CN109078652B - Preparation method and application of metal Ni-doped hierarchical pore ZSM-5 molecular sieve - Google Patents
Preparation method and application of metal Ni-doped hierarchical pore ZSM-5 molecular sieve Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
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Abstract
The invention discloses a preparation method of a metal Ni-doped hierarchical pore ZSM-5 molecular sieve. The method comprises the following steps: pre-treating and roasting the molecular sieve to remove a template agent and water; etching the molecular sieve by using HF acid solution to generate a multi-stage pore channel structure; loading high-activity metallic nickel by an impregnation method; and (6) tabletting and screening. Simultaneously discloses the molecular sieve is used for biomass catalytic fast pyrolysis. The invention adopts cheap and easily available zeolite HZSM-5 as a matrix, and simultaneously carries out desiliconization and dealuminization treatment by utilizing the cross microporosity of the five-membered ring and the ten-membered ring of the zeolite HZSM-5 to generate a multi-level pore channel which is beneficial to macromolecule entering. The method realizes hole expansion and simultaneously reduces the distribution of acid sites. On the basis, cheap metal nickel with strong hydrogen transfer capacity is added, so that high passing rate and high conversion rate of macromolecules in the catalytic process are realized. The catalyst prepared by the method has the characteristics of low price, easy obtaining and simple process, is mainly applied to catalytic pyrolysis experiments of biomass or coal, and has good prospect for catalytic reforming of pyrolysis volatile components.
Description
Technical Field
The invention relates to a preparation method of a high-activity catalyst, in particular to a method for preparing the high-activity catalyst under the combined action of metal and etched HZSM-5, and specifically relates to a preparation method of a metal Ni-doped hierarchical pore ZSM-5 molecular sieve, and the application of the metal Ni-doped hierarchical pore ZSM-5 molecular sieve in biomass catalytic fast pyrolysis, belonging to the field of catalytic material modification.
Background
The biomass is a renewable resource, is abundant in the world, and provides a prospect for replacing fossil fuels with liquid transportation materials. Poor stability due to the high oxygen content of bio-oil is considered to be a major problem for the difference between bio-oil and hydrocarbon fuels. So far, the catalytic deoxidation technology of the bio-oil is widely researched and applied and is considered to be an effective way for deoxidation and upgrading. The catalytic cracking of gas-phase tar improves the quality of tar mainly by improving light aromatic hydrocarbon (BTEXN), regulating and controlling the deoxidation rate and changing the distribution of pyrolysis organic compounds. There are three main catalysts: metal oxides, carbon-based catalysts and zeolite catalysts. Zeolite catalysis is the most interesting research content of researchers, and under the action of zeolite, light aromatic hydrocarbon is greatly improved, selectivity is increased, and HZSM-5 is the most prominent.
The HZSM-5 zeolite contains ten-membered rings, and the basic structural unit is composed of eight five-membered rings. The strength and type of the acid centers are similar to those of amorphous aluminum silicate, but the number of the acid centers is high and can be 10 times of that of the amorphous aluminum silicate. Its microporosity limits its large-scale application due to its short life as a reforming volatile aromatization catalyst. The hierarchical pore HZSM-5 molecular sieve can optimize the pore property of the catalyst and the synergistic effect of active sites, has good diffusion performance, can regulate and control acidity by adjusting the cation composition and the silica-alumina ratio in a framework in the production and use processes, is often used as a catalytic material, is widely applied to the field of petrochemical industry, and is a catalytic material with very high application potential. Wherein, the high-temperature treatment, the steam treatment and the alkali treatment damage micropores to form mesopores through framework desiliconization or dealumination, but the acid catalytic capability of the catalyst is reduced, and the catalyst is not favorable for reforming and aromatizing volatile matters. How to improve the cracking and hydrogen transfer capabilities of the molecular sieve and reduce the diffusion resistance of the catalytic reaction at the same time, so that the improvement of the activity and stability of the catalyst is the bottleneck of the research field of the catalyst.
