CN115055201A - Catalyst for preparing benzene through acetylene aromatization reaction and preparation and application thereof - Google Patents
Catalyst for preparing benzene through acetylene aromatization reaction and preparation and application thereof Download PDFInfo
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 39
- 238000005899 aromatization reaction Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 82
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000010948 rhodium Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 11
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 11
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 6
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000013335 mesoporous material Substances 0.000 claims abstract description 3
- 239000011777 magnesium Substances 0.000 claims description 36
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 16
- 101150003085 Pdcl gene Proteins 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 150000000703 Cerium Chemical class 0.000 claims description 4
- 159000000003 magnesium salts Chemical class 0.000 claims description 4
- 150000002940 palladium Chemical class 0.000 claims description 4
- 150000003283 rhodium Chemical class 0.000 claims description 4
- 150000003303 ruthenium Chemical class 0.000 claims description 4
- 239000002905 metal composite material Substances 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical group [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- -1 rhodium transition metal Chemical class 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 4
- 150000003624 transition metals Chemical class 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 239000000047 product Substances 0.000 abstract description 3
- 238000004220 aggregation Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 239000012495 reaction gas Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000006006 cyclotrimerization reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0325—Noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/42—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons homo- or co-oligomerisation with ring formation, not being a Diels-Alder conversion
- C07C2/48—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons homo- or co-oligomerisation with ring formation, not being a Diels-Alder conversion of only hydrocarbons containing a carbon-to-carbon triple bond
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/40—Special temperature treatment, i.e. other than just for template removal
Abstract
The invention discloses a high-performance catalyst for preparing benzene by acetylene aromatization and a preparation method and application thereof. The catalyst is a supported high-dispersion palladium/ruthenium/rhodium composite transition metal catalyst prepared by modifying the surface of an ordered mesoporous material MCM-41 carrier by adopting a metal auxiliary agent and then loading transition metals of active components of palladium, ruthenium and rhodium. In order to improve the reaction stability and catalytic performance of the catalyst, the dispersion performance of the active components can be improved and the aggregation of the active components can be prevented on the one hand by a way of doping the alkalescent metal auxiliary agent; on the other hand, the method can relieve the excessive polymerization of acetylene and reduce the selectivity of heavy aromatic byproducts in the product.
Description
Technical Field
The invention belongs to the field of chemistry and chemical engineering, and relates to a catalyst for preparing benzene by acetylene aromatization reaction, and preparation and application thereof.
Background
The light aromatic hydrocarbons such as benzene, toluene and xylene are used as basic chemical raw materials and widely applied to the preparation of chemical products such as rubber, fiber, plastic, dye and the like. In recent years, with the rapid development of synthetic materials and the increasing demand for other fine chemicals, the demand for aromatic hydrocarbons has continued to increase. At present, aromatic hydrocarbons are mainly derived from catalytic reforming and hydrocarbon cracking in petrochemical industry, and the shortage of petroleum resources makes the development of new technologies urgent. If acyclic simple molecules such as methane, methanol, acetylene and the like can be utilized to perform aromatization reaction and directly convert the molecules into light aromatic hydrocarbons with high added values, a new way for producing the aromatic hydrocarbons is developed.
Acetylene has extremely high reaction activity, and the cyclotrimerization reaction of acetylene is strongly exothermic, but when no catalyst is involved, the reaction is carried out at 400 ℃ and only a small amount of benzene is generated due to more side reactions. Reppe et al (Ann. chem. 1948, 560, 104) first reported in 1948 a NiBr2 catalyst, which can synthesize various substituted benzene derivatives by cyclotrimerization of alkynes using homogeneous catalysis. Since then, the aromatization reaction of alkyne has attracted the attention of researchers at home and abroad, and many transition metals and complexes thereof are found to be capable of catalyzing the aromatization reaction of acetylene.
Elstern wick et al (u.s.p. 4424401) disclose the performance of the zeolite catalyst ZSM-5 surface for acetylene aromatization reactions: under the condition of inert gas, water, hydrogen and alcohol, the ZSM-5 molecular sieve can better catalyze the reaction in a wider temperature range of 260-550 ℃, but is extremely easy to inactivate. Timmons et al (u.s.p. 5118893) disclose the aromatization of acetylene on the surface of a Ni, Co modified ZSM-5 catalyst in the presence of H2O, H2. As a result, it was found that the reaction stability was improved to some extent, but the aromatic selectivity was lowered.
