CN109926065B - Catalyst for preparing aniline from nitrobenzene, preparation method of catalyst and method for preparing aniline - Google Patents
Catalyst for preparing aniline from nitrobenzene, preparation method of catalyst and method for preparing aniline Download PDFInfo
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- CN109926065B CN109926065B CN201711355321.3A CN201711355321A CN109926065B CN 109926065 B CN109926065 B CN 109926065B CN 201711355321 A CN201711355321 A CN 201711355321A CN 109926065 B CN109926065 B CN 109926065B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 126
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 title claims abstract description 92
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 238000001179 sorption measurement Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 21
- 239000002002 slurry Substances 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 229910052593 corundum Inorganic materials 0.000 claims description 19
- 239000011148 porous material Substances 0.000 claims description 19
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 230000002779 inactivation Effects 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 26
- 239000012266 salt solution Substances 0.000 description 18
- 239000006227 byproduct Substances 0.000 description 14
- 239000007791 liquid phase Substances 0.000 description 11
- 239000002131 composite material Substances 0.000 description 10
- 238000004438 BET method Methods 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 229910002651 NO3 Inorganic materials 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 229910019934 (NH4)2MoO4 Inorganic materials 0.000 description 5
- 208000005374 Poisoning Diseases 0.000 description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 231100000572 poisoning Toxicity 0.000 description 5
- 230000000607 poisoning effect Effects 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- -1 hydrogen Chemical class 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- 208000001408 Carbon monoxide poisoning Diseases 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910015667 MoO4 Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical class O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process 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
- 239000012847 fine chemical Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 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
- 239000002904 solvent Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a catalyst for preparing aniline from nitrobenzene, which comprises a porous carrier, and an active component and an auxiliary agent which are loaded on the carrier, wherein the active component comprises Pt, and the auxiliary agent comprises MoO3And Co; the invention also provides a preparation method of the catalyst and a method for preparing aniline by using the catalyst. The invention adds MoO on the catalyst carrier3And Co, using MoO3And Co, especially MoO3The electronic configuration of Pt is changed by the synergistic effect between Pt and Pt, the CO adsorption capacity of Pt is reduced, and the inactivation of Pt due to CO adsorption can be effectively avoided.
Description
Technical Field
The invention belongs to the field of aniline preparation by nitrobenzene liquid phase hydrogenation, and particularly relates to a catalyst for preparing aniline by nitrobenzene liquid phase hydrogenation for a slurry bed, a preparation method of the catalyst, and a method for preparing aniline by nitrobenzene liquid phase hydrogenation.
Background
Aniline is an important intermediate for synthesizing many fine chemicals and has wide application. In recent years, the demand for isocyanate as a raw material for polyurethane has been increasing with the improvement of the productivity of polyurethane, and the isocyanate has a wide development and utilization prospect.
The nitrobenzene catalytic hydrogenation method is the main method for industrially producing aniline at present, and comprises three methods, namely a fixed bed gas phase catalytic hydrogenation method, a fluidized bed gas phase catalytic hydrogenation method and a slurry bed liquid phase hydrogenation method. The fixed bed gas phase catalytic hydrogenation method has the advantages of mature technology, simple equipment and operation, low investment and the like, but is easy to generate local overheating to cause side reaction and catalyst deactivation, and the catalyst needs to be replaced regularly. The fluidized bed gas phase catalytic hydrogenation method has the characteristics of easily controlled reaction temperature and long service life of the catalyst, but has the defects of complex equipment operation, large catalyst abrasion, high device investment cost, high maintenance cost and the like. The technology for preparing aniline by slurry bed liquid phase hydrogenation successfully solves the series of problems, so that the production technology of aniline is more mature, and in addition, the technology for preparing aniline by slurry bed liquid phase hydrogenation has the advantages of low energy consumption, large production capacity of devices, low cost and the like.