Disclosure of Invention
The invention aims to overcome the technical defects of reduction of active sites and weak catalytic capacity caused by reaming by using a conventional HZSM-5 desilication or dealumination method, and provides a preparation method of a metal Ni-doped hierarchical pore ZSM-5 molecular sieve, wherein the catalytic reaction resistance is reduced by desilication and dealumination on a molecular sieve carrier through HF acid etching, and the high-activity metal is loaded to increase the cracking and hydrogen transfer capacities and improve the yield of aromatic hydrocarbon.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a metal Ni-doped hierarchical pore HZSM-5 molecular sieve comprises the following steps:
step 1, molecular sieve roasting pretreatment, template and water removal
Grinding HZSM-5 molecular sieve into powder of less than 200 meshes, putting the powder into a muffle furnace, and raising the temperature to 500-oC (best 550)oC) Roasting for 5-6h, and introducing air flow at constant speed in the roasting process. Then cooling to room temperature, drying and storing;
step 2, etching the molecular sieve by using HF acid solution to generate a multilevel pore channel structure
a. The HF solution and the deionized water are mixed according to the mass ratio: mixing the components in a ratio of 1: 5-100 to prepare the HF acid etching solution.
b. Mixing the molecular sieve subjected to roasting pretreatment in the step 1 with an HF acid etching solution according to a mass ratio of 1: 10-12, mixing to obtain a mixed solution; magnetically stirring the mixed solution for more than 15 hours (the optimal stirring time is 15-17 hours), then carrying out suction filtration, and washing to be neutral; then placing a forced air drying oven at 110oC, drying; putting the dried sample into a muffle furnace, and heating to 600 ℃ at a set heating rateoC, roasting for 4-5 hours, and cooling to room temperature to obtain a grading sample F-Z5;
step 3, loading high-activity metallic nickel by dipping method
According to 0.2-3g Ni (NO)3)2•6H2Adding deionized water at the ratio of 15m L to O to prepare a nickel nitrate solution, mixing 10g of the graded sample F-Z5 prepared in the step 2 and the nickel nitrate solution at the ratio of 15m L, magnetically stirring for 4 hours, standing for more than 8 hours to obtain a green molecular sieve suspension, and drying the green molecular sieve suspension in an air drying oven under the drying condition that the temperature is 110 DEG CoC, drying for 8-12h, and stirring once every half hour for the first two hours in the drying process; the dried sample is heated from room temperature to 550 ℃ in a muffle furnace at a set heating rateoKeeping the temperature for 5-6h, introducing hydrogen 600 before useoC is reduced for 1h to be in a metal state, and the metal Ni-doped hierarchical pore ZSM-5 molecular sieve (Ni-FZ 5) is obtained.
Further, step 4. tabletting and screening
And (3) pressing the Ni-FZ5 molecular sieve prepared in the step (3) on a tablet press for 10 minutes at the pressure of 10MPa, pressing into a tablet shape, and crushing and screening to 16-40 meshes to obtain the catalyst with uniform particle size.
The metal Ni-doped hierarchical pore ZSM-5 molecular sieve prepared by the method is used for biomass catalytic fast pyrolysis:
in a falling bed reactor, the metal Ni-doped hierarchical pore ZSM-5 molecular sieve prepared by the method is used as a catalyst and is placed at the bottom of a quartz tube, the upper layer is separated by quartz wool, biomass particles dried by 16-40 meshes are placed in a feeding bottle, and the temperature is controlled at 20 DEGoThe temperature rise rate of C/min is increased to 600oIntroducing hydrogen gas at a speed of 100m L/min for reduction for 1h at C, changing into Ar, cooling to 500oC, feeding at the rate of 0.1g/min, and keeping for 15min after feeding to ensure that the biomass is fully pyrolyzed. And the obtained biomass volatile matter is reformed by a catalytic bed layer and then is collected by cold hydrazine. The detection shows that the catalyst has good selectivity on light aromatic hydrocarbon.