Schlieren et al (CN 105498757A) reported a supported high-dispersion Pd, Ru and Rh transition metal composite catalyst, which can reach acetylene conversion rate over 90% and benzene selectivity over 70%, but has poor reaction stability. Huangwei et al (CN 107042120A) reported that a modified supported palladium catalyst shows high acetylene conversion rate and benzene selectivity in the reaction process, but the conversion rate and the selectivity cannot be simultaneously considered, and the stability is still to be improved.
In summary, although there are some reports on the aromatization reaction of acetylene, the developed catalyst generally has the problems of easy carbon deposition and deactivation, poor reaction stability and the like, and is difficult to apply industrially.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a catalyst for preparing benzene by acetylene aromatization reaction, and preparation and application thereof. Especially, 100 percent of acetylene conversion rate and higher benzene selectivity can be stably maintained in a longer time.
The technical scheme for solving the technical problems is as follows:
a catalyst for preparing benzene by acetylene aromatization reaction comprises a metal auxiliary agent, a carrier and an active component; the metal auxiliary agent is cerium and/or magnesium; the carrier is an ordered mesoporous material MCM-41 carrier; the active components are palladium, ruthenium and rhodium.
The loading amount of the metal auxiliary agent is 0.5-20% of the mass of the carrier; preferably, the loading amount of the metal promoter is 0.5-18% of the mass of the carrier. More preferably, the metal promoter is present in an amount of from 0.5 to 10% by mass of the support.
The preparation method of the catalyst for preparing benzene by acetylene aromatization reaction comprises the following steps:
(1) roasting an MCM-41 carrier for 4-6h at 500-600 ℃ in an air atmosphere, cooling to below 100 ℃, and putting the MCM-41 carrier into a dryer for later use;
(2) adding the MCM-41 carrier subjected to roasting pretreatment into a cerium salt or/and magnesium salt aqueous solution at normal temperature in equal volume for soaking for 3-12h, then drying for 3-12h at the temperature of 110-;
(3) adding the modified MCM-41 carrier into a palladium salt aqueous solution at normal temperature and in the same volume, soaking for 3-12h, then drying for 3-12h at the temperature of 110-;
(4) adding the modified MCM-41 supported palladium catalyst into a mixed aqueous solution of ruthenium salt and rhodium salt at normal temperature in the same volume, soaking for 3-12h, drying for 3-12h at the temperature of 110-.
Preferably, the cerium salt in step (2) is Ce (NO) 3 ) 3 The dosage is 0.5 to 10 percent of the carrier by mass of Ce;
preferably, the magnesium salt in the step (2) is Mg (NO) 3 ) 2 The using amount is 0.5 to 10 percent of the carrier by the mass of Mg;
preferably, the palladium salt in the step (3) is PdCl 2 The dosage is 0.2 to 1.5 percent of the carrier by mass of Pd;
preferably, the ruthenium salt in the step (4) is RuCl 3 The amount of the Ru is 0.2-1.5% of the carrier by mass;
preferably, the rhodium salt in the step (4) is RhCl 3 The amount used is 0.2-1.5% of the support, calculated as Rh mass.
The specific application steps of the catalyst are as follows:
placing the catalyst in a reaction device, and carrying out in-situ activation pretreatment for 1-3 h at the temperature of 500-600 ℃ in a hydrogen atmosphere to reduce the active component into a metal state; then, a material component containing 10-50% volume of acetylene and 50-90% volume of nitrogen is introduced into the reactor to contact with the pre-reduced catalyst, and the temperature range and the acetylene volume space velocity are within 300-600 ℃ for 3000 h -1 Carrying out aromatization reaction under the condition.