At present, the liquid phase hydrogenation catalyst of the domestic slurry bed mostly adopts a noble metal catalyst of DuPont company patent, takes active carbon as a carrier, and takes loaded noble metal Pt/Pd as an active component. The catalyst has high hydrogenation catalytic activity, and the nitrobenzene conversion rate can reach 99.8%. However, there are several problems as follows: (1) for CO + CO in raw material hydrogen2The content index has higher requirements to avoid poisoning and inactivation of the Pt/Pd catalyst, thereby greatly increasing the cost of an upstream hydrogen supply device; (2) as an aniline matching device, the raw material benzene of the upstream nitrobenzene device usually contains 200-1000ppm of long-chain alkane with more than C12, and the part of the long-chain alkane enters the aniline device along with intermediate nitrobenzene; in addition, because of over-nitration, the intermediate nitrobenzene also usually contains 100-500ppm dinitrobenzene, the substance can generate heavy component tar after entering a hydrogenation reaction system, while the existing Pt/Pd/C catalyst carrier is usually activated carbon with smaller pore diameter, although the catalyst activity is facilitated, the requirement on the content indexes of heavy components such as heavy alkane in the raw material benzene, dinitrobenzene in the nitrobenzene and the like is higher, so as to avoid blocking the catalyst pore channel and inactivating the catalyst; (3) the content of over-hydrogenated byproducts is high, and the total amount of the byproducts cyclohexanone, cyclohexylamine and cyclohexanol generated by aromatic ring hydrogenation saturation is more than 5000 pm.
At present, there are many methods for reducing nitrobenzene liquid phase hydrogenation byproducts and catalyst poisoning disclosed in domestic and foreign patents, for example: U.S. Pat. No. 5, 6350911, 1 describes a liquid phase hydrogenation catalyst that contains an amount of Fe (OH)3The Pt catalyst using the activated carbon as a carrier is obtainedThe selectivity of the aniline is high, byproducts such as cyclohexanone and cyclohexanol are reduced, the content of the catalyst in the reaction mixture needs to be controlled to be more than 2%, and the production cost is high. In the patent publication EP04580061, aniline aromatic ring hydrogenation byproducts are reduced by adding a zinc compound and an alkali metal carbonate to the nitrobenzene hydrogenation system, but this process has the problem that it is difficult to separate the zinc salt and the carbonate from the reaction mixture.
Patent publication No. CN 1344585a describes a method for noble metal catalysts to resist carbon monoxide poisoning. Because carbon monoxide can be adsorbed on the surface of the noble metal catalyst to cause catalyst poisoning, the activity of the noble metal catalyst is reduced, and the carbon monoxide and hydrogen react to generate methane through nickel catalysis by loading nickel on the noble metal Pd/C catalyst, so that the carbon monoxide is prevented from poisoning the Pd/C catalyst, but the energy consumption and the hydrogen consumption are higher. For this reason, patent publication No. CN 1918091a describes a method for separating hydrogen from carbon monoxide in hydrocarbon compounds by using a modified clinoptilolite adsorbent, which avoids the high energy consumption cost and the consumption of hydrogen as a raw material due to methanation.
Disclosure of Invention
The invention aims to provide a catalyst for preparing aniline from nitrobenzene in a slurry bed and a preparation method thereof, and solves the problem that the existing catalyst is easy to be poisoned due to the existence of CO.
In order to achieve one aspect of the above purpose, the invention adopts the following technical scheme:
the catalyst for preparing aniline from nitrobenzene comprises a porous carrier, and an active component and an auxiliary agent which are loaded on the carrier, wherein the active component comprises Pt, and the auxiliary agent comprises MoO3And Co.
The skilled person understands that the active components obviously can also comprise other active components, such as the active components in the conventional catalyst for preparing aniline by liquid phase hydrogenation of nitrobenzene, such as nickel and the like, and can also ensure the hydrogenation reaction; preferably, the content of the other active components does not exceed 20 wt%, preferably 15 wt%, further preferably 10 wt%, more preferably 5 wt%, such as 2 wt%, 1 wt% or 0.5 wt% of the total amount of the active components, etc.
