CN118002122A - Alumina supported catalyst with large specific surface area and preparation method thereof - Google Patents
Alumina supported catalyst with large specific surface area and preparation method thereof Download PDFInfo
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- CN118002122A CN118002122A CN202211339869.XA CN202211339869A CN118002122A CN 118002122 A CN118002122 A CN 118002122A CN 202211339869 A CN202211339869 A CN 202211339869A CN 118002122 A CN118002122 A CN 118002122A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 101
- 239000002184 metal Substances 0.000 claims abstract description 98
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052709 silver Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 46
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- 229910001593 boehmite Inorganic materials 0.000 claims description 27
- 150000003839 salts Chemical class 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 20
- 239000012298 atmosphere Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 15
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 14
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 14
- 230000001681 protective effect Effects 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 14
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- -1 aluminum ions Chemical class 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 229920002717 polyvinylpyridine Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 150000001345 alkine derivatives Chemical class 0.000 abstract description 19
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 abstract description 16
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 10
- 239000006227 byproduct Substances 0.000 abstract description 6
- 238000007171 acid catalysis Methods 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000011068 loading method Methods 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000010949 copper Substances 0.000 description 12
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical group CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 150000000475 acetylene derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- LFKIGTZUWPXSIH-UHFFFAOYSA-N but-1-ene;2-methylprop-1-ene Chemical compound CCC=C.CC(C)=C LFKIGTZUWPXSIH-UHFFFAOYSA-N 0.000 description 1
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
The invention discloses an alumina-supported catalyst with large specific surface area and a preparation method thereof. The catalyst of the invention comprises a carbon-modified alumina carrier and an active component loaded on the carbon-modified alumina carrier; the active component comprises a first metal active component and optionally a second metal active component; the first metal active component comprises Cu; the second metal active component is selected from at least one of Ni, co, pt, pd, rh, ru, mn, co and Ag; the specific surface area of the carbon-modified alumina carrier is more than or equal to 300m 2/g. The catalyst adopts the carbon-modified alumina carrier with large specific surface area, the acidity of the carrier surface can be obviously reduced, and the catalyst is favorable for avoiding byproducts generated by acid catalysis, thereby improving the reaction selectivity. When the catalyst is used for removing alkyne through four-carbon distillate hydrogenation, the higher alkyne removal rate can be obtained under the condition of ensuring the lowest loss rate of butadiene.
Description
Technical Field
The invention relates to the technical field of alkyne removal by carbon four selective hydrogenation, in particular to an alumina supported catalyst with large specific surface area and a preparation method thereof.
Background
Alumina supported catalysts have been widely used in petrochemical plants. The carrier can increase the mechanical strength of the catalyst in the catalyst, reduce the abrasion of the catalyst, improve the specific surface area of the catalyst, be beneficial to the good dispersion of active components and can also take on the function of a cocatalyst.
The active alumina is a porous and high-dispersivity solid material, has the characteristics of high crushing strength, moderate specific surface area, adjustable pore diameter and pore space, good adsorption performance, wide crystal phase temperature range and the like, becomes one of the most widely used catalysts or catalyst carriers in chemical industry and petroleum industry, and plays an important role in the reaction processes of cracking petroleum components, hydrofining, hydrodesulfurization, reforming hydrogen production of hydrocarbon, purifying automobile exhaust and the like.
The selective hydrogenation of the four-carbon fraction to remove alkyne is to convert acetylene hydrocarbon such as methyl acetylene, ethyl acetylene, vinyl acetylene and the like in the four-carbon fraction into butadiene, butylene and a small amount of butane through hydrogenation reaction by using a selective hydrogenation catalyst, and the method can selectively remove the acetylene hydrocarbon in the four-carbon fraction, thereby simplifying the butadiene separation flow. However, most of hydrogenation catalysts taking alumina as a carrier in the prior art are noble metal catalysts, when non-noble metal copper catalysts are used for removing alkyne in four carbon fractions, the reaction space velocity is low, and the catalyst is easy to deactivate because of more byproducts caused by the surface acidity of the alumina carrier, so that the catalyst which can effectively remove alkyne in four carbon fractions at a high space velocity and ensure low loss rate of butadiene is the technical problem to be solved at present.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an alumina supported catalyst with large specific surface area and a preparation method thereof. The catalyst has higher outer surface area, high utilization rate of active components and high catalytic reaction activity, and the surface acidity of the carbon-modified alumina carrier with large specific surface area adopted by the catalyst can be obviously reduced, so that by-products generated by acid catalysis can be avoided, and the reaction selectivity is improved. When the catalyst is used for removing alkyne through four-carbon distillate hydrogenation, the higher alkyne removal rate can be obtained under the condition of ensuring the lowest loss rate of butadiene.
