CN113083306A - Preparation method and application of catalyst for improving content of phenolic compounds in low-rank coal microwave pyrolysis tar - Google Patents

Preparation method and application of catalyst for improving content of phenolic compounds in low-rank coal microwave pyrolysis tar Download PDF

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CN113083306A
CN113083306A CN202110229719.2A CN202110229719A CN113083306A CN 113083306 A CN113083306 A CN 113083306A CN 202110229719 A CN202110229719 A CN 202110229719A CN 113083306 A CN113083306 A CN 113083306A
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catalyst
tar
low
rank coal
phenolic compounds
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王光华
杨旭萌
王晴东
李文兵
蔡文轩
李笑原
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Wuhan University of Science and Engineering WUSE
Wuhan University of Science and Technology WHUST
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Wuhan University of Science and Engineering WUSE
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Abstract

The invention belongs to the technical field of microwave catalytic pyrolysis of low-rank coal. The invention provides a preparation method and application of a catalyst for improving the content of phenolic compounds in tar by microwave pyrolysis of low-rank coal, wherein the preparation raw materials comprise a catalytic active component, a cocatalyst and a catalyst carrier, wherein the catalytic active component plays a main catalytic role, and the addition of the cocatalyst can improve the connecting capacity of the catalyst carrier and the catalytic active component, so that the catalyst is free from leaching in the microwave catalytic reaction process of the low-rank coal, and the service life of the catalyst is prolonged; the carrier with large specific surface area is used as the catalyst carrier, so that the catalytic reaction rate and the cost reaction process can be effectively improved. The invention also provides application of the catalyst in low-rank coal microwave pyrolysis, the catalytic efficiency is high, the catalytic speed is high, the content of phenolic compounds in the pyrolyzed tar can be effectively improved, and the economic benefit of the tar is further improved.

Description

Preparation method and application of catalyst for improving content of phenolic compounds in low-rank coal microwave pyrolysis tar
Technical Field
The invention relates to the technical field of low-rank coal microwave pyrolysis, in particular to a preparation method and application of a catalyst for improving the content of phenolic compounds in low-rank coal microwave pyrolysis tar.
Background
The coal tar obtained by pyrolyzing low-rank coal is a very complex mixture of black brown, viscous and numerous high-aromatic hydrocarbons, the total number of the components is over ten thousands, and about 500 types which are found at present mainly contain organic substances such as phenols, naphthalenes, anthracenes, quinolines, asphalts and the like. The phenolic compound is an important chemical raw material, can be used as a raw material in the fields of producing plastics, fibers, killing insects, pharmacy, coloring agents, explosive manufacturing and the like, and is an excellent raw material for preparing diesel oil with high cetane number by hydrogenation. Therefore, the method for improving the content of the phenolic compounds in the coal tar is one of important ways for obtaining high-added-value chemicals of the coal tar and improving the coal pyrolysis economic value.
Under the condition of catalyst, the cracking of the components in the tar can be accelerated at a lower temperature, and the added catalyst promotes the reforming reaction from two aspects, namely, on one hand, the sufficient specific surface area of the catalyst provides points and places for the cracking reforming reaction of tar molecules, and on the other hand, the active components in the catalyst participate in the reforming reaction to reduce the activation energy of the reaction, accelerate the intermolecular reaction, further promote the cracking of macromolecular substances in the tar and increase the content of phenolic compounds.
The unique heating mechanism of microwave heating has the characteristics of high heating speed, uniform heating and selective heating, and can be used for pyrolyzing the low-rank coal, so that the low-rank coal can be quickly heated to the pyrolysis reaction temperature, and the pyrolysis speed is increased; in addition, the uniform temperature distribution reduces the secondary cracking reaction of tar molecules in the escaping process, reduces the loss of tar, selectively heats compounds with high dielectric constants such as oxygen-containing compounds in the tar, promotes the thermal decomposition of the compounds, increases the content of phenolic compounds in the tar, and improves the quality of the tar. Researches show that the catalyst suitable for microwave pyrolysis of low-rank coal comprises a metal catalyst, a molecular sieve catalyst and a carbon-based catalyst, wherein the molecular sieve catalyst and the carbon-based catalyst are mostly used as catalyst carriers due to rich physical pore structures and large specific surface areas, but the molecular sieve is high in price and easy to form carbon on the surface of the catalyst to cause catalyst inactivation; the metal catalyst comprises alkali metal, alkaline earth metal, transition metal, iron-based catalyst and natural mineral, however, the alkali metal can be crosslinked with coal molecules in the pyrolysis process, which is not beneficial to the generation of tar; the iron-based catalyst and part of transition metal synthesized by the general method have promotion effect on the yield of the microwave pyrolysis tar, but have weak promotion effect on the generation of the phenolic compounds.