The invention adopts a preparation method combining HZSM-5 reaming and active site increasing, and compared with the existing preparation method, the preparation method has the following characteristics:
the Ni-FZ5 can simultaneously achieve the effects of desiliconization and dealuminization, has a pore structure for allowing macromolecular oxygen-containing substances to rapidly pass through, and simultaneously keeps relatively more acid sites for catalytic conversion. After the metallic nickel is loaded, the metallic sites are added for catalytic conversion on the basis of the original smooth pore channel structure. When the catalyst is applied to the field of catalytic pyrolysis, the cracking, hydrogen transfer and decarboxylation decarbonylation reactions of volatile components are accelerated. Thereby increasing the yield of aromatic hydrocarbon and improving the deoxidation effect.
Drawings
FIG. 1 shows the pore size distributions (a) and N of HZSM-5 and nickel-loaded after etching2And (b) a comparison graph of the adsorption and desorption curves (b).
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
Step 1, grinding 15g of commercial molecular sieve HZSM-5Pulverizing into powder (below 200 mesh), placing into muffle furnace at a temperature of 10%oThe temperature rise rate of C/min is increased to 550oAnd C, roasting and keeping for 5 hours. And (4) in the roasting process, air flow is introduced slowly, and after the roasting process is finished, the mixture is cooled to room temperature and is dried and stored.
Step 2, 3.75 g of HF solution (37 wt%) and deionized water are weighed and mixed in a polytetrafluoroethylene beaker, the total volume is 150 m L, 0.5 mol/L HF acid etching solution is prepared, 15g of the molecular sieve pretreated in the step 1 is mixed with the hydrofluoric acid solution and stirred for 17 hours, then suction filtration is carried out, the mixture is washed to be neutral, and then the mixture is placed in an air-blast drying oven to be 110 hoursoAnd C, drying for 12 h. The dried sample was placed in a muffle furnace at 600 deg.CoC is 10oAnd C/min heating rate roasting for 4 h. After the completion of the reaction, the reaction mixture was cooled to room temperature to obtain a hierarchical zeolite.
Step 3. weigh 0.74g of Ni (NO)3)2•6H2Adding 15m L deionized water into O to prepare nickel nitrate solution, weighing 15g of the graded zeolite prepared in the step 2, mixing with the nickel nitrate solution, magnetically stirring for 4 hours, standing overnight, and drying the sample in a forced air drying oven under the drying condition of 110oC, 12h, stirring every half hour for the first two hours. Dried sample was placed in a muffle furnace at 10 deg.CoThe temperature rise speed of C/min is increased from room temperature to 550oC is reserved for 5h, and hydrogen 600 is introduced before useoC is reduced for 1h to be in a metallic state, and the metallic 1wt% Ni-doped hierarchical pore HZSM-5 molecular sieve (1 Ni-FZ 5) is obtained.
And 4, pressing the Ni-FZ5 molecular sieve processed in the example 3 on a tablet machine for 10 minutes at 10MPa into a sheet shape, and then crushing and screening the sheet shape to 16-40 meshes to obtain the catalyst with uniform particle size.
Example 2. the Ni-FZ5 molecular sieve prepared in example 1 was subjected to catalytic reforming of biomass volatiles in a falling bed reactor. The catalyst is placed at the bottom of the quartz tube, the upper layer is separated by quartz wool, and the biomass particles dried by 16-40 meshes are placed in a feeding bottle at the temperature of 20 DEGoThe temperature rise rate of C/min is increased to 600oIntroducing hydrogen gas at a speed of 100m L/min for reduction for 1h at C, changing into Ar, cooling to 500oC, feeding at the rate of 0.1g/min, and keeping for 15min after feeding to ensure that the biomass is fully pyrolyzed. The biomass obtainedThe volatile matter is reformed by the catalytic bed layer and then collected by cold hydrazine, and the detection shows that the volatile matter has good selectivity on light aromatic hydrocarbon.