It is an object of the present invention to provide an alumina-supported catalyst of a large specific surface area comprising a carbon-modified alumina carrier and an active component supported on the carbon-modified alumina carrier;
the active component comprises a first metal active component and optionally a second metal active component;
The first metal active component comprises Cu;
The second metal active component is selected from at least one of Ni, co, pt, pd, rh, ru, mn, co and Ag;
The specific surface area of the carbon-modified alumina carrier is more than or equal to 300m 2/g, preferably more than or equal to 320-460m 2/g.
The invention discovers that the acidity of the existing alumina carrier obviously leads to the occurrence of more byproducts in the reaction, and in order to solve the problem, the catalyst adopts the carbon-modified alumina carrier with large specific surface area, the surface acidity of the carrier can be obviously reduced, and the acid catalysis-generated byproducts can be avoided, thereby improving the reaction selectivity.
In the alumina-supported catalyst of large specific surface area according to the present invention, preferably,
Based on the weight of the carbon-modified alumina carrier as 100%,
The carbon content is 0.01-10wt%; preferably 0.1 to 1wt%.
In the alumina-supported catalyst of large specific surface area according to the present invention, preferably,
Based on 100% by weight of the catalyst,
The content of the first metal active component is 1 to 40wt%, preferably 10 to 30wt%, further preferably 14 to 27wt%;
When the second metal active component is contained, the content of the second metal active component is 0.001 to 0.5wt%, preferably 0.001 to 0.2wt%, and more preferably 0.05 to 0.15wt%.
The second object of the present invention is to provide a method for preparing the alumina-supported catalyst with a large specific surface area according to one of the objects of the present invention, comprising the steps of:
(1) Adding boehmite into a nitrogen-containing high polymer solution to react to obtain the boehmite modified by the nitrogen-containing high polymer;
(2) Roasting the nitrogenous high polymer modified boehmite in a protective atmosphere to obtain a carbon modified alumina carrier;
(3) And (3) contacting the carbon-modified alumina carrier with an active component precursor solution, carrying out aftertreatment, and roasting in a protective atmosphere to obtain the catalyst.
In the method for preparing an alumina-supported catalyst of large specific surface area according to the present invention, preferably,
In the step (1), the preparation method of the boehmite comprises the following steps:
(1-1) dropwise adding the sodium metaaluminate solution into the aluminum sulfate solution until the mixed solution is alkaline, and fully mixing to obtain a boehmite precursor;
(1-2) crystallizing the boehmite precursor, and performing post-treatment to obtain the boehmite.
In the method for preparing an alumina-supported catalyst of large specific surface area according to the present invention, preferably,
Step (1-1), wherein the molar ratio of sodium to aluminum in the sodium metaaluminate solution is 4.5:1, a step of; preferably, the sodium metaaluminate solution further comprises sodium hydroxide;
the sodium hydroxide has the function of regulating the pH value of the solution and also has the function of stabilizing sodium metaaluminate, because the sodium metaaluminate can react with carbon dioxide in the air in the aqueous solution;
the concentration of aluminum ions in the sodium metaaluminate solution is 0.1-0.8mol/L; and/or the number of the groups of groups,
The concentration of the aluminum sulfate solution is 0.1-0.7mol/L; and/or the number of the groups of groups,
The pH range corresponding to alkalinity is 8-11; and/or the number of the groups of groups,
The mixing mode is stirring, preferably stirring time is 10-60min; and/or the number of the groups of groups,
Step (1-2),
The crystallization treatment temperature is 70-120 ℃; and/or the number of the groups of groups,
The crystallization treatment time is 5-24 hours; and/or the number of the groups of groups,
The mode of post-treatment comprises at least one of filtration and washing;
Preferably, the crystallization treatment adopts hydrothermal crystallization treatment;
further preferably, the preparation method of the boehmite comprises the following steps:
(1) 22.56g of sodium hydroxide and 17.5g of sodium metaaluminate are weighed and dissolved in 250 ml of deionized water for later use.
