed, and the mixture is subjected to hydrothermal reaction in a reaction system, and is filtered, washed by deionized water, dried at 60 ℃ and activated under the condition of hydrogen atmosphere, so that the catalyst with the core-shell structure is prepared.
Comparative example 1
The procedure was as in example 1, except that in step (1), cuPt/ZSM-5 was prepared.
Comparative example 2
The ZSM-5 molecular sieve of all silicon is prepared by a conventional method.
Performance test
The hydroisomerization reaction was carried out using the biomass-derived normal alkane as a raw material, the catalysts prepared in each example and comparative example, at a reaction temperature of 350℃and a reaction pressure of 6MPa, and a hydrogen-oil volume ratio of 600NL/L, and the results are shown in Table 1:
Table 1 the catalysts of examples and comparative examples participate in the isomerisation cracking reaction results
| Name of the name | Biological aviation kerosene yield (%) | Biological aviation kerosene freezing point (DEG C) |
| Example 1 | 62 | -43 |
| Example 2 | 58 | -41 |
| Example 3 | 63 | -42 |
| Example 4 | 23 | -26 |
| Example 5 | 20 | -19 |
| Comparative example 1 | 35 | -36 |
| Comparative example 2 | 10 | -10 |
As can be seen from table 1: the catalyst with the core-shell structure has obvious advantages in the isomerism cracking reaction, the yield of the prepared biological aviation kerosene is up to 60%, and the freezing point is lower than-40 ℃; the catalyst obtained by loading only one metal has lower catalysis than the catalyst of the composite metal, so that the yield of the biological aviation kerosene is reduced, and the freezing point is higher; the catalyst with only the nuclear structure as in comparative example 1 has low yield of the prepared biological aviation kerosene, high freezing point and poor catalytic effect, and can not meet the requirements of practical application; the metal-free activity as shown in comparative example 2, the molecular sieve of the molecular sieve framework only has little catalytic activity and cannot be applied to isomerization reaction; the molecular sieve with the core-shell structure forms a composite metal active site with a synergistic effect on the inner core, and the catalytic performance of the molecular sieve is higher than that of a catalyst with single metal activity; when the inner core is encapsulated and fixed in the shell or partially fixed on the shell, better support is provided for the framework of the catalyst, so that the catalyst is not easy to collapse and deactivate, the metal particles cannot generate agglomeration phenomenon, and the metal particles are uniformly dispersed on the core and shell structure, so that the stability of the catalyst is further enhanced.
The present embodiment is only for explanation of the present invention and is not to be construed as limiting the present invention, and modifications to the present embodiment, which may not creatively contribute to the present invention as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present invention.
Claims (10)
1. A biological aviation kerosene catalyst with a core-shell structure is characterized in that an inner core is prepared by dipping a first molecular sieve carrier in a metal precursor solution, and then the inner core is packaged in a second molecular sieve;
the pore diameter of the second molecular sieve is larger than that of the first molecular sieve;
The metal precursor solution is a mixed solution of Pt and divalent metal.
2. The bio-aviation kerosene catalyst with a core-shell structure according to claim 1, wherein the content of active metals in terms of elements is 0.1-5% of divalent metals, 0.05-3% of Pt, and the metal content ratio of divalent metals to Pt is 20:1-1:10, based on the total amount of the catalyst.
3. The bio-aviation kerosene catalyst having a core-shell structure according to claim 1, wherein the divalent metal is any one of copper, iron and magnesium salts, and the Pt precursor solution is at least one of H2PtCl6、(NH4)2PtCl6、Pt(NH3)2Cl2、Pt(NH3)4(CH3COO)2、PdCl2.
4. The biological aviation kerosene catalyst with a core-shell structure according to claim 1, wherein the pore diameter of the first molecular sieve carrier is smaller than 0.5nm, and the mesoporous area is 50-250m 2/g.
5. The bio-aviation kerosene catalyst having a core-shell structure according to claim 1, wherein the pore size of the second molecular sieve support is greater than 0.6nm.
6. The bio-aviation kerosene catalyst having a core-shell structure according to claim 1, wherein the first molecular sieve is a 4A or 5A molecular sieve.
7. The biological aviation kerosene catalyst with a core-shell structure according to claim 1, wherein the second molecular sieve is one of a twelve-membered ring large pore zeolite or a fourteen-membered ring super large pore zeolite.
8. The method for preparing the catalyst with the core-shell structure according to any one of claims 1 to 7, which is characterized by comprising the following steps:
(1) Preparing an aqueous solution containing a metal precursor to obtain an impregnating solution, impregnating a first molecular sieve carrier in the impregnating solution to carry out metal loading, and then filtering, washing and drying to obtain a first molecular sieve core loaded with divalent metal and Pt;
(2) Mixing the first molecular sieve loaded with metal and Pt, a template agent, a silicon source or a silicon source, an aluminum source and water, performing hydrothermal reaction in a reaction system, filtering, drying and activating to prepare the catalyst with the core-shell structure.
9. The application of the catalyst with the core-shell structure in biological aviation kerosene, which is characterized in that the biological aviation kerosene is prepared by carrying out hydroisomerization reaction on raw oil from biomass and the catalyst with the core-shell structure in a reaction system, wherein the freezing point of the biological aviation kerosene is lower than-41 ℃.
10. The use of the catalyst with a core-shell structure in biological aviation kerosene according to claim 9, wherein the raw oil is bio-diesel of biomass origin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410147759.6A CN118002194A (en) | 2024-02-02 | 2024-02-02 | Biological aviation kerosene catalyst with core-shell structure and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410147759.6A CN118002194A (en) | 2024-02-02 | 2024-02-02 | Biological aviation kerosene catalyst with core-shell structure and application thereof |
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