CN115283006A - Catalyst ultrasonic modification method for preparing aromatic hydrocarbon by catalytic pyrolysis of biomass - Google Patents
Catalyst ultrasonic modification method for preparing aromatic hydrocarbon by catalytic pyrolysis of biomass Download PDFInfo
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Abstract
A catalyst ultrasonic modification method for preparing aromatic hydrocarbon by biomass catalytic pyrolysis comprises the following steps: (1) Dissolving ammonium molybdate in deionized water, stirring and dissolving, and then immersing powder HZSM-5 in the solution to obtain a mixed solution A; (2) Putting the mixed solution A of ammonium molybdate and HZSM-5 in an ultrasonic instrument, and carrying out ultrasonic treatment to obtain a sample B; (3) And (3) carrying out oil bath constant-temperature heating and stirring on the sample B subjected to ultrasonic treatment, drying the sample subjected to oil bath in an oven, and finally placing the dried HZSM-5 in a muffle furnace for high-temperature calcination to obtain the modified HZSM-5. By adopting the method provided by the invention, the HZSM-5 is modified by ultrasonic assistance, so that the Mo precursor can effectively permeate into the inner surface of the catalyst, and Mo species can be stably loaded on the surface of the catalyst. The modification method improves the utilization efficiency of Mo, the HZSM-5 catalytic performance can be obviously enhanced by lower Mo loading amount, and the yield of the target aromatic hydrocarbon of biomass catalytic pyrolysis is improved.
Description
Technical Field
The invention relates to an ultrasonic modification method of a catalyst for preparing aromatic hydrocarbon by catalytic pyrolysis of biomass, belonging to the field of biomass resource conversion and utilization.
Background
Aromatic hydrocarbons are important basic raw materials for petrochemical industry, and the production of traditional aromatic hydrocarbons mainly depends on petroleum processing. With the development of industrialization, the long-term use of fossil energy brings about a series of problems of resource crisis, environmental pollution and the like, and the development of sustainable, renewable and environment-friendly alternative resources is urgently needed. Biomass is the only renewable organic carbon source and exhibits carbon neutrality over the entire life cycle. The method for preparing the aromatic hydrocarbon by using the biomass as the raw material and applying the aromatic hydrocarbon in a large scale is an important measure for realizing carbon peak reaching and carbon neutralization, and can provide an effective way for clean utilization of agricultural and forestry waste biomass.
Catalytic pyrolysis is an efficient way for producing aromatic hydrocarbon by biomass one-step method, solid agriculture and forestry waste biomass (straw, wood chips and algae) is used as a raw material to be pyrolyzed to generate volatile organic matters, and then the volatile organic matters are subjected to catalytic conversion by a molecular sieve pore channel to obtain the aromatic hydrocarbon. HZSM-5 is the most commonly used molecular sieve catalyst for preparing aromatic hydrocarbon by biomass shape-selective catalysis, and has good shape selectivity for benzene, toluene and xylene. The catalytic performance and the catalytic life of the HZSM-5 are greatly determined by the distribution of acid sites (Bronsted or Lewis types), and the pyrolysis macromolecule oxygen-containing compound is easy to polymerize and coke on the strong acid sites of the HZSM-5, so that the catalyst is quickly deactivated, and the conversion of biomass to aromatic hydrocarbon is limited. In order to increase the yield of the target aromatic hydrocarbon product, it is necessary to modify HZSM-5 to improve the distribution of acid sites in the catalyst, to facilitate the formation of aromatic hydrocarbons and to extend the catalyst life.
The molybdenum metal loading can adjust the strength and distribution of HZSM-5 acid sites, and generally, HZSM-5 is modified by dipping in a Mo metal precursor solution, and the metal precursor most possibly falls on the surface of silicon oxide, and only a small amount of the metal precursor falls on the site of four-coordinate aluminum and cannot be effectively combined with HZSM-5 active sites. This results in inefficient use of the metal active ingredient, requiring more metal loading to effectively modulate the catalyst acid sites. The large amount of metal loading can cause the accumulation of metal species in zeolite channels, which sharply reduces the pore volume and pore diameter of the catalyst, limits the diffusion of reactants and products in the channels, reduces the yield of aromatic hydrocarbons and causes the deactivation of the catalyst. Therefore, there is a need to improve the existing HZSM-5 modification methods, promote dispersion of Mo precursors and efficient binding of metals to active sites on the zeolite framework, optimize HZSM-5 acid site distribution at lower Mo loadings and increase target aromatics yields.
