CN115709096A - High-activity catalyst for preparing benzene by disproportionation of toluene - Google Patents
High-activity catalyst for preparing benzene by disproportionation of toluene Download PDFInfo
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- CN115709096A CN115709096A CN202110969937.XA CN202110969937A CN115709096A CN 115709096 A CN115709096 A CN 115709096A CN 202110969937 A CN202110969937 A CN 202110969937A CN 115709096 A CN115709096 A CN 115709096A
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- molecular sieve
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- toluene
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- disproportionation
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title claims abstract description 111
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 230000000694 effects Effects 0.000 title claims abstract description 23
- 238000007323 disproportionation reaction Methods 0.000 title claims abstract description 21
- 239000002808 molecular sieve Substances 0.000 claims abstract description 95
- 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 95
- 230000005496 eutectics Effects 0.000 claims abstract description 58
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 9
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 239000011230 binding agent Substances 0.000 claims abstract description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 12
- 235000019270 ammonium chloride Nutrition 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
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- 239000000843 powder Substances 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
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- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
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- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
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- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
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- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
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- 238000001833 catalytic reforming Methods 0.000 description 2
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of molecular sieve catalytic materials, and discloses a high-activity toluene disproportionation benzene preparation catalyst, which consists of a hydrogen type eutectic molecular sieve, a binder, an active metal or metal oxide and an auxiliary agent, has the characteristics of high toluene conversion rate, high benzene selectivity and high stability, has overall performance superior to that of a single-component common molecular sieve and two simple mixed molecular sieve catalysts, is simple in preparation process, and meets the requirements of large-scale industrial production and application. Compared with the eutectic molecular sieve, the hydrogen-type eutectic molecular sieve obtained by modifying and modifying the eutectic molecular sieve avoids toxicity to the catalyst and improves the overall performance of the catalyst.
Description
Technical Field
The invention belongs to the field of molecular sieve catalytic materials, and particularly relates to a high-activity catalyst for preparing benzene by toluene disproportionation.
Background
Aromatic hydrocarbons are important basic raw materials in petrochemical industry, and among the total tens of millions of known organic compounds, the aromatic compounds account for about 30%, wherein the yield and the scale of benzene (B), toluene (T) and xylene (X) are second to that of ethylene and propylene, and the aromatic hydrocarbons are called primary basic organic raw materials, are mainly used for synthesizing high-molecular polyester fibers and plastics, and have extremely wide application in the fields of medicines, pesticides, dyes and the like.
At present, the large-scale industrial production of aromatic hydrocarbon is realized by an aromatic hydrocarbon combination unit, a typical aromatic hydrocarbon combination unit comprises a device for producing aromatic hydrocarbon such as naphtha hydrogenation, catalytic reforming, pyrolysis gasoline hydrogenation and the like and an aromatic hydrocarbon conversion and aromatic hydrocarbon separation device, and main products are benzene and xylene (mainly paraxylene PX and orthoxylene OX). The key technologies involved are: catalytic reforming, aromatic extraction, toluene disproportionation, transalkylation, xylene isomerization, PX separation and other aromatic conversion technologies. The toluene disproportionation unit is one of key units in an aromatic hydrocarbon combination device, and plays an important role in material flow conversion hub and effective adjustment of aromatic hydrocarbon raw material and product structure.
In addition to the disproportionation of toluene to produce benzene and xylene, there have been more conventional toluene dealkylation benzene-making processes, which include both catalytic dealkylation and thermal dealkylation. Typical operating conditions for catalytic dealkylation are 575-650 ℃, 2.5-6.0MPa, and thermal dealkylation temperature as high as 760 ℃. The basic process flow of the two is similar, and the temperature of the exothermic reaction section is controlled by hydrogen-rich gas circulation. The liquid product is stabilized by removing light components, treated by argil and finally rectified to obtain a benzene product, and the toluene and heavy components are recycled to the device.
The U.S. Arco and hydrocarbon research companies developed HAD thermal dealkylation processes that operated at low concentrations to give higher benzene yields. The THD process developed by Gulf corporation, usa is similar to this. These processes are suitable for converting process streams from BTX separations that contain primarily aromatic hydrocarbons such as toluene. The MHC process of mitsubishi chemistry is a thermal dealkylation process that can handle large quantities of non-aromatic components, allowing the use of less pure hydrogen, reducing the requirement for make-up hydrogen.