It is understood by those skilled in the art that the promoter may obviously also comprise other promoter components, such as promoter components in the conventional catalyst for liquid phase hydrogenation of nitrobenzene to aniline, such as iron and the like; preferably, the content of the other auxiliary components does not exceed 20 wt%, preferably 15 wt%, further preferably 10 wt%, more preferably 5 wt%, such as 2 wt%, 1 wt% or 0.5 wt% of the total amount of the auxiliary, etc.
According to the catalyst of the invention, preferably, Pt represents 0.1% to 5%, preferably 0.5% to 4% by weight, such as 1%, 2% or 3%, of the total mass of the catalyst; co accounts for 1% -10%, preferably 2% -8%, such as 3%, 5% or 6% of the total mass of the catalyst; MoO3From 1% to 10%, preferably from 2% to 8%, such as 3%, 5% or 6% by weight of the total catalyst. In a further preferred embodiment, the total weight of the active component and the auxiliary agent is from 2.1 wt% to 25 wt%, preferably from 5 wt% to 20 wt%, more preferably from 10 wt% to 15 wt%, based on the total weight of the catalyst; the weight ratio of the active component to the auxiliary agent is 0.005: 1-2.5: 1, preferably 0.1:1 to 0.5: 1. In the present invention, unless otherwise specified, the percentage is a mass content.
It will be appreciated by those skilled in the art that the support may be a porous support commonly used in the art, such as zeolite molecular sieves, Al2O3、SiO2、TiO2Any one of MgO, activated carbon or amorphous alumino-silicates or mixtures thereof. In the present invention, in view of the problem of over-hydrogenation that may occur in the reaction, it is preferable for the catalyst of the present invention that the carrier comprises Al2O3And ZnO, wherein Al2O3The content is 50-90%, such as 60%, 70% or 80% of the total mass of the carrier; the ZnO content is 10-50%, such as 20%, 30% or 40% of the total mass of the support.
In the present invention, it is preferable for the catalyst of the present invention that the specific surface area of the carrier is 100-400m in consideration of the problem of the deactivation by plugging of the channels which may occur in the catalyst during the reaction2G, e.g. 200 or 300m2A mean pore diameter of 10 to 30nm, for example 20nm, having mesoporesThe pore diameter can effectively avoid the problem of inactivation caused by the blockage of pore channels by long-chain waxy alkane and hydrogenation by-product tar, greatly prolongs the service life of the catalyst, and simultaneously reduces the index requirement on the raw material benzene and the control difficulty of nitration reaction.
In order to achieve another aspect of the above objects, the present invention provides a method for preparing the above catalyst, comprising the steps of:
(1) loading: adding soluble metal salts corresponding to metal elements in the active component and the auxiliary agent into deionized water according to a proportion to prepare a first aqueous solution, adding a carrier according to a corresponding proportion into the first aqueous solution, and drying after uniform adsorption to obtain an adsorbed carrier;
(2) reduction: reducing the adsorbed carrier in a hydrazine hydrate aqueous solution under the reflux condition, and then filtering and washing;
(3) roasting: roasting the reduction product obtained in the step (2) in an inert atmosphere to obtain Pt-Co-MoO3/Al2O3-a ZnO catalyst.
In the present invention, the soluble metal salt includes, but is not limited to, one or more of halide, nitrate, organic acid salt, etc. of the metal, which are well known in the art and will not be described herein. The amount ratio of each metal element in the aqueous solution may be determined in accordance with the ratio of each active component and the auxiliary component in the foregoing catalyst, and the concentration of the aqueous solution may be 1 to 30 wt%, such as 5 wt%, 10 wt%, or 20 wt%.
Among the above methods, methods for adsorbing the metal salt solution by using the carrier are well known in the art, and those skilled in the art understand that the adsorption amount of the metal salt in the carrier can be adjusted by adjusting the solution concentration, the impregnation time, and the like, thereby controlling the content of the active component or the auxiliary agent in the catalyst, and the adsorption process can also be performed once or repeatedly for a plurality of times. In one embodiment, the volume ratio of the metal salt solution to the support may also be controlled within a suitable range so that the metal salt solution can be substantially completely absorbed by the support or the resulting solid-liquid mixture of support and solution is subjected to evaporative drying to remove excess solvent.