Disclosure of Invention
The invention provides an ultrasonic modification method of a catalyst for preparing aromatic hydrocarbon by catalytic pyrolysis of biomass, aiming at the defects of the prior art. The method can enhance the synergistic effect between Mo and the active sites of the catalyst, improve the performance of the catalyst under the condition of lower Mo loading capacity, and improve the yield of aromatic hydrocarbon in biomass catalytic pyrolysis.
The technical problem of the invention is solved by the following technical scheme:
a catalyst ultrasonic modification method for preparing aromatic hydrocarbon by biomass catalytic pyrolysis comprises the following steps:
(1) Dissolving ammonium molybdate in deionized water, stirring and dissolving, and then immersing powder HZSM-5 in the solution to obtain a mixed solution A;
(2) Putting the mixed solution A of ammonium molybdate and HZSM-5 in an ultrasonic instrument, and carrying out ultrasonic treatment to obtain a sample B;
(3) And (3) carrying out oil bath constant-temperature heating and stirring on the sample B subjected to ultrasonic treatment, drying the sample subjected to oil bath in an oven, and finally placing the dried HZSM-5 in a muffle furnace for high-temperature calcination to obtain the modified HZSM-5.
In the method for improving the yield of the biomass catalytic pyrolysis aromatic hydrocarbon, in the step (1), the powder HZSM-5 has a silica-alumina ratio of (18-38): 1.
in the method for improving the yield of the biomass catalytic pyrolysis aromatic hydrocarbon, in the step (1), the mass ratio of the ammonium molybdate to the HZSM-5 is (0.005-0.02): 1.
according to the method for improving the yield of the biomass catalytic pyrolysis aromatic hydrocarbon, in the step (1), the mass ratio of HZSM-5 to deionized water is (0.5-2): 1.
in the method for improving the yield of the aromatic hydrocarbon by catalytic pyrolysis of the biomass, in the step (2), the power of ultrasonic treatment is 50-150W.
In the method for improving the yield of the biomass catalytic pyrolysis aromatic hydrocarbon, in the step (2), the ultrasonic treatment time is 50-100min.
According to the method for improving the yield of the biomass catalytic pyrolysis aromatic hydrocarbon, in the step (3), the drying time is not less than 8 hours.
In the method for improving the yield of the catalytic pyrolysis aromatic hydrocarbon of the biomass, in the step (3), the high-temperature calcination temperature is 500-700 ℃, and the calcination time is 4 hours.
The invention has the following advantages:
by adopting the method provided by the invention, the HZSM-5 is modified by ultrasonic assistance, so that the Mo precursor can effectively permeate into the inner surface of the catalyst, and Mo species can be stably loaded on the surface of the catalyst. Varying the sonication conditions can control the distribution of the Mo precursors and anchor them partially to the framework Al sites. When a small amount of Mo is loaded, mo can reach the HZSM-5 channel and efficiently combine with the strong Bronsted acid sites, and the synergistic effect between Mo species and the HZSM-5 surface active sites is obviously enhanced. The problem of catalyst pore channel blockage caused by a large amount of Mo precursor falling on the outer surface of HZSM-5 in the traditional impregnation method is solved. The modification method improves the utilization efficiency of Mo, can obviously enhance the HZSM-5 catalytic performance by using a lower Mo loading amount, and improves the yield of the target aromatic hydrocarbon in the catalytic pyrolysis of the biomass.
Drawings
FIG. 1 shows NH of HZSM-5 obtained in example 1, comparative example 3 and comparative example 1 of the present invention 3 TPD profile, wherein (a) -example 3, (b) -example 1, (c) -comparative example 1.