Claims (4)
1. A preparation method of a metal Ni-doped hierarchical pore ZSM-5 molecular sieve comprises the following steps:
step 1, molecular sieve roasting pretreatment, template and water removal
Grinding the HZSM-5 molecular sieve into powder of less than 200 meshes, putting the powder into a muffle furnace, raising the temperature to 500-600 ℃ at a set temperature rise speed, roasting the powder for 5 to 6 hours, introducing air flow at a constant speed in the roasting process, cooling the powder to room temperature, and drying and storing the powder;
step 2, etching the molecular sieve by using HF acid solution to generate a multilevel pore channel structure
The mass ratio of the HF solution to the deionized water is as follows: 1: 5-100, and preparing an HF acid etching solution;
b. mixing the molecular sieve subjected to roasting pretreatment in the step 1 with an HF acid etching solution according to a mass ratio of 1: 10-12, mixing to obtain a mixed solution; magnetically stirring the mixed solution for more than 15 hours, then carrying out suction filtration, and washing to be neutral; then placing the mixture in an air drying oven to dry at 110 ℃; putting the dried sample into a muffle furnace, heating to 600 ℃ at a set heating speed, roasting for 4-5 h, and cooling to room temperature to obtain a graded sample F-Z5;
step 3, loading high-activity metallic nickel by dipping method
According to 0.2-3g Ni (NO)3)2·6H2Adding deionized water into O at the ratio of 15m L to prepare a nickel nitrate solution, mixing 10g of the graded sample F-Z5 prepared in the step 2 and the 15m L nickel nitrate solution at the ratio of the two, magnetically stirring for 4 hours, standing for more than 8 hours to obtain a green molecular sieve suspension, then putting the green molecular sieve suspension into a forced air drying oven for drying under the conditions that the temperature is 110 ℃, the drying time is 8-12 hours, stirring is carried out every half hour for two hours before the drying process, the dried sample is heated from room temperature to 550 ℃ at a set heating rate in a muffle furnace, keeping the temperature for 5-6 hours, reducing for 1 hour from 600 ℃ by introducing hydrogen before use to obtain the metal Ni-doped hierarchical-pore ZSM-5 molecular sieve.
2. The method for preparing metallic Ni-doped hierarchical pore ZSM-5 molecular sieve according to claim 1, wherein: in the step 1, the HZSM-5 molecular sieve is ground into powder of less than 200 meshes, the powder is put into a muffle furnace to be heated to 550 ℃ at a set heating speed, and the powder is roasted for 5 to 6 hours.
3. The method for preparing metallic Ni-doped hierarchical pore ZSM-5 molecular sieve according to claim 1 or 2, characterized in that:
step 4, tabletting and screening
And (3) pressing the metal Ni-doped hierarchical pore ZSM-5 molecular sieve prepared in the step (3) on a tablet press for 10 minutes at the pressure of 10MPa, pressing into a sheet shape, and crushing and screening to 16-40 meshes.
4. The metallic Ni-doped hierarchical pore ZSM-5 molecular sieve prepared by the method of claim 1, 2 or 3 is used for biomass catalytic fast pyrolysis:
in a falling bed reactor, a metal Ni-doped hierarchical pore ZSM-5 molecular sieve is placed at the bottom of a quartz tube as a catalyst, the upper layer is separated by quartz cotton, biomass particles after 16-40 meshes are placed in a feeding bottle, hydrogen is introduced for 100m L/min to reduce for 1h when the temperature rises to 600 ℃ at the heating rate of 20 ℃/min, then Ar is changed, the temperature is reduced to 500 ℃ and the feeding rate of 0.1g/min is kept, 15min is kept after the feeding is finished to ensure that the biomass is fully pyrolyzed, and the obtained biomass volatile is collected by cold hydrazine after being reformed by a catalytic bed layer.
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