(2) Weighing 83.4g of aluminum sulfate in 2500-250 ml of deionized water, dripping the sodium metaaluminate solution prepared in the step 1) into the aluminum sulfate solution with the concentration of 0.1-0.7mol/L until the pH value is 9.5-10, and stirring for 10-60min at room temperature to obtain the boehmite precursor.
(3) Crystallizing at 70-120deg.C for 5-24 hr to obtain boehmite with large specific surface area of 300-380m 2/g. The boehmite prepared in the invention is boehmite with large specific surface area.
In the method for preparing an alumina-supported catalyst of large specific surface area according to the present invention, preferably,
In the step (1), the step of (a),
The nitrogen-containing high molecular polymer is selected from one or a combination of polyvinyl imidazole, polyvinylpyrrolidone or polyvinyl pyridine; and/or the number of the groups of groups,
In the nitrogen-containing high polymer solution, the solvent is selected from one or a combination of methanol and ethanol; and/or the number of the groups of groups,
The mass ratio of the boehmite to the nitrogen-containing high molecular polymer is 1-100: 1, a step of; and/or the number of the groups of groups,
The reaction temperature is 100-120 ℃; and/or the number of the groups of groups,
The reaction time is 4-10 h; and/or the number of the groups of groups,
Preferably, the method comprises the steps of,
The concentration of the nitrogen-containing high molecular polymer solution is 0.1-2wt%; further preferably 0.6 to 1.8wt%.
In the method for preparing an alumina-supported catalyst of large specific surface area according to the present invention, preferably,
In the step (2), the step of (C),
The roasting temperature is 400-800 ℃; and/or the number of the groups of groups,
Roasting for 2-10 h; and/or the number of the groups of groups,
The protective atmosphere is at least one selected from nitrogen atmosphere and inert atmosphere; preferably, the inert atmosphere is at least one of a nitrogen atmosphere, an argon atmosphere and a helium atmosphere.
In the method for preparing an alumina-supported catalyst of large specific surface area according to the present invention, preferably,
In step (3), the active component precursor solution includes a soluble metal salt of a first metal active component and optionally a soluble metal salt of a second metal active component; preferably, the method comprises the steps of,
When the soluble metal salt of the second metal active component is not contained, firstly, the carbon-modified alumina carrier is contacted with a precursor solution of the first metal active component for one time, and then is subjected to aftertreatment and roasting for one time in a protective atmosphere to obtain the catalyst; or alternatively
When the soluble metal salt containing the second metal active component is contained, firstly, the carbon-modified alumina carrier is contacted with a precursor solution of the first metal active component for one time, and then is subjected to aftertreatment, and is subjected to primary roasting in a protective atmosphere to obtain a primary roasting product; and then, the primary roasting product is in secondary contact with a precursor solution of a second metal active component, after-treatment, and secondary roasting is carried out in protective atmosphere, so that the catalyst is obtained.
In the method for preparing an alumina-supported catalyst of large specific surface area according to the present invention, preferably,
The soluble metal salt of the first metal active component is selected from soluble nitrates of the first metal active component; and/or the number of the groups of groups,
The soluble metal salt of the second metal active component is selected from at least one of soluble nitrate, soluble acetate and soluble chloride of the second metal active component; and/or the number of the groups of groups,
Calculated as the sum of the mass of the metal element in the soluble metal salt of the first metal active component, optionally the mass of the metal element in the soluble metal salt of the second metal active component, the carrier mass is 100%,
The mass content of the metal element in the soluble metal salt of the first metal active component is 1 to 40wt%, preferably 10 to 30wt%, further preferably 14 to 27wt%;
When the second metal active component is contained, the mass content of the metal element in the soluble metal salt of the second metal active component is 0.001 to 0.5wt%, preferably 0.001 to 0.2wt%, and more preferably 0.05 to 0.15wt%.
Preferably, the method comprises the steps of,
The concentration of the soluble metal salt of the first metal active component in the active component precursor solution is 10-66.7wt%; and/or the number of the groups of groups,
The concentration of the soluble metal salt of the second metal active component in the active component precursor solution is 4-8wt%;
Still further preferably, the method further comprises the step of,
The mass ratio of the metal element in the soluble metal salt of the first metal active component to the carbon-modified alumina carrier is 1:99-46, preferably 1:9-3:7, preparing a base material;
the mass ratio of the metal elements in the soluble metal salt of the carbon-modified alumina carrier and the second metal active component is 1:10000-1: 200; preferably 1:10000-1:500.