Detailed Description
The invention comprises the following steps:
a catalyst ultrasonic modification method for preparing aromatic hydrocarbon by biomass catalytic pyrolysis comprises the following steps:
(1) Dissolving ammonium molybdate in deionized water, stirring and dissolving, and then immersing powder HZSM-5 in the solution to obtain a mixed solution A;
(2) Putting the mixed solution A of ammonium molybdate and HZSM-5 in an ultrasonic instrument, and carrying out ultrasonic treatment to obtain a sample B;
(3) And (3) carrying out oil bath constant-temperature heating and stirring on the sample B subjected to ultrasonic treatment, drying the sample subjected to oil bath in an oven, and finally placing the dried HZSM-5 in a muffle furnace for high-temperature calcination to obtain the modified HZSM-5.
In the step (1), the powder HZSM-5 has a silica-alumina ratio of (18-38): 1. the powder HZSM-5 has a silica-alumina ratio in the range of (18-38): 1, HZSM-5 with the silicon-aluminum ratio can enhance the aluminum sites and acidity of the catalyst framework, prevent Mo species from polymerizing on the surface of the catalyst and is beneficial to bond breaking and shape selective conversion of biomass pyrolysis steam.
In the step (1), the mass ratio of the ammonium molybdate to the HZSM-5 is (0.005-0.02): 1. the mass ratio of ammonium molybdate to HZSM-5 is (0.005-0.02): 1, the range is favorable for optimizing the distribution of acid sites of the HZSM-5 catalyst, and simultaneously, certain MoOx species serving as extra-framework species are prevented from blocking channels, so that the shape-selective deoxidation performance of the catalyst is enhanced.
In the step (1), the mass ratio of HZSM-5 to deionized water is (0.5-2): 1. the mass ratio of the HZSM-5 to the deionized water is (0.5-2): 1 is beneficial to ultrasonic cavitation and promotes the uniform distribution of metal on the surface of the catalyst.
In the step (2), the power of ultrasonic treatment is 50-150W. The ultrasonic treatment time is 0-100min. The ultrasonic treatment power is 50-150W, the ultrasonic power is beneficial to the formation of aluminum and molybdenum species in the framework, the synergistic effect of Mo species and the Bronsted acid sites on the surface of HZSM-5 is enhanced, and the yield of aromatic hydrocarbon is improved. The ultrasonic treatment time is 50-100min, the distribution of Mo species is regulated and controlled, and part of Mo species is anchored to a skeleton Al site, so that the catalytic activity of the Mo species is effectively enhanced.
In the step (3), the drying time is not less than 8h. The drying time is not less than 8h, so that the activity reduction caused by hydrothermal dealumination in the catalyst calcination process is avoided.
In the step (3), the high-temperature calcination temperature is 500-700 ℃, and the calcination time is 4h. The high-temperature calcination temperature is 500-700 ℃, the calcination time is 4h, the catalyst activity is favorably enhanced, and the HZSM-5 framework is prevented from being damaged.
The invention is further illustrated by the following examples.
The ammonium molybdate manufacturer used in the following examples was: shanghai Michelin Biochemical technology Ltd, HZSM-5 manufacturer: tianjin south China catalyst Co., ltd.
Example 1:
dissolving 0.05g of ammonium molybdate in 10ml of deionized water, stirring and dissolving, and then adding 5g of HZSM-5 powder with the silica-alumina ratio of 25; and heating and stirring the mixed sample in an oil bath kettle at a constant temperature of 105 ℃, then drying the sample in an oven for 10 hours, and finally calcining the dried HZSM-5 in a muffle furnace at a high temperature of 550 ℃ for 4 hours to obtain the modified HZSM-5.
The biomass catalytic pyrolysis test is carried out on a fixed bed reactor, the reactor is maintained at 550 ℃, the carrier gas adopts normal-pressure nitrogen, and the modified HZSM-5 catalyst is placed at the lower part of the reactor, so that the biomass pyrolysis steam breaks bonds under the action of the catalyst and is subjected to shape-selective deoxidation to be converted into a target aromatic hydrocarbon product. The biomass adopts pine sawdust, and the mass space velocity of the biomass to the catalyst is 2h -1 。
The quantitative analysis result of the biomass catalytic pyrolysis product shows that the yield of the aromatic hydrocarbon carbon is 16.9 percent.