According to the production method of the present invention, preferably, the support is composed of a metal oxide, and the production method of the support includes: dissolving soluble metal salts corresponding to metal elements in the carrier component in deionized water according to a proportion to prepare a second aqueous solution with a molar concentration of 0.1-5mol/L, preferably 0.5-4mol/L, such as 1, 1.5, 2, 2.5, 3 or 3.5 mol/L; adding a template agent into the second aqueous solution, heating the second aqueous solution to 30-60 ℃, adjusting the pH value to 8-10 by using ammonia water, stirring for 1-5 hours, such as 2, 3 or 4 hours, precipitating metal salt in a gel form, and then aging for 12-48 hours at 90-150 ℃, such as 100, 120 or 140 ℃; the aged material is filtered, washed, dried to obtain solid powder, and calcined at 500-800 deg.C, such as 600 or 700 deg.C, for 6-12 hours, such as 8 or 10 hours, to further remove the template agent to obtain the carrier.
According to the production method of the present invention, preferably, the component of the carrier is Al2O3And ZnO; the template agent is cetyltrimethylammonium chloride, and the molar ratio of the dosage of the cetyltrimethylammonium chloride to the aluminum salt is 0.1-0.3:1, such as 0.2: 1.
the invention also provides a method for preparing aniline, which is to prepare aniline by hydrogenation of nitrobenzene in the presence of a catalyst in a slurry bed reactor, wherein the catalyst is the catalyst or the phase catalyst prepared by the preparation method.
According to the production method of the present invention, preferably, the method for producing aniline comprises the steps of:
(a) formulating said catalyst with nitrobenzene into a catalyst slurry having a catalyst concentration of 0.5-5 wt%, such as 1, 2 or 3 wt%;
(b) preheating raw material nitrobenzene to 80-150 ℃, for example, mixing the raw material nitrobenzene with catalyst slurry at 100 or 200 ℃, and then feeding the mixture into the bottom of a slurry bed reactor, wherein the mass ratio of the catalyst to the nitrobenzene in the feed is 0.007-0.01;
(c) feeding hydrogen from a jet system to the bottom of the reactor and dispersing the hydrogen in the nitrobenzene/catalyst slurry mixture in a mass ratio of hydrogen to nitrobenzene such that the hydrogen excess is controlled to be not less than 8%, such as 9% or 10%, preferably 0.04 to 0.07, such as 0.05 or 0.06;
wherein the reaction pressure is controlled by hydrogen flow at a gauge pressure of 1.2-2.0MPa, such as 1.5 or 1.8MPa, and the reaction temperature is adjusted at 150 ℃ and 300 ℃, such as 180, 200 or 250 ℃ by quenching water fed into the reactor.
Compared with the prior art, the invention has the following advantages:
1. the invention adds MoO on the catalyst carrier3And Co, using MoO3And Co, especially MoO3The electronic configuration of Pt is changed by the synergistic effect with Pt, the CO adsorption capability of Pt is reduced, and the inactivation of Pt due to CO adsorption can be effectively avoided;
2. in the present invention, Al is added2O3Researches show that aiming at the catalyst of the invention, the carrier can effectively reduce the generation of a large amount of byproducts by excessive hydrogenation on aromatic rings, and simultaneously, the problem that zinc salt is directly added into a reaction system and is difficult to separate in the prior art is also avoided;
3. according to the invention, by adjusting the specific surface area and pores of the catalyst, the problem of deactivation caused by blocking of pore channels by long-chain waxy alkanes and hydrogenation by-product tar can be effectively avoided, and the service life of the catalyst is greatly prolonged.
Detailed Description
The present invention will be described in further detail with reference to examples, but is not limited to the examples.
The specific surface area and the average pore diameter of the catalyst are measured by a BET method;
unless otherwise specified, the reagents used below were all analytical grade.