In the method for preparing an alumina-supported catalyst of large specific surface area according to the present invention, preferably,
In the step (3), the contact modes are at least one of dipping and spraying independently;
The temperature of the contact is 15-40 ℃ independently of each other; and/or the number of the groups of groups,
The contact time is 10-60min independently; and/or the number of the groups of groups,
The temperature of calcination is each independently 400-800 ℃; and/or the number of the groups of groups,
The roasting time is 2-10h independently; and/or the number of the groups of groups,
The mode of the post-treatment comprises a drying treatment independently; and/or the number of the groups of groups,
The protective atmospheres are each independently selected from at least one of a nitrogen atmosphere and an inert atmosphere;
Preferably, the drying temperature in the post-treatment is 100-130 ℃; and/or drying for 8-15h.
The invention also provides a method for removing alkyne by hydrogenation of the carbon four fractions, which comprises the following steps:
performing alkyne removal reaction on the carbon four fraction containing alkyne and hydrogen under the action of a catalyst to obtain the carbon four fraction from which alkyne is removed;
The catalyst is a catalyst according to one of the objects of the present invention or a catalyst prepared by the preparation method according to the second object of the present invention.
In the process for the hydrodeacetylene removal of carbon four cuts according to the invention, it is preferred,
In the carbon four fraction containing alkyne, the volume fraction of alkyne is 0.3-1.2%.
In the process for the hydrodeacetylene removal of carbon four cuts according to the invention, it is preferred,
The reaction space velocity of the carbon four fraction measured by liquid volume is 2-20 h -1; preferably 8-16h -1;
The molar ratio of the hydrogen to the carbon four fraction is 0.2-10: 1, a step of; preferably 1 to 5:1, a step of;
the temperature of alkyne removal reaction is 30-60 ℃; preferably 40-50 ℃;
The pressure of alkyne removal reaction is 0.5-2.0 MPa; preferably 0.5-1.5MPa.
The carbon-modified alumina-supported catalyst with large specific surface area of the invention can remove alkyne in liquid-phase carbon four-fraction to below 60ppm, and the loss rate of 1, 3-butadiene is controlled below 2%.
The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein. In the following, the individual technical solutions can in principle be combined with one another to give new technical solutions, which should also be regarded as specifically disclosed herein.
All publications, patent applications, patents, and other references mentioned in this specification are incorporated herein by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the meaning commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, definitions, will control.
Compared with the prior art, the invention has at least the following advantages:
(1) The carbon-modified alumina-supported catalyst with large specific surface area has higher outer surface area, more uniform distribution of active components, high utilization rate and high catalytic reaction activity.
(2) The surface acidity of the carbon-modified alumina carrier with a large specific surface area can be obviously reduced, which is beneficial to avoiding byproducts generated by acid catalysis, thereby improving the reaction selectivity.
In conclusion, the carbon-modified alumina-supported catalyst with large specific surface area belongs to a new structure carrier catalyst, and the surface-supported carbon effectively reduces the acidity of the catalyst and improves the selectivity of the catalyst, so that the catalyst has high catalytic activity and small active component loading.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
In addition, the specific features described in the following embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, so long as the concept of the present invention is not deviated, and the technical solution formed thereby is a part of the original disclosure of the present specification, and also falls within the protection scope of the present invention.
The raw materials used in examples and comparative examples, if not particularly limited, are all as disclosed in the prior art, and are, for example, available directly or prepared according to the preparation methods disclosed in the prior art.
Characterization method of XRF:
After the sample is pressed into tablets and molded, an X-ray photoelectron spectrometer is adopted, and after vacuumizing, the element composition and the relative content on the surface of the sample are analyzed.
Example 1
(1) 22.56G of NaOH and 17.5g of sodium metaaluminate are weighed and dissolved in 250 ml of deionized water to prepare 0.5mol/L sodium metaaluminate solution.
(2) 88.4G of aluminum sulfate is weighed into 500 ml of deionized water, the sodium metaaluminate solution prepared in the step 1) is dripped into the aluminum sulfate solution with the concentration of 0.5mol/L until the pH value is 9.5, and the mixture is stirred for 30min at room temperature, so as to obtain the boehmite precursor.