The invention has the following beneficial effects:
according to the catalyst for preparing benzene by acetylene aromatization reaction and the application thereof, the MCM-41 loaded palladium/ruthenium/rhodium transition metal composite catalyst is doped with Ce and Mg, so that on one hand, the dispersion performance of active components can be better improved, and the aggregation among the active components is prevented; on the other hand, the introduction of the alkaline metal auxiliary agent can relieve the excessive polymerization of acetylene and reduce the selectivity of heavy aromatic byproducts in the product, thereby effectively improving the reaction stability of the catalyst.
The catalyst can obtain 100 percent of acetylene conversion rate and over 82 percent of benzene selectivity in aromatization reaction and can stably run for 5-8 hours.
The method for improving the aromatization reaction performance of acetylene provided by the invention is simple to operate, has mild conditions, meets the requirements of industrial application, and is convenient for large-scale industrial production.
Detailed Description
The present invention is described in detail with reference to the following examples, which are only preferred embodiments of the present invention, and are not intended to limit the present invention, and it should not be understood that the scope of the above subject matter of the present invention is limited to the following examples, and all the technologies realized based on the present disclosure belong to the protection scope of the present invention. Reagents, equipment and methods employed in the present invention are reagents, equipment and methods conventionally commercially available in the art and conventionally used methods, unless otherwise specified.
Example 1
Preparation of modified MCM-41 Carrier
(1) Roasting MCM-41 in air atmosphere at 500 ℃ for 6h, cooling to room temperature, weighing 50g of roasted MCM-41 carrier, and adding the same volume of the carrier to Ce (NO) 3 ) 3 In aqueous solution, Ce (NO) 3 ) 3 The loading amount is recorded as 7 percent of MCM-41 by mass of Ce, and the soaking is carried out for 6 hours at room temperature. And drying the obtained mixture at the temperature of 110 ℃, heating to 500 ℃ at the speed of 10 ℃/min in the air atmosphere, and roasting for 3h to obtain the Ce modified MCM-41 carrier, which is recorded as Ce (7)/MCM-41.
(2) Roasting MCM-41 in air atmosphere at 500 ℃ for 6h, cooling to room temperature, weighing 50g of roasted MCM-41 carrier, and adding Mg (NO) in equal volume 3 ) 2 In aqueous solution, Mg (NO) 3 ) 2 The loading capacity is recorded as 2 percent of MCM-41 by the mass of Mg, and the soaking is carried out for 6 hours at room temperature. And drying the obtained mixture at the temperature of 110 ℃, heating to 500 ℃ at the speed of 10 ℃/min in the air atmosphere, and roasting for 3h to obtain the Mg modified MCM-41 carrier, which is recorded as Mg (2)/MCM-41.
(3) Roasting MCM-41 in air atmosphere at 500 ℃ for 6h, cooling to room temperature, weighing 50g of roasted MCM-41 carrier, and adding the same volume of the carrier to Ce (NO) 3 ) 3 And Mg (NO) 3 ) 2 In mixed aqueous solution, Ce (NO) 3 ) 3 And Mg (NO) 3 ) 2 The loading amounts are recorded as 5 percent and 1 percent of MCM-41 by the mass of Ce and Mg, and the mixture is soaked for 6 hours at room temperature. The resulting mixture is inDrying at 110 ℃, heating to 500 ℃ at 10 ℃/min in air atmosphere, and roasting for 3h to obtain the Ce and Mg modified MCM-41 carrier, which is marked as Ce (5) Mg (1)/MCM-41.
Example 2
Preparation of Pd/Ru/Rh/MCM-41 catalyst
Roasting MCM-41 in air atmosphere at 500 ℃ for 6h, cooling to room temperature, weighing 10 g of roasted MCM-41 carrier, and adding the carrier with the same volume to PdCl 2 In aqueous solution, PdCl 2 The loading capacity is 0.5 percent of that of MCM-41 according to the mass of Pd, and the impregnation is carried out for 6 hours at room temperature. Drying the obtained mixture at the temperature of 110 ℃, heating to 500 ℃ at the speed of 10 ℃/min in the air atmosphere, and roasting for 3h to obtain the MCM-41 loaded Pd/MCM-41 catalyst, which is recorded as Pd (0.5)/MCM-41.