Example 1:
mixing 24.5g AlCl3、21.4gZn(NO3)2Dissolving in 1L deionized water, adding 28.1g cetyltrimethylammonium chloride into the above salt solution, heating the salt solution to 30 deg.C in water bath, adjusting pH to 8 by dripping ammonia water, stirring for 1 hr to form gel precipitate, and aging at 90 deg.C for 12 hr. The mixture was then cooled, filtered, and washed with copious amounts of deionized water to remove the templating agent to yield a white solid powder. Then the solid powder is placed in a muffle furnaceRoasting, raising the temperature to 500 ℃ at 1 ℃/min, and continuously roasting for 6 hours to further remove the template agent to obtain the mesoporous Al2O3And a ZnO composite carrier. Take 0.13gH2PtCl6·6H2O、1.95gCoCl2·6H2O、0.64g(NH4)2MoO4Dissolving in deionized water, and dissolving mesoporous Al2O3And adding a ZnO composite carrier into the salt solution, electromagnetically stirring for 6 hours, drying to obtain a powdery solid, performing reflux reduction in a hydrazine hydrate aqueous solution for 2 hours, filtering the reduced catalyst, washing the catalyst to be neutral by using a large amount of deionized water, and roasting in a medium muffle furnace to obtain mesoporous Pt-Co-MoO3/Al2O3-ZnO catalyst No. 1 having a specific surface area of 327m by BET method2The average pore diameters were 29nm, respectively.
Comparative example 1
Compared with example 1, the difference is that4)2MoO4With CoCl of the same mass2·6H2O is substituted to obtain catalyst 1-1#, and the specific surface area is 211m by BET method2The average pore diameters were 17nm, respectively.
Example 2:
mixing 27.7g AlCl3、16.4gZn(NO3)2Dissolving in 1L deionized water, adding 26.9g cetyltrimethylammonium chloride into the above salt solution, heating the salt solution to 30 deg.C in water bath, adjusting pH to 8 by dripping ammonia water, stirring for 1 hr to form gel precipitate, and aging at 90 deg.C for 12 hr. The mixture was then cooled, filtered, and washed with copious amounts of deionized water to remove the templating agent to yield a white solid powder. Then placing the solid powder into a muffle furnace for roasting, raising the temperature to 500 ℃ at 1 ℃/min, and continuously roasting for 6 hours to further remove the template agent, thus obtaining the mesoporous Al2O3And a ZnO composite carrier. Take 6.1gH2PtCl6·6H2O、16.2gCoCl2·6H2O、5.6g(NH4)2MoO4Dissolving in deionized water, and dissolving mesoporous Al2O3And ZnO composite carrier is added into the salt solution, and is dried after being electromagnetically stirred for 6 hours to obtain powdery solid,refluxing and reducing the catalyst in a hydrazine hydrate aqueous solution for 2 hours, filtering the reduced catalyst, washing the catalyst to be neutral by using a large amount of deionized water, and roasting the catalyst in a medium muffle furnace to obtain mesoporous Pt-Co-MoO3/Al2O3-ZnO catalyst No. 2 having a specific surface area of 272m by the BET method2The average pore diameters were 24nm in each case.
Example 2-1
The difference compared with example 2 is that AlCl is added3And Zn (NO)3)2Zn (NO) in (1)3)2Replacement with AlCl of equivalent mass3To obtain catalyst 2-1#, which has a specific surface area of 189m as determined by BET method2The average pore diameters were 15nm, respectively.