(3) Transferring the suspension into an autoclave, and crystallizing at 80 ℃ for 4 hours to obtain the boehmite with large specific surface area.
(4) 100G of the boehmite with a large specific surface area obtained above was immersed in an ethanol solution of polyvinyl imidazole with a concentration of 1wt% (wherein the amount of polyvinyl imidazole was 1 g), then transferred into a hydrothermal kettle, reacted at 100℃for 10 hours, cooled and filtered, dried at 80℃for 4 hours, and then placed in a nitrogen atmosphere, and calcined at 400℃for 10 hours to obtain a support (carbon-modified alumina support).
(5) 20G of the carrier was placed in a 16wt% copper nitrate aqueous solution (in which the amount of copper nitrate as a metal element was 3.52 g), immersed for 20 minutes at room temperature, then the carrier was taken out, drained, dried at 120℃for 12 hours, and calcined at 400℃for 3 hours in a nitrogen atmosphere to obtain a catalyst.
The specific surface area of the carbon-modified alumina carrier prepared by the method is 320m 2/g; the carbon content in the carbon-modified alumina support was 0.12wt%.
The copper loading in the catalyst was 14.9wt% as characterized by XRF;
example 2
Steps (1-3) are the same as in example 1.
(4) 100G of boehmite having a large specific surface area obtained in example 1 was immersed in an ethanol solution of polyvinyl imidazole having a concentration of 1wt% (wherein the amount of polyvinyl imidazole was 1 g), then transferred to a hydrothermal vessel, reacted at 100℃for 10 hours, cooled and filtered, dried at 80℃for 4 hours, and then placed in a nitrogen atmosphere, and calcined at 400℃for 10 hours to obtain a support (carbon-modified alumina support).
(5) 20G of the carrier was placed in a 20wt% aqueous solution of copper nitrate (wherein the amount of copper nitrate as a metal element was 4.4 g), the carrier was taken out after immersing at room temperature for 20 minutes, drained, dried at 120℃for 12 hours, and calcined at 400℃for 3 hours in a nitrogen atmosphere to obtain a catalyst.
The copper loading in the catalyst was 17.8wt% as characterized by XRF.
Example 3
Steps (1-3) are the same as in example 1.
(4) 100G of boehmite having a large specific surface area obtained in example 1 was immersed in an ethanol solution of polyvinyl imidazole having a concentration of 1wt% (wherein the amount of polyvinyl imidazole was 1 g), then transferred to a hydrothermal vessel, reacted at 100℃for 10 hours, cooled and filtered, dried at 80℃for 4 hours, and then placed in a nitrogen atmosphere, and calcined at 400℃for 10 hours to obtain a support (carbon-modified alumina support).
(5) 20G of the carrier was placed in a 30wt% copper nitrate aqueous solution (in which the amount of copper nitrate as a metal element was 5.4 g), immersed at room temperature for 20 minutes, then taken out of the carrier, drained, dried at 120℃for 12 hours, and calcined at 400℃for 3 hours in a nitrogen atmosphere to obtain a catalyst.
The copper loading in the catalyst was 21.0wt% as characterized by XRF.
Example 4
Steps (1-3) are the same as in example 1.
(4) 100G of boehmite having a large specific surface area obtained in example 1 was immersed in an ethanol solution of polyvinyl imidazole having a concentration of 1wt% (wherein the amount of polyvinyl imidazole was 1 g), then transferred to a hydrothermal vessel, reacted at 100℃for 10 hours, cooled and filtered, dried at 80℃for 4 hours, and then placed in a nitrogen atmosphere, and calcined at 400℃for 10 hours to obtain a support (carbon-modified alumina support).
(5) 20G of the carrier was placed in a 45wt% copper nitrate aqueous solution (in which the amount of copper nitrate was 7.2g in terms of metal element), immersed at room temperature for 20 minutes, then taken out of the carrier, drained, dried at 120℃for 12 hours, and calcined at 400℃for 3 hours in a nitrogen atmosphere to obtain a catalyst.
The copper loading in the catalyst was 26.2wt% as characterized by XRF.
Example 5
Steps (1-3) are the same as in example 1.