The "Detol" process developed by Houdry, which uses toluene as a raw material, "Pyrotol" process, which uses hydrocracked gasoline as a raw material, "Litol" process, which uses coked crude benzene as a raw material, are catalytic dealkylation processes. Wherein the basic purpose of the Houdry Pyrotol process is the dealkylation of aromatics in pyrolysis gasoline. The Pyrotol process flow is very similar to the Litol process, requiring a feed pretreatment to remove pentane, and at least a portion of the C9+ fraction. The cut feedstock is vaporized and passed through a pretreatment reactor to selectively hydrogenate diolefins, cyclodiolefins, and styrene. In the Pyrotol reactor, the aromatic hydrocarbons are dealkylated to produce benzene. Other reactions include non-aromatics cracking to light hydrocarbons (primarily C1-C3) and desulfurization. The unreacted toluene and heavy aromatics are recycled back to the reaction section. At present, the dealkylation benzene preparation process has high energy consumption, low yield and easy pollution, and meanwhile, the hydrodealkylation Cr2O3/Al2O3 catalyst has high activity temperature and poor carbon deposition resistance, and the catalyst is easy to cause temperature runaway inactivation in actual industrial production and use, and is replaced by a toluene disproportionation benzene production-increasing process in the industry nowadays. At present, the method further improves the catalyst feeding airspeed, improves the benzene yield, reduces the reaction hydrogen-hydrocarbon ratio, saves energy and reduces consumption, and still is the development direction of preparing benzene by toluene disproportionation.
For the reaction of preparing benzene by toluene disproportionation, the conversion rate and selectivity of toluene disproportionation are directly related to the pore structure of the catalyst and the strength of acidic acid, the structure and composition of the eutectic molecular sieve catalyst are accurately optimized, and the method has an important role in obtaining a high-performance catalyst with high selectivity, high aromatic hydrocarbon processing capacity, high conversion rate, low hydrogen consumption and high benzene purity.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a high-activity catalyst for preparing benzene by toluene disproportionation, which has the characteristics of high toluene conversion rate, high benzene selectivity and high stability.
The above purpose of the invention is realized by the following technical scheme: the catalyst for preparing benzene by disproportionation of toluene with high activity is composed of hydrogen-type eutectic molecular sieve, adhesive, active metal or metal oxide and assistant.
The hydrogen type eutectic molecular sieve is formed by modifying an eutectic molecular sieve, and the method comprises the following specific steps: placing the eutectic molecular sieve in an aqueous solution containing 0.15% of ammonium chloride by volume fraction, wherein the volume ratio of the eutectic molecular sieve to the aqueous solution of ammonium chloride is 3:20, ion exchange is carried out for 6 hours at the temperature of 90 ℃, mother liquor is filtered out, the ion exchange is repeated for 2 to 4 times, and the mixed ammonium type zeolite is obtained after washing and drying for 2 hours at the temperature of 120 ℃. And roasting the obtained ammonium type molecular sieve at 550 ℃ for 4 hours to obtain the hydrogen type eutectic molecular sieve.
In the catalyst, the mass fraction of the hydrogen-type eutectic molecular sieve is 40-90%, the mass fraction of the binder is 10-60%, the mass fraction of the active metal or metal oxide is 0.1-20%, and the mass fraction of the auxiliary agent is 1-2%.
The mole ratio of silicon oxide to aluminum oxide in the hydrogen-type eutectic molecular sieve is 5-80, and the specific surface area is 300-800 m 2 Per gram, pore volume of 0.25-0.80 cm 3 /g。
The hydrogen type eutectic molecular sieve is one or more modified products of ZSM-5/ZSM-12, ZSM-5/beta, MOR/ZSM-12, ZSM-5/MOR and Y/MCM-22 eutectic molecular sieves.
The eutectic molecular sieve is a composite crystal of two molecular sieves with different crystal structures, wherein the weight ratio of the two molecular sieves is 1/9-9/1.
The metal species in the active metal or metal oxide comprises one or more of rhodium, nickel, cobalt, copper, molybdenum, silver, iridium, lanthanum, yttrium, ruthenium, zirconium, antimony and niobium.
The metal component of the active metal or metal oxide is present in the catalyst bulk composition or is present alone in the molecular sieve component.
The binder is one or more of silica sol, alumina, natural clay, attapulgite, water glass, methylcellulose, polyvinyl alcohol, paraffin, starch, plastic resin, bentonite and dextrin.
The auxiliary agent is an extrusion aid, a hole expanding and/or strength auxiliary agent. Is selected from one or more of sesbania powder, dry starch, methylcellulose, sodium carboxymethylcellulose, glycerol, lubricating oil, graphite, stearic acid, paraffin, rosin and polyacrylamide.