Example 3:
mixing 29.9g of AlCl3、11.5gZn(NO3)2Dissolving in 1L deionized water, adding 25.3g cetyltrimethylammonium chloride into the above salt solution, heating the salt solution to 30 deg.C in water bath, adjusting pH to 8 by dripping ammonia water, stirring for 1 hr to form gel precipitate, and aging at 90 deg.C for 12 hr. The mixture was then cooled, filtered, and washed with copious amounts of deionized water to remove the templating agent to yield a white solid powder. Then placing the solid powder into a muffle furnace for roasting, raising the temperature to 500 ℃ at 1 ℃/min, and continuously roasting for 6 hours to further remove the template agent, thus obtaining the mesoporous Al2O3And a ZnO composite carrier. Take 3.9gH2PtCl6·6H2O、9.3gCoCl2·6H2O、3.1g(NH4)2MoO4Dissolving in deionized water, and dissolving mesoporous Al2O3And adding a ZnO composite carrier into the salt solution, electromagnetically stirring for 6 hours, drying to obtain a powdery solid, performing reflux reduction in a hydrazine hydrate aqueous solution for 2 hours, filtering the reduced catalyst, washing the catalyst to be neutral by using a large amount of deionized water, and roasting in a medium muffle furnace to obtain mesoporous Pt-Co-MoO3/Al2O3-ZnO catalyst # 3 having a specific surface area of 258m by BET method2The average pore diameters were 21nm in each case.
Example 3-1
And embodiments thereofAnd 3, compared with the catalyst, the difference is that in the preparation process of the carrier, the condition that the pH is adjusted to 8 by dropwise adding ammonia water is adjusted to 10 by dropwise adding ammonia water to obtain the catalyst No. 3-1, and the specific surface area is 214m by the determination of a BET method2The average pore diameters were 16nm, respectively.
Example 4:
mixing 37.9g of AlCl3、8.2gZn(NO3)2Dissolving in 1L deionized water, adding 28.2g cetyltrimethylammonium chloride into the above salt solution, heating the salt solution to 30 deg.C in water bath, adjusting pH to 8 by dripping ammonia water, stirring for 1 hr to form gel precipitate, and aging at 90 deg.C for 12 hr. The mixture was then cooled, filtered, and washed with copious amounts of deionized water to remove the templating agent to yield a white solid powder. Then placing the solid powder into a muffle furnace for roasting, raising the temperature to 500 ℃ at 1 ℃/min, and continuously roasting for 6 hours to further remove the template agent, thus obtaining the mesoporous Al2O3And a ZnO composite carrier. Take 2.1gH2PtCl6·6H2O、6.9gCoCl2·6H2O、2.3g(NH4)2MoO4Dissolving in deionized water, and dissolving mesoporous Al2O3And adding a ZnO composite carrier into the salt solution, electromagnetically stirring for 6 hours, drying to obtain a powdery solid, performing reflux reduction in a hydrazine hydrate aqueous solution for 2 hours, filtering the reduced catalyst, washing the catalyst to be neutral by using a large amount of deionized water, and roasting in a medium muffle furnace to obtain mesoporous Pt-Co-MoO3/Al2O3ZnO catalyst No. 4, having a specific surface area of 243m by the BET method2The average pore diameters were 19nm, respectively.
Example 5:
mixing 44.2g AlCl3、4.4gZn(NO3)2Dissolving in 1L deionized water, adding 29.7g cetyltrimethylammonium chloride into the above salt solution, heating the salt solution to 30 deg.C in water bath, adjusting pH to 8 by dripping ammonia water, stirring for 1 hr to form gel precipitate, and aging at 90 deg.C for 12 hr. The mixture was then cooled, filtered, and washed with copious amounts of deionized water to remove the templating agent to yield a white solid powder. Then placing the solid powder into a muffle furnace for roasting, raising the temperature to 500 ℃ at 1 ℃/min, and continuously roastingFiring for 6 hours to further remove the template agent, thus obtaining the mesoporous Al2O3And a ZnO composite carrier. Take 7.9gH2PtCl6·6H2O、24.1gCoCl2·6H2O、8.2g(NH4)2MoO4Dissolving in deionized water, and dissolving mesoporous Al2O3And adding a ZnO composite carrier into the salt solution, electromagnetically stirring for 6 hours, drying to obtain a powdery solid, performing reflux reduction in a hydrazine hydrate aqueous solution for 2 hours, filtering the reduced catalyst, washing the catalyst to be neutral by using a large amount of deionized water, and roasting in a medium muffle furnace to obtain mesoporous Pt-Co-MoO3/Al2O3-ZnO catalyst No. 5 having a specific surface area of 218m by BET method2The average pore diameters were 14nm, respectively.