Based on the above, the catalyst with strong wave absorption performance and high selective catalytic activity is developed, and the catalyst for improving the content of the phenolic compounds in the tar of the low-rank coal microwave pyrolysis product is particularly important.
Disclosure of Invention
The invention provides a catalyst for improving the content of phenolic compounds in tar by microwave pyrolysis of low-rank coal, which comprises a catalytic active substance, a cocatalyst and a catalyst carrier; the catalytic active substance is one or more of nickel oxide and iron oxide; the catalyst promoter is one or more of molybdenum oxide, magnesium oxide and cobalt oxide; the catalyst carrier is one or more of alumina, semicoke, H-ZSM-5 molecular sieve and USY molecular sieve.
The catalyst for improving the content of the phenolic compounds in the tar by the microwave pyrolysis of the low-rank coal comprises a catalytic active substance, wherein the catalytic active substance is one or more of nickel oxide and iron oxide; the nickel oxide is nickel oxide (NiO); the iron oxide is ferric oxide (Fe)2O3). The proportion of the active substances of the catalyst is not specially specified, and can be arbitrarily proportioned. The catalytic active substance has high dielectric constant, can adjust a pyrolysis reaction structure, reduce the content of heavy components, improve the content of phenolic compounds, improve the wave absorbing capacity of the whole low-rank coal and accelerate the pyrolysis reaction.
In the present invention, the molar ratio of the catalytically active material to the metal ions in the cocatalyst is preferably 1: (0.05-10), more preferably 1: (0.5 to 8), and more preferably 1: (2-6); the mass ratio of the catalyst carrier to the catalytically active material is preferably 1: (0.005-1), more preferably 1: (0.05 to 0.8), and more preferably 1: (0.1-0.5).
The invention provides a preparation method of the catalyst, which comprises the following steps:
mixing metal salt corresponding to a catalytic active substance and metal salt corresponding to a cocatalyst with water to obtain metal salt solution;
secondly, mixing the metal salt solution with a sodium dodecyl benzene sulfonate aqueous solution, and adjusting the pH value to 9-10 to obtain a suspension;
thirdly, separating the suspension, and performing first roasting on the obtained solid sediment to obtain a nano catalyst precursor;
mixing the nano catalyst precursor with a catalyst carrier and a dispersing agent, dispersing, and sequentially performing microwave irradiation and secondary roasting on the obtained dispersion liquid to obtain a catalyst for improving the content of phenolic compounds in the low-rank coal microwave pyrolysis tar;
the metal salt corresponding to the catalytic active substance is one or more of nickel salt and ferric salt; the metal salt corresponding to the cocatalyst is one or more of molybdenum salt, magnesium salt and cobalt salt;
the catalyst carrier is one or more of alumina, semicoke, H-ZSM-5 molecular sieve and USY molecular sieve.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
The invention mixes the metal salt corresponding to the catalytic active substance and the metal salt corresponding to the cocatalyst with water to obtain the metal salt solution. In the invention, the metal salt corresponding to the catalytic active substance is one or more of nickel salt and ferric salt; the nickel salt is preferably Ni (NO)3)2·6H2O; the iron salt is preferably Fe (NO)3)3·9H2And O. When the metal salts corresponding to the catalytic active substances are preferably selected from the above-mentioned metal salts, the ratio of the metal salts of different types is not particularly limited, and any ratio can be used.
In the invention, the metal salt corresponding to the cocatalyst is one or more of molybdenum salt, magnesium salt and cobalt salt; the molybdenum salt is preferably ammonium molybdate tetrahydrate H24Mo7N6O24·4H2O; the magnesium salt is preferably magnesium nitrate hexahydrate Mg (NO)3)2·6H2O; the cobalt salt is preferably cobalt nitrate hexahydrate Co (NO)3)2·6H2O; when the metal salts corresponding to the promoters are preferably selected from the above-mentioned metal salts, the ratio of the metal salts of different types is not particularly limited, and any ratio can be used.