Compared with the prior art, the invention has the beneficial effects that:
1. the catalyst prepared by modifying and modifying the eutectic molecular sieve has the characteristics of high toluene conversion rate, high benzene selectivity and high stability, and the overall performance of the catalyst is superior to that of a single-component ordinary molecular sieve catalyst and a simple mixed molecular sieve catalyst. And the preparation process is simple, and the requirements of large-scale industrial production and application are met.
2. Compared with the eutectic molecular sieve, the hydrogen-type eutectic molecular sieve obtained by modifying the eutectic molecular sieve avoids toxicity to the catalyst, improves the overall performance of the catalyst, and has the advantages that the specific surface area of the eutectic molecular sieve is 8-12% higher than that of a mixture of two kinds of molecular sieves with the same weight ratio, and the pore volume of the eutectic molecular sieve is 7-10% higher than that of the mixture of the two kinds of molecular sieves with the same weight ratio.
Detailed Description
The invention is described in more detail below with reference to specific examples, without limiting the scope of the invention. Unless otherwise specified, the experimental methods adopted by the invention are all conventional methods, and experimental equipment, materials, reagents and the like used in the experimental method can be obtained from commercial sources.
Example 1
Placing a ZSM-5/ZSM-12 eutectic molecular sieve in an aqueous solution containing 0.15% of ammonium chloride by volume fraction, wherein the volume ratio of the eutectic molecular sieve to the aqueous solution of ammonium chloride is 3:20, ion exchange is carried out for 6 hours at the temperature of 90 ℃, mother liquor is filtered out, the ion exchange is repeated for 2 to 4 times, and the mixed ammonium type zeolite is obtained after washing and drying for 2 hours at the temperature of 120 ℃. And roasting the obtained ammonium molecular sieve at 550 ℃ for 4 hours to obtain the hydrogen ZSM-5/ZSM-12 eutectic molecular sieve.
Mixing and kneading a hydrogen type ZSM-5/ZSM-12 eutectic molecular sieve (the weight ratio of which is 4.5/5.5 measured by XRD powder diffraction analysis), silica sol and sesbania powder according to the proportion of 80. Roasting the mixture for 2 hours in a muffle furnace at the temperature of 520 ℃, and screening to obtain the ZSM-5/ZSM-12 eutectic molecular sieve catalyst. Then, 4% by weight of Mo was supported on the catalyst by vacuum impregnation, and the catalyst was calcined at 500 ℃ for 2 hours to obtain a 4% Mo-ZSM-5/ZSM-12 catalyst. 4% of Mo-ZSM-5/ZSM-12 catalyst and then 0.1wt% of Rh was supported on the catalyst by the equivalent-volume impregnation method, to obtain 4% of Mo-0.1% of Rh-ZSM-5/ZSM-12 eutectic molecular sieve catalyst.
Loading the catalyst into a fixed bed microreactor, respectively filling inert glass beads at the upper and lower parts, wherein the reaction raw material is toluene, the reaction temperature is 410 ℃, the reaction pressure is 3.0MPa, and the reaction pressure is H 2 In the atmosphere, the mass space velocity of the raw material is 2.0h -1 The activity was evaluated under the conditions of (1), and the reaction product was quantitatively analyzed by gas chromatography, and the analysis results are shown in Table 1.
Example 2
Placing the MOR/ZSM-12 eutectic molecular sieve in an aqueous solution containing ammonium chloride with the volume fraction of 0.15%, wherein the volume ratio of the eutectic molecular sieve to the aqueous solution of ammonium chloride is 3:20, ion exchange is carried out for 6 hours at the temperature of 90 ℃, mother liquor is filtered out, the ion exchange is repeated for 2 to 4 times, and the mixed ammonium type zeolite is obtained after washing and drying for 2 hours at the temperature of 120 ℃. And roasting the obtained ammonium type molecular sieve at 550 ℃ for 4 hours to obtain the hydrogen type MOR/ZSM-12 eutectic molecular sieve.
Loading 3wt% of Cu and 0.5wt% of Ni on hydrogen MOR/ZSM-12 eutectic molecular sieve (weight ratio of 2.5/7.5 as determined by XRD powder diffraction analysis) by isovolumetric impregnation to obtain 3% of Cu-0.5% of Ni-MOR/ZSM-12 molecular sieve, and kneading and extruding 3% of Ni-MOR/ZSM-12 molecular sieve, alumina and methylcellulose in a ratio of 80. Roasting in a muffle furnace at 520 deg.C for 2 hr, and sieving to obtain 3% of Cu-0.5% of the eutectic molecular sieve catalyst, ni-MOR/ZSM-12.