The catalytic performance of the catalysts prepared in the above examples and comparative examples was tested in a slurry bed reactor for hydrogenation of nitrobenzene to aniline, under the following conditions:
(a) preparing a catalyst slurry with the concentration of 3 wt% by using the prepared catalyst and nitrobenzene;
(b) preheating raw material nitrobenzene to 130 ℃, mixing the raw material nitrobenzene with catalyst slurry, and feeding the mixture into the bottom of a slurry bed reactor, wherein the mass ratio of the catalyst to the nitrobenzene in the feed is 0.008;
(c) hydrogen is sent to the bottom of the reactor through an injection system and is dispersed in the nitrobenzene/catalyst slurry mixture, the mass ratio of the hydrogen to the nitrobenzene is controlled so that the hydrogen excess rate is not less than 8 percent, and the preferred mass ratio is 0.06;
wherein the reaction pressure is controlled at 1.4MPa by hydrogen flow, and the reaction temperature is adjusted at 180 ℃ by quenching water added into the reactor.
Wherein the content of long paraffin with more than C12 and dinitrobenzene in the raw material nitrobenzene is 700ppm in total; the CO content of the raw material hydrogen was 50ppm (350 ppm in total of the long-chain paraffin having a carbon number of 12 or more and dinitrobenzene contained in the raw material nitrobenzene).
The test results are given in table 1 below:
TABLE 1 Effect of hydrogenation
As can be seen from the data in Table 1, MoO3The method has strong capability of reducing the CO adsorption of Pt, can effectively avoid the inactivation of Pt due to CO adsorption, and greatly improves the conversion rate of nitrobenzene. In the absence of MoO3In the experiment of catalyst No. 1-1, the catalyst was deactivated by CO poisoning, the nitrobenzene conversion rate was only 35.43%, but the catalyst contained MoO3The conversion in the experiment of catalyst 1 was 99.98%. And the activity of the catalyst is reduced, so that the content of the over-hydrogenated by-products is also greatly reduced.
Al2O3The catalyst carrier prepared by the mixture of the catalyst carrier and ZnO can effectively reduce the generation of a large amount of byproducts by excessive hydrogenation on aromatic rings. In the ZnO-free catalyst 2-1# experiment, the level of over-hydrogenated by-products was as high as 2012ppm, while in the ZnO-containing catalyst 2 experiment the level of over-hydrogenated by-products was only 664 ppm.
The specific surface area and pores of the catalyst are adjusted, so that the problem of deactivation caused by blocking of pore channels by long-chain waxy alkanes and hydrogenation by-product tar can be effectively avoided. When the aperture of the catalyst is 24nm, the nitrobenzene conversion rate is highest, the catalyst activity is higher, and the content of byproducts is in a better level.
Claims (11)
1. The catalyst for preparing aniline from nitrobenzene comprises a porous carrier, and an active component and an auxiliary agent which are loaded on the carrier, and is characterized in that the active component comprises Pt, and the auxiliary agent comprises MoO3And Co;
wherein, Pt accounts for 0.1 to 5 percent of the total mass of the catalyst, Co accounts for 1 to 10 percent of the total mass of the catalyst, and MoO3Accounting for 1-10% of the total mass of the catalyst;
wherein the carrier comprises Al2O3And ZnO, wherein Al2O3The content of the ZnO accounts for 50-90% of the total mass of the carrier, and the content of the ZnO accounts for 10-50% of the total mass of the carrier.
2. The catalyst of claim 1, wherein the combined weight of the active component and the promoter is from 2.1 wt% to 25 wt% of the total weight of the catalyst; the weight ratio of the active component to the auxiliary agent is 0.005: 1-2.5: 1.
3. the catalyst of claim 2, wherein the combined weight of the active component and the promoter is from 5 wt% to 20 wt% of the total weight of the catalyst; the weight ratio of the active component to the auxiliary agent is 0.1:1-0.5: 1.