The process of mixing the metal salt corresponding to the catalytically active material and the metal salt corresponding to the cocatalyst with water is not particularly limited in the present invention, and may be performed according to a process well known in the art. In the invention, in the metal salt solution, the concentration of the metal salt corresponding to the catalytic active substance is preferably 0.05-0.2 mol/L; the concentration of the metal salt corresponding to the cocatalyst is preferably 0.05-0.2 mol/L.
After the metal salt solution is obtained, the metal salt solution is mixed with a sodium dodecyl benzene sulfonate aqueous solution, and the pH value is adjusted to 9-10 to obtain a suspension. In the invention, the concentration of the sodium dodecyl benzene sulfonate aqueous solution is preferably 0.80-1.60 g/L, more preferably 0.90-1.50 g/L, and further preferably 1.00-1.40 g/L, and the mass ratio of the sodium dodecyl benzene sulfonate in the sodium dodecyl benzene sulfonate aqueous solution to the metal salt corresponding to the catalytic active substance is preferably 1: (1 to 100), more preferably 1: (5-95), more preferably 1: (10-90). The invention utilizes sodium dodecyl benzene sulfonate as a surfactant, utilizes the steric hindrance effect among macromolecules of the surfactant, regulates the particle size of the catalyst to be in a nanometer level, and prevents active components of the catalyst and a cocatalyst from being agglomerated.
In the invention, the mixing temperature of the metal salt solution and the sodium dodecyl benzene sulfonate aqueous solution is preferably 50-100 ℃, more preferably 60-90 ℃, and more preferably 70-80 ℃; the mixing is preferably carried out under stirring, and the stirring process is not particularly limited in the present invention and may be carried out according to a process well known in the art.
According to the invention, the pH value is preferably adjusted to 9-10 by dropwise adding a potassium hydroxide solution, and continuously stirring to obtain a suspension. The stirring process is not particularly limited in the present invention, and may be carried out according to a process known in the art. In the invention, the concentration of the potassium hydroxide solution is preferably 1-5 mol/L, more preferably 1.5-4.5 mol/L, and more preferably 2.0-4.0 mol/L; the continuous stirring time is preferably 1-4 h, more preferably 1.5-3.5 h, and even more preferably 2-3 h; the rotation speed of the continuous stirring is preferably 200 rpm. The invention utilizes potassium hydroxide solution as a precipitant.
In the present invention, the suspension contains a hydroxide of a metal salt corresponding to the catalytically active material and a hydroxide of a metal salt corresponding to the promoter.
After obtaining the suspension, the invention separates the suspension, and carries out first roasting on the obtained solid sediment to obtain the nano catalyst precursor. In the present invention, the separation is preferably performed by centrifugation, and the centrifugation process is not particularly limited in the present invention, and a solid deposit can be obtained according to a process well known in the art.
After the separation is completed, the obtained solid product is preferably repeatedly washed by using deionized water and absolute ethyl alcohol respectively, filtered until the pH is =7, dried and cooled to obtain a solid deposit. In the invention, the drying temperature is preferably 90-120 ℃, more preferably 95-115 ℃, and more preferably 100-110 ℃; the drying time is preferably 1 to 4 hours, more preferably 1.5 to 3.5 hours, and even more preferably 2 to 3 hours. The cooling process is not particularly limited in the present invention, and may be performed according to a process well known in the art.
In the present invention, the first firing is preferably performed under a nitrogen atmosphere; the first firing is preferably carried out in a muffle furnace; the rate of temperature rise to the temperature of the first calcination is preferably 5 ℃/min; the first roasting temperature is preferably 300-600 ℃, more preferably 350-550 ℃, and more preferably 400-500 ℃; the time is preferably 1.0 to 4.0 hours, more preferably 1.5 to 3.5 hours, and still more preferably 2.0 to 3.0 hours. After the first calcination is completed, the present invention preferably cools to room temperature to obtain a nano-catalyst precursor. The cooling process is not particularly limited in the present invention, and may be performed according to a process well known in the art.
In the first roasting process, the metal salt corresponding to the catalytic active substance and the metal salt corresponding to the cocatalyst are converted into metal oxides.