The sample was added in equal volume to RuCl 3 And RhCl 3 In a mixed aqueous solution of RuCl 3 And RhCl 3 The loading amounts are 0.4 percent and 1.1 percent of MCM-41 in terms of the mass of Ru and Rh, and the impregnation is carried out for 10 hours at room temperature. Drying the obtained mixture at the temperature of 110 ℃, heating to 550 ℃ at the speed of 10 ℃/min in the air atmosphere, and roasting for 5 h to obtain the MCM-41 loaded Pd/Ru/Rh/MCM-41 composite catalyst which is recorded as Pd (0.5) Ru (0.4) Rh (1.1)/MCM-41. Tabletting, crushing and sieving to 20-40 mesh.
Example 3
Preparation of Pd/Ru/Rh/Ce/MCM-41 catalyst
A10 g sample of Ce (7)/MCM-41 prepared in example 1 was impregnated in an equal volume with PdCl 2 Aqueous solution, PdCl 2 The load is 0.5 percent of MCM-41 by mass of Pd, and the solution is prepared into aqueous solution and then soaked for 6 hours at room temperature. And drying the obtained mixture at the temperature of 110 ℃, heating to 550 ℃ at the temperature of 10 ℃/min in the air atmosphere, and roasting for 3h to obtain the Pd/Ce/MCM-41 catalyst loaded by Ce/MCM-41, and recording the Pd (0.5)/Ce (7)/MCM-41.
The sample was immersed in an equal volume of RuCl 3 And RhCl 3 In a mixed aqueous solution of (1), RuCl 3 And RhCl 3 The loading amounts are respectively marked as 0.4 percent and 1.1 percent of MCM-41 by the mass of Ru and Rh, and the solution is prepared and then soaked for 10 hours at room temperature. Drying the obtained mixture at the temperature of 110 ℃, heating to 550 ℃ at the temperature of 10 ℃/min in the air atmosphere, and roasting for 5 h to obtain the Ce/MCM-41 negativeThe loaded Pd/Ru/Rh/Ce/MCM-41 composite catalyst is marked as Pd (0.5) Ru (0.4) Rh (1.1)/Ce (7)/MCM-41. Tabletting, crushing and sieving to 20-40 mesh.
Example 4
Preparation of Pd/Ru/Rh/Mg/MCM-41 catalyst
A10 g sample of Mg (2)/MCM-41 prepared in example 1 was immersed in an equal volume with the addition of PdCl 2 Aqueous solution, PdCl 2 The load is 0.6 percent of MCM-41 by mass of Pd, and the solution is prepared into aqueous solution and then soaked for 12 hours at room temperature. And drying the obtained mixture at the temperature of 110 ℃, heating to 550 ℃ at the temperature of 10 ℃/min in the air atmosphere, and roasting for 3h to obtain the Mg/MCM-41 loaded Pd/Mg/MCM-41 catalyst, which is recorded as Pd (0.6)/Mg (2)/MCM-41.
The sample was immersed in an equal volume of RuCl 3 And RhCl 3 In a mixed aqueous solution of (1), RuCl 3 And RhCl 3 The loading amounts are respectively marked as 1.1 percent and 0.4 percent of MCM-41 by the mass of Ru and Rh, and the solution is prepared and then soaked for 6 hours at room temperature. Drying the obtained mixture at the temperature of 110 ℃, heating to 550 ℃ at the temperature of 10 ℃/min in the air atmosphere, and roasting for 5 h to obtain the MCM-41 loaded Pd/Ru/Rh/Mg/MCM-41 composite catalyst which is marked as Pd (0.6) Ru (1.1) Rh (0.4)/Mg (2)/MCM-41. Tabletting, crushing and sieving to 20-40 mesh.
Example 5
Preparation of Pd/Ru/Rh/Ce/Mg/MCM-41 catalyst
10 g of the Ce (5) Mg (1)/MCM-41 sample prepared in example 1 was impregnated with PdCl in equal volumes 2 Aqueous solution, PdCl 2 The load is 0.6 percent of MCM-41 by mass of Pd, and the solution is prepared into aqueous solution and then soaked for 12 hours at room temperature. And drying the obtained mixture at the temperature of 110 ℃, heating to 550 ℃ at the temperature of 10 ℃/min in the air atmosphere, and roasting for 3h to obtain the Pd/Ce/Mg/MCM-41 catalyst loaded by Ce/Mg/MCM-41, and recording the Pd (0.6)/Ce (5) Mg (1)/MCM-41.