Example 2:
0.05g of ammonium molybdate was dissolved in 10ml of deionized water and stirred to dissolve, then 5g of a mixture of 25:1 HZSM-5 powder; putting the mixture solution of ammonium molybdate and HZSM-5 in an ultrasonic instrument, and carrying out ultrasonic treatment for 50min under the power of 120W; and heating and stirring the sample subjected to ultrasonic treatment in an oil bath pan at the constant temperature of 105 ℃, then putting the sample into an oven for drying for 10 hours, and finally putting the dried HZSM-5 into a muffle furnace for high-temperature calcination at the high temperature of 550 ℃ for 4 hours to obtain the modified HZSM-5.
The biomass catalytic pyrolysis test is carried out on a fixed bed reactor, the reactor is maintained at 550 ℃, the carrier gas adopts normal-pressure nitrogen, and the modified HZSM-5 catalyst is placed at the lower part of the reactor, so that the biomass pyrolysis steam breaks bonds under the action of the catalyst and is subjected to shape-selective deoxidation to be converted into a target aromatic hydrocarbon product. The biomass adopts pine sawdust, and the mass space velocity of the biomass to the catalyst is 2h -1 。
The quantitative analysis result of the biomass catalytic pyrolysis product shows that the yield of the aromatic hydrocarbon carbon is 18.9 percent.
Example 3:
0.05g of ammonium molybdate was dissolved in 10ml of deionized water and stirred to dissolve, then 5g of a mixture of silica and alumina in a ratio of 25:1 HZSM-5 powder; putting the mixture solution of ammonium molybdate and HZSM-5 in an ultrasonic instrument, and carrying out ultrasonic treatment for 80min under the power of 120W; and heating and stirring the sample subjected to ultrasonic treatment in an oil bath pan at a constant temperature of 105 ℃, then drying the sample in an oven for 10 hours, and finally calcining the dried HZSM-5 in a muffle furnace at a high temperature of 550 ℃ for 4 hours to obtain the modified HZSM-5.
The biomass catalytic pyrolysis test is carried out on a fixed bed reactor, the reactor is maintained at 550 ℃, the carrier gas adopts normal-pressure nitrogen, and the modified HZSM-5 catalyst is placed at the lower part of the reactor, so that the biomass pyrolysis steam breaks bonds under the action of the catalyst and is subjected to shape-selective deoxidation to be converted into a target aromatic hydrocarbon product. The biomass adopts pine sawdust, and the mass space velocity of the biomass to the catalyst is 2h -1 。
The quantitative analysis result of the biomass catalytic pyrolysis product shows that the yield of the aromatic hydrocarbon carbon is 19.5 percent.
Example 4:
0.05g of ammonium molybdate was dissolved in 10ml of deionized water and stirred to dissolve, then 5g of a mixture of 25:1 HZSM-5 powder; putting the mixture solution of ammonium molybdate and HZSM-5 in an ultrasonic instrument, and carrying out ultrasonic treatment for 100min under the power of 120W; and heating and stirring the sample subjected to ultrasonic treatment in an oil bath pan at a constant temperature of 105 ℃, then drying the sample in an oven for 10 hours, and finally calcining the dried HZSM-5 in a muffle furnace at a high temperature of 550 ℃ for 4 hours to obtain the modified HZSM-5.
The biomass catalytic pyrolysis test is carried out on a fixed bed reactor, the reactor is maintained at 550 ℃, the carrier gas adopts normal-pressure nitrogen, and the modified HZSM-5 catalyst is placed at the lower part of the reactor, so that the biomass pyrolysis steam breaks bonds under the action of the catalyst and is subjected to shape-selective deoxidation to be converted into a target aromatic hydrocarbon product. The biomass adopts pine sawdust, and the mass space velocity of the biomass to the catalyst is 2h -1 。
The quantitative analysis result of the biomass catalytic pyrolysis product shows that the yield of the aromatic hydrocarbon carbon is 18.6%.