Loading the catalyst into a fixed bed microreactor, respectively filling inert glass beads at the upper and lower parts, wherein the reaction raw material is toluene, and reacting at 416 DEG CPressure of 3.0MPa in H 2 In the atmosphere, the mass space velocity of the raw material is 2.0h -1 The activity was evaluated under the conditions of (1), and the reaction product was quantitatively analyzed by gas chromatography, and the analysis results are shown in Table 1.
Example 3
Placing the MOR/ZSM-5 eutectic molecular sieve in an aqueous solution containing 0.15% ammonium chloride by volume fraction, wherein the volume ratio of the eutectic molecular sieve to the aqueous solution of ammonium chloride is 3:20, ion exchange is carried out for 6 hours at the temperature of 90 ℃, mother liquor is filtered out, the ion exchange is repeated for 2 to 4 times, and the mixed ammonium type zeolite is obtained after washing and drying for 2 hours at the temperature of 120 ℃. And roasting the obtained ammonium type molecular sieve at 550 ℃ for 4 hours to obtain the hydrogen type MOR/ZSM-5 eutectic molecular sieve.
Mixing and kneading a hydrogen MOR/ZSM-5 eutectic molecular sieve (the weight ratio of which is 6.5/3.5 measured by XRD powder diffraction analysis), alumina and sesbania powder according to the proportion of 75. Roasting the mixture for 2 hours at 520 ℃ in a muffle furnace, and screening to obtain the MOR/ZSM-5 eutectic molecular sieve. Then, by vacuum impregnation, 0.15wt% Ru was supported on the catalyst, followed by calcination at 500 ℃ for 2 hours, to obtain 0.15% Ru-MOR/ZSM-5 catalyst. Loading 2wt% La on the catalyst by an equivalent volume impregnation of 0.15% Ru-MOR/ZSM-5 catalyst yielding 0.15% Ru-2% La-MOR/ZSM-5 eutectic molecular sieve catalyst.
Loading the catalyst into a fixed bed microreactor, respectively loading inert glass beads on the upper and lower parts of the microreactor, wherein the reaction raw material is toluene, the reaction temperature is 405 ℃, the reaction pressure is 3.0MPa, and the reaction pressure is H 2 In the atmosphere, the mass space velocity of the raw material is 2.0h -1 The activity was evaluated under the conditions of (1), and the reaction product was quantitatively analyzed by gas chromatography, and the analysis results are shown in Table 1.
Example 4
Placing the MOR/beta eutectic molecular sieve in an aqueous solution containing 0.15% of ammonium chloride by volume fraction, wherein the volume ratio of the eutectic molecular sieve to the aqueous solution of ammonium chloride is 3:20, ion exchange is carried out for 6 hours at the temperature of 90 ℃, mother liquor is filtered out, the ion exchange is repeated for 2 to 4 times, and the mixed ammonium type zeolite is obtained after washing and drying for 2 hours at the temperature of 120 ℃. And roasting the obtained ammonium type molecular sieve at 550 ℃ for 4 hours to obtain the hydrogen type MOR/beta eutectic molecular sieve.
Loading 2wt% of Mo, 1wt% of Ag and 0.2wt% of Ir simultaneously into the hydrogen MOR/beta eutectic molecular sieve by the equal-volume impregnation method (the weight ratio measured by XRD powder diffraction analysis is 9.5/0.5), and then kneading, extruding and molding the impregnated molecular sieve, alumina and methylcellulose according to the proportion of 70. Roasting in a muffle furnace at 520 ℃ for 2 hours, and screening to obtain 2% Mo-1% Ag-0.2% Ir-MOR/beta eutectic molecular sieve catalyst.
Loading the catalyst into a fixed bed microreactor, respectively filling inert glass beads at the upper and lower parts, wherein the reaction raw material is toluene, the reaction temperature is 408 ℃, the reaction pressure is 3.0MPa, and the reaction pressure is H 2 In the atmosphere, the mass space velocity of the raw material is 2.0h -1 The activity was evaluated under the conditions of (1), and the reaction product was quantitatively analyzed by gas chromatography, and the analysis results are shown in Table 1.