The sample was immersed in an equal volume of RuCl 3 And RhCl 3 In a mixed aqueous solution of (1), RuCl 3 And RhCl 3 The loading amounts are respectively marked as 0.6 percent and 1.2 percent of MCM-41 by the mass of Ru and Rh, and the solution is prepared and then soaked for 6 hours at room temperature. Drying the obtained mixture at 110 deg.C, heating to 10 deg.C/min in air atmosphereRoasting at 550 ℃ for 5 hours to obtain the MCM-41 loaded Pd/Ru/Rh/Ce/Mg/MCM-41 composite catalyst which is recorded as Pd (0.6) Ru (0.6) Rh (1.2)/Ce (5) Mg (1)/MCM-41. Tabletting, crushing and sieving to 20-40 mesh.
Example 6
Evaluation of reaction
The acetylene aromatization reaction is carried out on a fixed bed reaction device, a stainless steel reactor with the inner diameter of 10 mm is used, and the reaction pressure is normal pressure. 2g of each of Pd (0.5) Ru (0.4) Rh (1.1)/MCM-41 and Pd (0.5) Ru (0.4) Rh (1.1)/Ce (7)/MCM-41 prepared in examples 2 and 3 was charged into a reactor, and the temperature was raised to 500 ℃ at 10 ℃/min in a hydrogen atmosphere and held for 2 hours. After reduction, switching to N 2 Purging for 1 h in atmosphere, then introducing 10% C 2 H 2 + 90%N 2 (volume composition) of reaction gas, and the space velocity of the reaction gas is 600 h -1 . The flow rates of the gases in the experiments were controlled by mass flowmeters, and the reaction products were analyzed on-line using a gas chromatograph equipped with dual FID detectors, the results of which are shown in tables 1-2.
TABLE 1 Pd (0.5) Ru (0.4) Rh (1.1)/MCM-41 catalyst result of the reaction for preparing benzene from acetylene
TABLE 2 result of acetylene to benzene reaction using Pd (0.5) Ru (0.4) Rh (1.1)/Ce (7)/MCM-41 catalyst
Example 7
Evaluation of reaction
The acetylene aromatization reaction is carried out on a fixed bed reaction device, a stainless steel reactor with the inner diameter of 10 mm is used, and the reaction pressure is normal pressure. 2g of Pd (0.6) Ru (1.1) Rh (0.4)/Mg (2)/MCM-41 prepared in example 4 were charged into a reactor, and the temperature was raised to 500 ℃ at 10 ℃/min in a hydrogen atmosphere and held for 2 hours. After reduction, switching to N 2 Purging for 1 h in atmosphere, cooling to 450 ℃, and introducing 20% C 2 H 2 + 80%N 2 (volume composition) of reaction gas, reactionThe air space velocity is 1200 h -1 . The flow of gas in the experiment was controlled by mass flow meters and the reaction products were analyzed on-line using a gas chromatograph equipped with dual FID detectors, the results of which are given in table 3.
TABLE 3 result of reaction of Pd (0.6) Ru (1.1) Rh (0.4)/Mg (2)/MCM-41 catalyst for preparing benzene from acetylene
Example 8
Evaluation of reaction
The acetylene aromatization reaction is carried out on a fixed bed reaction device, a stainless steel reactor with the inner diameter of 10 mm is used, and the reaction pressure is normal pressure. 2g of Pd (0.6) Ru (0.6) Rh (1.2)/Ce (5) Mg (1)/MCM-41 prepared in example 5 were charged into a reactor, and the temperature was raised to 500 ℃ at 10 ℃/min in a hydrogen atmosphere and held for 2 hours. After reduction, switching to N 2 Purging for 1 h in atmosphere, raising the temperature to 550 ℃, and introducing 40% C 2 H 2 + 60%N 2 (volume composition) of reaction gas, and the space velocity of the reaction gas is 2400 h -1 . The flow of gas in the experiment was controlled by mass flow meters and the reaction products were analyzed on-line using a gas chromatograph equipped with dual FID detectors, the results of which are given in table 4.