After the nano catalyst precursor is obtained, the nano catalyst precursor is mixed with the catalyst carrier and the dispersing agent for dispersing, and the obtained dispersion liquid is sequentially subjected to microwave irradiation and secondary roasting to obtain the catalyst for improving the content of the tar phenolic compound by the microwave pyrolysis of the low-rank coal. In the invention, the dispersant is preferably ethanol, and the dosage ratio of the catalyst carrier to the ethanol is preferably (1-2) g: (5-15) mL. In the invention, the mixing is preferably carried out under a stirring condition, and the stirring speed is preferably 100-300 rpm, more preferably 120-280 rpm, and more preferably 140-260 rpm; the stirring time is not specially limited, and the materials can be uniformly mixed. In the invention, the dispersion is preferably carried out under ultrasonic conditions, the frequency of the ultrasonic is preferably 40KHz, and the time is preferably 1-30 min, more preferably 5-25 min, and even more preferably 10-20 min. The invention fully immerses the catalyst carrier in the catalytic active substance and the cocatalyst solution by ultrasound, and the catalytic active substance and the cocatalyst are loaded on the catalyst carrier in an ionic state and permeate into the carrier, so that the catalytic active substance and the cocatalyst are effectively loaded on the catalyst carrier.
After the dispersion is completed, the present invention preferably performs a microwave irradiation by filtering and washing the resultant product three times. In the invention, the frequency of the microwave irradiation is preferably 2450MHz, the power is preferably 400-1200W, more preferably 500-1100W, and even more preferably 600-1000W; the time of the microwave irradiation is preferably 5-25 min, more preferably 8-22 min, and even more preferably 11-19 min. The invention utilizes the molecular heating mechanism of microwave irradiation, is beneficial to the improvement of the pore channel structure of the catalyst carrier and the increase of the specific surface area while realizing the rapid drying, can enhance the pore diameter structure and the distribution of the catalyst, and improves the catalytic effect; meanwhile, the catalytic active substances are prevented from slowly moving outwards along with the water vapor, so that the catalytic active substances are enriched on the outer surface of the catalyst carrier, and the catalytic active substances are prevented from being unevenly distributed.
In the present invention, the rate of temperature rise to the temperature of the second calcination is preferably 5 ℃/min; the second roasting temperature is preferably 300-600 ℃, more preferably 350-550 ℃, and more preferably 400-500 ℃; the roasting time is preferably 1.0 to 4.0 hours, more preferably 1.5 to 3.5 hours, and even more preferably 2.0 to 3.0 hours. The invention removes volatile impurities in the catalyst through second roasting to obtain the catalyst with close and stable adhesion.
In the method, the solution of the catalytic active substance and the cocatalyst is mixed with the solution of the sodium dodecyl benzene sulfonate, potassium hydroxide is used as a precipitator, the steric hindrance effect of macromolecules of the sodium dodecyl benzene sulfonate surfactant is utilized to regulate and control the particle size of the catalyst to be in a nanometer level, then the catalyst carrier is fully immersed in the catalytic active substance and the cocatalyst solution through ultrasound, the catalytic active substance and the cocatalyst are loaded on the catalyst carrier in an ionic state and permeate into the carrier, and then the unique heating mechanism of microwaves is utilized, so that the pore diameter structure and distribution of the catalyst can be enhanced during quick drying, and the catalytic effect is improved.
The invention provides the preparation of the catalyst for improving the content of the naphthenic hydrocarbon in the tar by the microwave pyrolysis of the low-rank coal.
In the present invention, the method of application preferably comprises the steps of: mixing the low-rank coal powder with a catalyst for improving the naphthenic hydrocarbon content in the tar by low-rank coal microwave pyrolysis, introducing high-purity helium, performing microwave catalytic pyrolysis reaction in a microwave field under the condition of oxygen isolation, and collecting the liquefied tar by using double liquid nitrogen condensation to obtain the tar with high naphthenic hydrocarbon content.
In the present invention, the particle size of the low-rank pulverized coal is preferably 200 mesh or less; the mass of the low-rank coal powder is preferably 1-60 g, more preferably 10-50 g, and even more preferably 20-40 g; in the invention, the mass of the catalyst for improving the content of naphthene in tar by microwave pyrolysis of low-rank coal is preferably 1-10% of that of the low-rank coal, more preferably 2-9%, and even more preferably 3-8%. In the invention, the purity of the high-purity helium gas is preferably more than or equal to 99.9996%.