Comparative example 1
Loading 2wt% mo onto the hydrogen-type MOR molecular sieve by an equivalent volume impregnation method, then kneading, strip-forming and crushing 2% mo-MOR molecular sieve, alumina, polyvinyl alcohol, sesbania powder in a ratio of 70. Calcination at 520 ℃ for 2 hours in a muffle furnace, screening to obtain 2% Mo-1% Ag-0.2% Re-MOR molecular sieve catalyst.
Loading the catalyst into a fixed bed microreactor, respectively loading inert glass beads on the upper and lower parts of the microreactor, wherein the reaction raw material is toluene, the reaction temperature is 405 ℃, the reaction pressure is 3.0MPa, and the reaction pressure is H 2 In the atmosphere, the mass space velocity of the raw material is 2.0h -1 The activity was evaluated under the conditions of (1), and the reaction product was quantitatively analyzed by gas chromatography, and the analysis results are shown in Table 1.
Comparative example 2
Loading 4% of Mo, 0.1% of Rh onto the hydrogen-type ZSM-5 molecular sieve simultaneously by the method of equivalent-volume impregnation, and then kneading, bar-extruding and crushing the impregnated molecular sieve, attapulgite and sesbania powder in a proportion of 70. Roasting at 520 deg.C in a muffle furnace for 2 hours, and screening to obtain 4% of Mo-0.1% of Rh-ZSM-5 molecular sieve catalyst.
Loading the catalyst into a fixed bed microreactor, respectively filling inert glass beads at the upper part and the lower part, wherein the reaction raw material is toluene, the reaction temperature is 420 ℃, the reaction pressure is 3.0MPa, and the reaction pressure is H 2 In the atmosphere, the mass space velocity of the raw material is 2.0h -1 The activity was evaluated under the conditions of (1), and the reaction product was quantitatively analyzed by gas chromatography, and the analysis results are shown in Table 1.
Comparative example 3
Mixing hydrogen type ZSM-5 and ZSM-12 molecular sieves (the weight ratio is 4.5/5.5), kneading silica sol and sesbania powder according to the proportion of 80. Roasting the mixture for 2 hours in a muffle furnace at the temperature of 520 ℃, and screening to obtain the ZSM-5/ZSM-12 eutectic molecular sieve catalyst. Then 4% by vacuum impregnation, 4wt% Mo was supported on the catalyst, resulting in 4% Mo-ZSM-5/ZSM-12 catalyst after 2 hours of calcination at 500C. 4% of the Mo-ZSM-5/ZSM-12 catalyst and then 0.1wt% of Rh was loaded on the catalyst by the equivalent-volume impregnation method, to obtain 4% of the Mo-0.1% of the Rh-ZSM-5/ZSM-12 mixed molecular sieve catalyst.
Loading the catalyst into a fixed bed microreactor, respectively filling inert glass beads at the upper part and the lower part, wherein the reaction raw material is toluene, the reaction temperature is 410 ℃, the reaction pressure is 3.0MPa, and the reaction pressure is H 2 In the atmosphere, the mass space velocity of the raw material is 2.0h -1 The activity was evaluated under the conditions of (1), and the reaction product was quantitatively analyzed by gas chromatography, and the analysis results are shown in Table 1.
Comparative example 4
Loading 3wt% of Cu and 0.5wt% of Ni on two mixed molecular sieves of hydrogen MOR and ZSM-12 (weight ratio of 4.5/5.5) by the method of isovolumetric impregnation to obtain 3% of Cu-0.5% of Ni-MOR/ZSM-12 molecular sieve, and then kneading, strip-molding and crushing catalyst particles having a length of 2 to 4mm from 3% to 0.5% of Ni-MOR/ZSM-12 molecular sieve, alumina, methylcellulose in a ratio of 80. Roasting in a muffle furnace 520C for 2 hours, screening to obtain 3% Cu-0.5% of Ni-MOR/ZSM-12 mixed molecular sieve catalyst.
The catalyst is loaded into a fixed bed micro-reactor, inert glass beads are respectively filled up and down,the reaction raw material is toluene, the reaction temperature is 416 ℃, the reaction pressure is 3.0MPa, and the reaction temperature is H 2 In the atmosphere, the mass space velocity of the raw material is 2.0h -1 The activity was evaluated under the conditions of (1), and the reaction product was quantitatively analyzed by gas chromatography, and the analysis results are shown in Table 1. The comparative analysis results of the pore volume and the specific surface area of the catalyst prepared from the mixed molecular sieve and the eutectic molecular sieve are shown in Table 2.