TABLE 4 reaction results of preparing benzene from acetylene by Pd (0.6) Ru (0.6) Rh (1.2)/Ce (5) Mg (1)/MCM-41 catalyst
Comparing table 1 and tables 2-4, it can be found that the MCM-41 supported catalyst doped with Ce and/or Mg has higher benzene selectivity and reaction stability than the catalyst supported by unmodified MCM-41. The catalyst can also realize that the benzene selectivity is over 82 percent under various reaction conditions, the acetylene conversion rate is 100 percent, and the time for keeping the stability of the catalyst can reach 5 to 7 hours.
It should be understood by those skilled in the art that the above-mentioned embodiments only express the embodiments of the present invention, and the description is more specific and detailed, but not construed as limiting the scope of the present invention, but all technical solutions obtained by equivalent substitution or equivalent transformation should be included in the scope of the present invention claimed in the present invention.
Claims (5)
1. The catalyst for preparing benzene by acetylene aromatization reaction is characterized by comprising a metal auxiliary agent, a carrier and an active component; the metal auxiliary agent is cerium and/or magnesium; the carrier is an ordered mesoporous material MCM-41 carrier; the active components are palladium, ruthenium and rhodium.
2. The catalyst for preparing benzene by acetylene aromatization reaction according to claim 1, wherein the loading amount of the metal promoter in the catalyst is 0.5-20% of the mass of the carrier.
3. A method for preparing a catalyst for benzene production by acetylene aromatization according to any one of claims 1-2, comprising the steps of:
(1) roasting an MCM-41 carrier for 4-6h at the temperature of 500-600 ℃ in an air atmosphere, reducing the temperature to be below 100 ℃, and putting the MCM-41 carrier into a dryer for later use;
(2) adding the MCM-41 carrier subjected to roasting pretreatment into a cerium salt or/and magnesium salt aqueous solution at normal temperature in equal volume for soaking for 3-12h, then drying for 3-12h at the temperature of 110-;
(3) adding the modified MCM-41 carrier into a palladium salt aqueous solution at normal temperature and in the same volume, soaking for 3-12h, then drying for 3-12h at the temperature of 110-;
(4) adding the modified MCM-41 supported palladium catalyst into a mixed aqueous solution of ruthenium salt and rhodium salt at normal temperature in the same volume for dipping for 3-12h, then drying for 3-12h at the temperature of 110-150 ℃ in the air atmosphere, and roasting for 2-6h at the temperature of 500-600 ℃ to obtain the modified MCM-41 supported palladium/ruthenium/rhodium transition metal composite catalyst, namely the catalyst for preparing benzene by acetylene aromatization reaction.
4. The method of claim 3, wherein the cerium salt in step (2) is Ce (NO) 3 ) 3 The dosage is 0.5 to 10 percent of the carrier by mass of Ce;
the magnesium salt in the step (2) is Mg (NO) 3 ) 2 The using amount is 0.5 to 10 percent of the carrier by the mass of Mg;
the palladium salt in the step (3) is PdCl 2 The dosage is 0.2 to 1.5 percent of the carrier by mass of Pd;
the ruthenium salt in the step (4) is RuCl 3 The amount of the Ru is 0.2-1.5% of the carrier by mass;
the rhodium salt in the step (4) is RhCl 3 The amount used is 0.2 to 1.5% by mass of Rh as the carrier.
5. The use of the catalyst for the preparation of benzene by the aromatization reaction of acetylene according to claim 1, which comprises the following steps:
placing the catalyst in a reaction device, and carrying out in-situ activation pretreatment for 1-3 h at the temperature of 500-600 ℃ in a hydrogen atmosphere to reduce the active component into a metal state; then, a material component containing 10-50% volume of acetylene and 50-90% volume of nitrogen is introduced into the reactor to contact with the pre-reduced catalyst, and the temperature range and the acetylene volume space velocity are within 300-600 ℃ for 3000 h -1 Carrying out aromatization reaction under the condition.
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