Example 5:
0.05g of ammonium molybdate was dissolved in 10ml of deionized water and stirred to dissolve, then 5g of a mixture of 25:1 HZSM-5 powder; putting the mixture solution of ammonium molybdate and HZSM-5 in an ultrasonic instrument, and carrying out ultrasonic treatment for 80min under the power of 50W; and heating and stirring the sample subjected to ultrasonic treatment in an oil bath pan at the constant temperature of 105 ℃, then putting the sample into an oven for drying for 10 hours, and finally putting the dried HZSM-5 into a muffle furnace for high-temperature calcination at the high temperature of 550 ℃ for 4 hours to obtain the modified HZSM-5.
The biomass catalytic pyrolysis test is carried out on a fixed bed reactor, the reactor is maintained at 550 ℃, the carrier gas adopts normal-pressure nitrogen, and the modified HZSM-5 catalyst is placed at the lower part of the reactor, so that the biomass pyrolysis steam breaks bonds under the action of the catalyst and is subjected to shape-selective deoxidation to be converted into a target aromatic hydrocarbon product. The biomass adopts pine sawdust, and the mass space velocity of the biomass to the catalyst is 2h -1 。
The quantitative analysis result of the biomass catalytic pyrolysis product shows that the yield of the aromatic hydrocarbon carbon is 18.2%.
Example 6:
0.05g of ammonium molybdate was dissolved in 10ml of deionized water and stirred to dissolve, then 5g of a mixture of 25:1 HZSM-5 powder; putting the mixture solution of ammonium molybdate and HZSM-5 into an ultrasonic instrument, and carrying out ultrasonic treatment for 80min under the power of 150W; and heating and stirring the sample subjected to ultrasonic treatment in an oil bath pan at a constant temperature of 105 ℃, then drying the sample in an oven for 10 hours, and finally calcining the dried HZSM-5 in a muffle furnace at a high temperature of 550 ℃ for 4 hours to obtain the modified HZSM-5.
The biomass catalytic pyrolysis test is carried out on a fixed bed reactor, the reactor is maintained at 550 ℃, the carrier gas adopts normal-pressure nitrogen, and the modified HZSM-5 catalyst is placed at the lower part of the reactor, so that the biomass pyrolysis steam breaks bonds under the action of the catalyst and is subjected to shape-selective deoxidation to be converted into a target aromatic hydrocarbon product. The biomass adopts pine sawdust, and the mass space velocity of the biomass to the catalyst is 2h -1 。
The quantitative analysis result of the biomass catalytic pyrolysis product shows that the yield of the aromatic hydrocarbon carbon is 17.3 percent.
Example 7:
0.025g of ammonium molybdate was dissolved in 10ml of deionized water and stirred to dissolve, then 5g of a mixture of silica and alumina in a ratio of 25:1 HZSM-5 powder; putting the mixture solution of ammonium molybdate and HZSM-5 in an ultrasonic instrument, and carrying out ultrasonic treatment for 80min under the power of 120W; and heating and stirring the sample subjected to ultrasonic treatment in an oil bath pan at a constant temperature of 105 ℃, then drying the sample in an oven for 10 hours, and finally calcining the dried HZSM-5 in a muffle furnace at a high temperature of 550 ℃ for 4 hours to obtain the modified HZSM-5.
The biomass catalytic pyrolysis test is carried out on a fixed bed reactor, the reactor is maintained at 550 ℃, the carrier gas adopts normal-pressure nitrogen, and the modified HZSM-5 catalyst is placed at the lower part of the reactor, so that the biomass pyrolysis steam breaks bonds under the action of the catalyst and is subjected to shape-selective deoxidation to be converted into a target aromatic hydrocarbon product. The biomass adopts pine sawdust, and the mass space velocity of the biomass to the catalyst is 2h -1 。
The quantitative analysis result of the biomass catalytic pyrolysis product shows that the yield of the aromatic hydrocarbon carbon is 18.1%.