In the invention, the frequency of the microwave field is preferably 2450MHz, the power is preferably 600-1200W, more preferably 700-1100W, and more preferably 800-1000W; the time of the microwave catalytic pyrolysis reaction is preferably 20-80 min, more preferably 30-70 min, and even more preferably 40-60 min; the final temperature of the microwave pyrolysis reaction is preferably 600-900 ℃, and more preferably 700-800 ℃.
The cooling and collecting processes are not particularly limited in the present invention and may be performed according to processes well known in the art.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
2.9081g (0.01 mol) Ni (NO)3)2·6H2O、1.2080g（0.005mol）Cu(NO3)2·3H2Adding O into 100mL of deionized water, stirring until the O is completely dissolved to obtain a metal salt solution, dissolving 0.1163g of sodium dodecyl benzene sulfonate in 100mL of deionized water, stirring until the O is completely dissolved to obtain a sodium dodecyl benzene sulfonate aqueous solution (1.163 g/L), uniformly stirring and mixing the metal salt solution and the sodium dodecyl benzene sulfonate aqueous solution at 80 ℃, dropwise adding 3mol/L of a potassium hydroxide solution into the obtained mixed solution, adjusting the pH =10, continuously stirring at the rotation speed of 200rpm at 80 ℃ for 2 hours to obtain a suspension, centrifugally separating the suspension, repeatedly washing the obtained solid product with deionized water and ethanol respectively, performing suction filtration until the pH =7, drying the obtained solid deposit in a 110 ℃ oven for 2 hours, cooling to room temperature, then placing in a muffle furnace, heating to 600 ℃ at the speed of 5 ℃/min, performing first roasting for 4 hours, cooling to room temperature to obtain a nano catalyst precursor;
dissolving 2g of the nano catalyst precursor and 6g of semi-coke powder (below 200 meshes) in 150mL of ethanol under the stirring condition of 200rpm, performing ultrasonic dispersion, setting the ultrasonic frequency to be 40KHz, performing ultrasonic treatment for 15min, filtering and washing the obtained product for three times, placing the product in a microwave field, setting the frequency to be 2450MHz, performing microwave irradiation for 15min, placing the obtained product in a muffle furnace, heating to 400 ℃ at the speed of 5 ℃/min, and performing secondary roasting for 4h to obtain the catalyst for improving the naphthenic hydrocarbon content in the tar by microwave pyrolysis of low-rank coal.
Example 2
2.9081g of Ni (NO)3)2·6H2O、2.4160g Cu(NO3)2·3H2Adding O into 100mL of deionized water, stirring until the O is completely dissolved to obtain a metal salt solution, dissolving 0.1163g of sodium dodecyl benzene sulfonate in 100mL of deionized water, stirring until the O is completely dissolved to obtain a sodium dodecyl benzene sulfonate aqueous solution (1.163 g/L), uniformly stirring and mixing the metal salt solution and the sodium dodecyl benzene sulfonate aqueous solution at 80 ℃, dropwise adding 3mol/L of a potassium hydroxide solution into the obtained mixed solution, adjusting the pH =10, continuously stirring at the rotation speed of 200rpm at 80 ℃ for 2 hours to obtain a suspension, centrifugally separating the suspension, repeatedly washing the obtained solid product with deionized water and ethanol respectively, performing suction filtration until the pH =7, drying the obtained solid deposit in a 110 ℃ oven for 2 hours, cooling to room temperature, then placing in a muffle furnace, heating to 600 ℃ at the speed of 5 ℃/min, performing first roasting for 4 hours, cooling to room temperature to obtain a nano catalyst precursor;
dissolving 2g of the nano catalyst precursor and 6g of semi-coke powder (below 200 meshes) in 150mL of ethanol under the stirring condition of 200rpm, performing ultrasonic dispersion, setting the ultrasonic frequency to be 40KHz, performing ultrasonic treatment for 15min, filtering and washing the obtained product for three times, placing the product in a microwave field, setting the frequency to be 2450MHz, performing microwave irradiation for 15min, placing the obtained product in a muffle furnace, heating to 400 ℃ at the speed of 5 ℃/min, and performing secondary roasting for 4h to obtain the catalyst for improving the naphthenic hydrocarbon content in the tar by microwave pyrolysis of low-rank coal.