4. The catalyst of claim 3, wherein the combined weight of the active component and the promoter is from 10 wt% to 15 wt% of the total weight of the catalyst.
5. The catalyst as claimed in any one of claims 1 to 4, wherein the specific surface area of the carrier is 100-400m2(ii)/g, the average pore diameter is 10-30 nm.
6. A process for preparing a catalyst as claimed in any one of claims 1 to 5, comprising the steps of:
(1) loading: adding soluble metal salt corresponding to metal elements in the active component and the auxiliary agent into deionized water according to a certain proportion to prepare a first aqueous solution, and adding carrier Al with a certain proportion into the first aqueous solution2O3ZnO, after being uniformly adsorbed, drying to obtain the carrier after adsorption;
(2) reduction: reducing the adsorbed carrier in a hydrazine hydrate aqueous solution under the reflux condition, and then filtering and washing;
(3) roasting: roasting the reduction product obtained in the step (2) in an inert atmosphere to obtain Pt-Co-MoO3/Al2O3-a ZnO catalyst.
7. The method of claim 6, wherein the support is made of a metal oxide Al2O3And ZnO groupThe preparation method of the carrier comprises the following steps: dissolving soluble metal salts corresponding to metal elements in the carrier component in deionized water according to a proportion to prepare a second aqueous solution with the molar concentration of 0.1-5 mol/L; adding a template agent of cetyltrimethylammonium chloride into the second aqueous solution, heating the second aqueous solution to 30-60 ℃, adjusting the pH value to 8-10 by using ammonia water, stirring for 1-5 hours, precipitating metal salt in a gel form, and then aging for 12-48 hours at 90-150 ℃; and filtering, washing and drying the aged material to obtain solid powder, and roasting at the temperature of 500-800 ℃ for 6-12 hours to further remove the template agent to obtain the carrier.
8. The method of claim 7, wherein the molar ratio of the template to the aluminum salt is 0.1-0.3: 1.
9. A method for preparing aniline by hydrogenating nitrobenzene in the presence of a catalyst in a slurry bed reactor, wherein the catalyst is the catalyst according to any one of claims 1 to 5 or the catalyst prepared by the preparation method according to any one of claims 6 to 8.
10. The method for preparing aniline according to claim 9, wherein the method for preparing aniline comprises the following steps:
(a) preparing the catalyst and nitrobenzene into catalyst slurry with the concentration of 0.5-5 wt%;
(b) preheating raw material nitrobenzene to 80-150 ℃, mixing the raw material nitrobenzene with catalyst slurry, and feeding the mixture into the bottom of a slurry bed reactor, wherein the mass ratio of the catalyst to the nitrobenzene in the feed is 0.007-0.01;
(c) hydrogen is sent to the bottom of the reactor from an injection system and is dispersed in the nitrobenzene/catalyst slurry mixture, and the mass ratio of the hydrogen to the nitrobenzene is controlled so that the hydrogen excess rate is not lower than 8 percent;
wherein the reaction pressure is controlled at 1.2-2.0MPa by hydrogen flow, and the reaction temperature is adjusted at 150-300 ℃ by quenching water added into the reactor.
11. The method for producing aniline according to claim 10, wherein the mass ratio of hydrogen to nitrobenzene in step (c) is 0.04-0.07.
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| CN101912778A (en) * | 2010-09-01 | 2010-12-15 | 郴州高鑫铂业有限公司 | Method for preparing carbon-supported nano Pt-M fuel cell catalyst |
| CN106810419A (en) * | 2015-11-30 | 2017-06-09 | 山东华鲁恒升化工股份有限公司 | For graphene-supported metal composite in acetic acid preparation of ethanol through hydrogenation catalyst and preparation method thereof |
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| CN101912778A (en) * | 2010-09-01 | 2010-12-15 | 郴州高鑫铂业有限公司 | Method for preparing carbon-supported nano Pt-M fuel cell catalyst |
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