Example 8:
0.1g of ammonium molybdate was dissolved in 10ml of deionized water and stirred to dissolve, then 5g of a mixture of aluminum and silicon in a ratio of 25:1 HZSM-5 powder; putting the mixture solution of ammonium molybdate and HZSM-5 in an ultrasonic instrument, and carrying out ultrasonic treatment for 80min under the power of 120W; and heating and stirring the sample subjected to ultrasonic treatment in an oil bath pan at a constant temperature of 105 ℃, then drying the sample in an oven for 10 hours, and finally calcining the dried HZSM-5 in a muffle furnace at a high temperature of 550 ℃ for 4 hours to obtain the modified HZSM-5.
The biomass catalytic pyrolysis test is carried out on a fixed bed reactor, the reactor is maintained at 550 ℃, the carrier gas adopts normal-pressure nitrogen, and the modified HZSM-5 catalyst is placed at the lower part of the reactor, so that the biomass pyrolysis steam breaks bonds under the action of the catalyst and is subjected to shape-selective deoxidation to be converted into a target aromatic hydrocarbon product. The biomass adopts pine sawdust, and the mass space velocity of the biomass to the catalyst is 2h -1 。
The quantitative analysis result of the biomass catalytic pyrolysis product shows that the yield of the aromatic hydrocarbon carbon is 18.9 percent.
Example 9:
0.05g of ammonium molybdate was dissolved in 10ml of deionized water and stirred to dissolve, then 5g of a mixture of aluminum and silicon in a ratio of 18:1 HZSM-5 powder; putting the mixture solution of ammonium molybdate and HZSM-5 in an ultrasonic instrument, and carrying out ultrasonic treatment for 80min under the power of 120W; and heating and stirring the sample subjected to ultrasonic treatment in an oil bath pan at a constant temperature of 105 ℃, then drying the sample in an oven for 10 hours, and finally calcining the dried HZSM-5 in a muffle furnace at a high temperature of 550 ℃ for 4 hours to obtain the modified HZSM-5.
The biomass catalytic pyrolysis test is carried out on a fixed bed reactor, the reactor is maintained at 550 ℃, the carrier gas adopts normal-pressure nitrogen, and the modified HZSM-5 catalyst is placed at the lower part of the reactor, so that the biomass pyrolysis steam breaks bonds under the action of the catalyst and is subjected to shape-selective deoxidation to be converted into a target aromatic hydrocarbon product. The biomass adopts pine sawdust, and the mass space velocity of the biomass to the catalyst is 2h -1 。
The quantitative analysis result of the biomass catalytic pyrolysis product shows that the yield of the aromatic hydrocarbon carbon is 18.8%.
Example 10:
0.05g of ammonium molybdate was dissolved in 10ml of deionized water and stirred to dissolve, then 5g of a solution of 38:1 HZSM-5 powder; putting the mixture solution of ammonium molybdate and HZSM-5 in an ultrasonic instrument, and carrying out ultrasonic treatment for 80min under the power of 120W; and heating and stirring the sample subjected to ultrasonic treatment in an oil bath pan at a constant temperature of 105 ℃, then drying the sample in an oven for 10 hours, and finally calcining the dried HZSM-5 in a muffle furnace at a high temperature of 550 ℃ for 4 hours to obtain the modified HZSM-5.
The biomass catalytic pyrolysis test is carried out on a fixed bed reactor, the reactor is maintained at 550 ℃, the carrier gas adopts normal-pressure nitrogen, and the modified HZSM-5 catalyst is placed at the lower part of the reactor, so that the biomass pyrolysis steam breaks bonds under the action of the catalyst and is subjected to shape-selective deoxidation to be converted into a target aromatic hydrocarbon product. The biomass adopts pine sawdust, and the mass space velocity of the biomass to the catalyst is 2h -1 。
The quantitative analysis result of the biomass catalytic pyrolysis product shows that the yield of the aromatic hydrocarbon carbon is 17.6 percent.
Example 11:
0.05g of ammonium molybdate was dissolved in 2.5ml of deionized water and stirred to dissolve, then 5g of a mixture of silica and alumina in a ratio of 25:1 HZSM-5 powder; putting the mixture solution of ammonium molybdate and HZSM-5 in an ultrasonic instrument, and carrying out ultrasonic treatment for 80min under the power of 120W; and heating and stirring the sample subjected to ultrasonic treatment in an oil bath pan at a constant temperature of 105 ℃, then drying the sample in an oven for 10 hours, and finally calcining the dried HZSM-5 in a muffle furnace at a high temperature of 550 ℃ for 4 hours to obtain the modified HZSM-5.