Example 3
2.9081g of Ni (NO)3)2·6H2O、3.6240g Cu(NO3)2·3H2Adding O into 100mL of deionized water, stirring until the O is completely dissolved to obtain a metal salt solution, dissolving 0.1163g of sodium dodecyl benzene sulfonate into 100mL of deionized water, stirring until the O is completely dissolved to obtain a sodium dodecyl benzene sulfonate aqueous solution (1.163 g/L), uniformly stirring and mixing the metal salt solution and the sodium dodecyl benzene sulfonate aqueous solution at 80 ℃, dropwise adding 3mol/L of potassium hydroxide solution into the obtained mixed solution, adjusting the pH to be =10, and performing stirring at 80 ℃ to obtain a metal salt solutionContinuously stirring at the rotation speed of 200rpm for 2 hours to obtain a suspension, centrifugally separating the suspension, repeatedly cleaning an obtained solid product by respectively using deionized water and ethanol, performing suction filtration until the pH is =7, drying the obtained solid deposit in a 110 ℃ oven for 2 hours, cooling to room temperature, then placing in a muffle furnace, heating to 600 ℃ at the speed of 5 ℃/min, performing first roasting for 4 hours, and cooling to room temperature to obtain a nano-catalyst precursor;
dissolving 2g of the nano catalyst precursor and 6g of semi-coke powder (below 200 meshes) in 150mL of ethanol under the stirring condition of 200rpm, performing ultrasonic dispersion, setting the ultrasonic frequency to be 40KHz, performing ultrasonic treatment for 15min, filtering and washing the obtained product for three times, placing the product in a microwave field, setting the frequency to be 2450MHz, performing microwave irradiation for 15min, placing the obtained product in a muffle furnace, heating to 400 ℃ at the speed of 5 ℃/min, and performing secondary roasting for 4h to obtain the catalyst for improving the naphthenic hydrocarbon content in the tar by microwave pyrolysis of low-rank coal.
Application example 1
The catalysts prepared in examples 1 to 3 were subjected to effect verification:
uniformly mixing 20g of low-rank coal powder below 200 meshes and 1.2g of catalyst, uniformly loading the mixture into a quartz tube, placing the quartz tube into a microwave field of 800W and 2450MHz, irradiating the quartz tube for 50min by microwaves, recording the temperature change in the process in a table 1, performing double liquid nitrogen condensation on the generated high-temperature steam, and collecting liquefied tar.
And carrying out GC-MS detection on the collected tar, wherein the detection equipment is a Thermo Fisher ISQ type GC-MS analyzer, the conditions are an FID detector, a DB-5MS (30.0 m multiplied by 0.25 mm) capillary tube, the carrier gas is helium, the injection port temperature is 300 ℃, the temperature raising program is constant at 150 ℃ for 5min, the temperature is raised to 280 ℃ at the speed of 2 ℃/min, and the temperature is kept for 10 min. The results of the tests are reported in table 1.
Comparative application
Taking 20g of low-rank coal powder below 200 meshes, uniformly filling the low-rank coal powder into a quartz tube, placing the quartz tube in a microwave field of 800W and 2450MHz, introducing high-purity helium (the purity is more than or equal to 99.9996%), irradiating the high-purity helium for 50min by using microwaves, recording the temperature rise time for rising the temperature to 800 ℃ in the process in a table 1, carrying out double liquid nitrogen condensation on the generated high-temperature steam, and collecting liquefied tar. Performing GC-MS detection on tar, wherein the detection equipment is a Thermo Fisher ISQ type GC-MS analyzer under the conditions of an FID detector, a DB-5MS (30.0 m multiplied by 0.25 mm) capillary tube, helium is used as carrier gas, the injection port temperature is 300 ℃, the temperature raising program is 150 ℃, the temperature is kept for 5min, the temperature is raised to 280 ℃ at the speed of 2 ℃/min, and the temperature is kept for 10 min. The results of the tests are reported in table 1.