Table 1:
table 2:
compared with the comparative example, the conversion rate of the example is obviously improved by 9-26%, the benzene selectivity is improved by 5-12%, and the specific surface and pore volume of the molecular sieve obtained by using the eutectic molecular sieve as the raw material are obviously improved, and the activity of the catalyst is enhanced.
The embodiments described above are merely preferred embodiments of the invention, rather than all possible embodiments of the invention. Any obvious modifications to the above would be obvious to those of ordinary skill in the art, but would not bring the invention so modified beyond the spirit and scope of the present invention.
Claims (10)
1. The catalyst for preparing benzene by disproportionation of toluene with high activity is characterized by consisting of a hydrogen-type eutectic molecular sieve, a binder, an active metal or metal oxide and an auxiliary agent.
2. The catalyst for benzene production by disproportionation of toluene with high activity according to claim 1, wherein the mass fraction of hydrogen-type eutectic molecular sieve in the catalyst for benzene production by disproportionation of toluene with high activity is 40-90%, the mass fraction of the binder is 10-60%, the mass fraction of the active metal or metal oxide is 0.1-20%, and the mass fraction of the auxiliary agent is 1-2%.
3. The catalyst for preparing benzene by disproportionation of toluene with high activity according to claim 1, wherein the hydrogen-type eutectic molecular sieve is modified by a eutectic molecular sieve, and the specific steps are as follows: placing the eutectic molecular sieve in an aqueous solution containing 0.15% of ammonium chloride by volume fraction, wherein the volume ratio of the eutectic molecular sieve to the aqueous solution of ammonium chloride is 3:20, performing ion exchange at 90 ℃ for 6 hours, filtering out mother liquor, repeating the ion exchange for 2-4 times, washing, and drying at 120 ℃ for 2 hours to obtain mixed ammonium type zeolite; and roasting the obtained ammonium type molecular sieve at 550 ℃ for 4 hours to obtain the hydrogen type eutectic molecular sieve.
4. The catalyst as claimed in claim 1, wherein the hydrogen-type eutectic molecular sieve has a molar ratio of silica to alumina of 5-80 and a specific surface area of 300-800 m 2 Per g, pore volume of 0.25-0.80 cm 3 /g。
5. The catalyst for preparing benzene by disproportionation of toluene with high activity as claimed in claim 1, wherein the hydrogen-type eutectic molecular sieve is one or more modified products of ZSM-5/ZSM-12, ZSM-5/beta, MOR/ZSM-12, ZSM-5/MOR, Y/MCM-22 eutectic molecular sieves.
6. The catalyst for benzene production by disproportionation of toluene with high activity according to claim 1, wherein the metal species in the active metal or metal oxide comprises one or more of rhodium, nickel, cobalt, copper, molybdenum, silver, iridium, lanthanum, yttrium, ruthenium, zirconium, antimony, and niobium; the metal component of the active metal or metal oxide is present in the catalyst bulk composition or is present alone in the molecular sieve component.
7. The catalyst as claimed in claim 1, wherein the binder is one or more selected from silica sol, alumina, natural clay, attapulgite, water glass, methylcellulose, polyvinyl alcohol, paraffin, starch, plastic resin, bentonite, and dextrin.
8. The catalyst as claimed in claim 1, wherein the assistant is an extrusion aid, pore-expanding and/or strength assistant, and is selected from one or more of sesbania powder, dry starch, methyl cellulose, sodium carboxymethyl cellulose, glycerol, lubricating oil, graphite, stearic acid, paraffin, rosin and polyacrylamide.
9. The catalyst as claimed in claim 3, wherein the eutectic molecular sieve is a composite crystal of two molecular sieves with different crystal structures, and the weight ratio of the two molecular sieves is 1/9-9/1.
10. The use of the high activity disproportionation benzene catalyst of claim 1 in the disproportionation of toluene to produce benzene.
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| CN101987298A (en) * | 2009-08-07 | 2011-03-23 | 中国石油天然气股份有限公司 | Metal-modified eutectic zeolite catalyst with EUO (Europium Oxide) structure as well as preparation method and application thereof |
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| CN101987298A (en) * | 2009-08-07 | 2011-03-23 | 中国石油天然气股份有限公司 | Metal-modified eutectic zeolite catalyst with EUO (Europium Oxide) structure as well as preparation method and application thereof |
| CN112299433A (en) * | 2019-07-29 | 2021-02-02 | 中国石油天然气股份有限公司 | Hydrogen type ZSM-5/EU-1 eutectic zeolite, aromatic isomerization catalyst, preparation method and application |
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