The biomass catalytic pyrolysis test is carried out on a fixed bed reactor, the reactor is maintained at 550 ℃, the carrier gas adopts normal-pressure nitrogen, and the modified HZSM-5 catalyst is placed at the lower part of the reactor, so that the biomass pyrolysis steam breaks bonds under the action of the catalyst and is subjected to shape-selective deoxidation to be converted into a target aromatic hydrocarbon product. The biomass adopts pine sawdust, and the mass space velocity of the biomass to the catalyst is 2h -1 。
The quantitative analysis result of the biomass catalytic pyrolysis product shows that the yield of the aromatic hydrocarbon carbon is 17.1 percent.
Comparative example 1:
5g of silicon-aluminum ratio is 25: putting the HZSM-5 powder of 1 into an oven for drying for 10h, and finally putting the dried HZSM-5 into a muffle furnace for calcining at 550 ℃ for 4h to obtain the HZSM-5.
The biomass catalytic pyrolysis test is carried out on a fixed bed reactor, the reactor is maintained at 550 ℃, the carrier gas adopts normal-pressure nitrogen, and the HZSM-5 catalyst is arranged at the lower part of the reactor, so that the biomass pyrolysis steam breaks bonds under the action of the catalyst and is subjected to shape-selective deoxidation to be converted into a target aromatic hydrocarbon product. The biomass adopts pine sawdust, and the mass space velocity of the biomass to the catalyst is 2h -1 。
The quantitative analysis result of the biomass catalytic pyrolysis product shows that the yield of the aromatic hydrocarbon carbon is 15.2%.
Claims (8)
1. A method for improving the yield of aromatic hydrocarbon in catalytic pyrolysis of biomass is characterized by comprising the following steps:
(1) Dissolving ammonium molybdate in deionized water, stirring and dissolving, and then immersing powder HZSM-5 in the solution to obtain a mixed solution A;
(2) Putting the mixed solution A of ammonium molybdate and HZSM-5 in an ultrasonic instrument, and carrying out ultrasonic treatment to obtain a sample B;
(3) And (3) carrying out oil bath constant-temperature heating and stirring on the sample B subjected to ultrasonic treatment, drying the sample subjected to oil bath in an oven, and finally placing the dried HZSM-5 in a muffle furnace for high-temperature calcination to obtain the modified HZSM-5.
2. The method for improving the yield of the catalytic pyrolysis of the biomass for the aromatic hydrocarbons according to claim 1, wherein the method comprises the following steps: in the step (1), the powder HZSM-5 has a silica-alumina ratio of (18-38): 1.
3. the method for improving the yield of the catalytic pyrolysis of the biomass for the aromatic hydrocarbons according to claim 1, wherein the method comprises the following steps: in the step (1), the mass ratio of the ammonium molybdate to the HZSM-5 is (0.005-0.02): 1.
4. the method for improving the yield of the catalytic pyrolysis of the biomass for the aromatic hydrocarbons according to claim 1, wherein the method comprises the following steps: in the step (1), the mass ratio of HZSM-5 to deionized water is (0.5-2): 1.
5. the method for improving the yield of aromatic hydrocarbons produced by catalytic pyrolysis of biomass according to claim 1, wherein: in the step (2), the power of ultrasonic treatment is 50-150W.
6. The method for improving the yield of aromatic hydrocarbons produced by catalytic pyrolysis of biomass according to claim 1, wherein: in the step (2), the ultrasonic treatment time is 50-100min.
7. The method for improving the yield of the catalytic pyrolysis of the biomass for the aromatic hydrocarbons according to claim 1, wherein the method comprises the following steps: in the step (3), the drying time is not less than 8h.
8. The method for improving the yield of aromatic hydrocarbons produced by catalytic pyrolysis of biomass according to claim 1, wherein: in the step (3), the high-temperature calcination temperature is 500-700 ℃, and the calcination time is 3-6h.
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