TABLE 1 data after catalytic microwave pyrolysis of catalysts of examples 1-6
Case(s) Tar yield (%) Phenolic Compound content (%) The time taken for the temperature to rise to 800 ℃ (indirectly representing the rate of temperature rise)
Comparative application 5.67 15.91 58min
Example 1 catalyst 6.15 21.75 50min
Example 2 catalyst 8.26 24.63 44min
Example 3 catalyst 7.53 22.14 39min
As can be seen from table 1, compared with the microwave pyrolysis of the simple low-rank coal raw coal (application comparative example), the catalyst provided by the invention can catalyze the microwave pyrolysis of the low-rank coal to prepare the catalyst with high naphthene content tar, the catalysts prepared by the two preparation methods provided by the invention both have obvious catalytic effects, and the tar yield and the phenolic compound content are both improved, wherein the tar yield and the naphthene content in example 2 are higher and respectively reach 8.26% and 24.63%, and the microwave absorbing capacity of the whole reactant is improved due to the fact that the metal oxide with high dielectric constant is used as the catalytic active substance and the cocatalyst, and can be increased to 800 ℃ in a short time, and the rate of the pyrolysis reaction is accelerated.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (6)

1. A preparation method and application of a catalyst for improving the content of phenolic compounds in tar by microwave pyrolysis of low-rank coal are characterized by comprising a catalytic active component, a cocatalyst and a catalyst carrier; the catalytic active component is one or more of nickel oxide and iron oxide; the catalyst promoter is one or more of molybdenum oxide, magnesium oxide and cobalt oxide; the catalyst carrier is one or more of alumina, semicoke, H-ZSM-5 molecular sieve and USY molecular sieve.
2. The catalyst for improving the content of phenolic compounds in tar through low-rank coal microwave pyrolysis as claimed in claim 1, wherein the molar ratio of the catalytically active substance to the metal ions in the cocatalyst is 1: (0.05-10); the mass ratio of the catalyst carrier to the catalytic active substance is 1: (0.005-1).
3. The preparation method of the catalyst for improving the content of the phenolic compounds in the tar by the microwave pyrolysis of the low-rank coal as claimed in claim 1 or 2 is characterized by comprising the following steps:
mixing metal salt corresponding to a catalytic active substance and metal salt corresponding to a cocatalyst with water to obtain metal salt solution;
mixing the metal salt solution with a sodium dodecyl benzene sulfonate aqueous solution, and adjusting the pH value to 9-10 to obtain a suspension;
separating the suspension, and performing first roasting on the obtained solid sediment to obtain a nano catalyst precursor;
mixing the nano catalyst precursor with a catalyst carrier and a dispersing agent, dispersing, and sequentially performing microwave irradiation and secondary roasting on the obtained dispersion liquid to obtain a catalyst for improving the content of phenolic compounds in tar through low-rank coal microwave pyrolysis;
the metal salt corresponding to the catalytic active substance is one or more of nickel salt and ferric salt; the metal salt corresponding to the cocatalyst is one or more of molybdenum salt, magnesium salt and cobalt salt;
the catalyst carrier is one or more of alumina, semicoke, H-ZSM-5 molecular sieve and USY molecular sieve.
4. The preparation method according to claim 3, wherein the concentration of the sodium dodecyl benzene sulfonate aqueous solution is 0.80-1.60 g/L, and the mass ratio of the sodium dodecyl benzene sulfonate in the sodium dodecyl benzene sulfonate aqueous solution to the metal salt corresponding to the catalytic active substance is 1: (1-100).
5. The preparation method according to claim 3, wherein the power of the microwave irradiation is 400-1200W, and the time of the microwave irradiation is 5-25 min.
6. The catalyst for improving the content of the phenolic compounds in the tar by microwave pyrolysis of low-rank coal according to claim 1 or 2 or the catalyst for improving the content of the phenolic compounds in the tar by microwave pyrolysis of low-rank coal, which is prepared by the preparation method according to any one of claims 3 to 5, is applied to preparation of the tar with high content of the phenolic compounds by microwave pyrolysis of low-rank coal.
CN202110229719.2A 2021-03-02 2021-03-02 Preparation method and application of catalyst for improving content of phenolic compounds in low-rank coal microwave pyrolysis tar Pending CN113083306A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113578346A (en) * 2021-08-13 2021-11-02 江苏大学 Copper/silver alloy nano catalyst and preparation method and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113578346A (en) * 2021-08-13 2021-11-02 江苏大学 Copper/silver alloy nano catalyst and preparation method and application thereof

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