(4) 100G of boehmite having a large specific surface area obtained in example 1 was immersed in an ethanol solution of polyvinyl imidazole having a concentration of 1wt% (wherein the amount of polyvinyl imidazole was 1 g), then transferred to a hydrothermal vessel, reacted at 100℃for 10 hours, cooled and filtered, dried at 80℃for 4 hours, and then placed in a nitrogen atmosphere, and calcined at 400℃for 10 hours to obtain a support (carbon-modified alumina support).
(5) 20 G of the carrier was put in a 16wt% aqueous solution of copper nitrate (wherein the amount of copper nitrate is 3.52g in terms of metal element) and immersed at room temperature for 20 minutes, then the carrier was taken out, drained, dried at 120℃for 12 hours, and calcined at 400℃for 3 hours in a nitrogen atmosphere to obtain a primary calcined product.
(6) And (3) placing the primary roasting product obtained in the step (5) into a mixed solution consisting of 0.1wt% of palladium nitrate aqueous solution (wherein the use amount of palladium nitrate is 0.016g based on metal elements), soaking for 20 minutes at room temperature, taking out the carrier, draining, drying at 120 ℃ for 12 hours, and roasting at 400 ℃ for 3 hours in a nitrogen atmosphere to obtain the catalyst.
The catalyst was characterized by XRF with a copper loading of 14.8wt% and a palladium loading of 0.06wt%.
Example 6
Steps (1-3) are the same as in example 1.
(4) 100G of boehmite having a large specific surface area obtained in example 1 was immersed in an ethanol solution of polyvinyl imidazole having a concentration of 1wt% (wherein the amount of polyvinyl imidazole was 1 g), then transferred to a hydrothermal vessel, reacted at 100℃for 10 hours, cooled and filtered, dried at 80℃for 4 hours, and then placed in a nitrogen atmosphere, and calcined at 400℃for 10 hours to obtain a support (carbon-modified alumina support).
(5) 20 G of the carrier was put in a 20wt% aqueous solution of copper nitrate (wherein the amount of copper nitrate is 4.4g in terms of metal element), the carrier was taken out after immersing at room temperature for 20 minutes, drained, dried at 120℃for 12 hours, and calcined at 400℃for 3 hours in a nitrogen atmosphere to obtain a primary calcined product.
(6) And (3) placing the primary roasting product obtained in the step (5) in a 0.2wt% palladium nitrate aqueous solution (wherein the palladium nitrate is used in an amount of 0.032g calculated as metal element), soaking for 20 minutes at room temperature, taking out the carrier, draining, drying at 120 ℃ for 12 hours, and roasting at 400 ℃ for 3 hours in a nitrogen atmosphere to obtain the catalyst.
The catalyst was characterized by XRF with a copper loading of 18wt% and a palladium loading of 0.13wt%.
Comparative example 1
The catalyst preparation was carried out as in example 2, except that alumina microspheres (specific surface 236m 2/g) were directly used as a carrier.
The copper loading in the catalyst was 17.5wt% as characterized by XRF.
Comparative example 2
The catalyst preparation was carried out as in example 5, except that alumina microspheres (specific surface 236m 2/g) were directly used as a carrier.
The catalyst was characterized by XRF with a copper loading of 14.0wt% and a palladium loading of 0.058wt%.
Comparative example 3
The catalyst preparation was carried out as in example 6, except that alumina microspheres (specific surface 236m 2/g) were directly used as a carrier.
The catalyst was characterized by XRF with a copper loading of 17.6wt% and a palladium loading of 0.125wt%.
Comparative example 4
The catalyst was prepared in the same manner as in step (1-4) of example 5, except that step (5) of example 5 was not included and step (6) of example 5 was included only: and (3) placing the carrier obtained in the step (4) into a mixed solution consisting of 0.1wt% of palladium nitrate aqueous solution (wherein the use amount of the palladium nitrate is 0.016g based on metal elements), immersing the carrier at room temperature for 20 minutes, taking out the carrier, draining, drying at 120 ℃ for 12 hours, and roasting at 400 ℃ for 3 hours in a nitrogen atmosphere to obtain the catalyst.
The palladium loading in the catalyst was 0.079wt% as characterized by XRF.
Example 7
Catalyst evaluations were performed in a reactor, which is an existing two-stage fixed bed reactor (stage I and stage II). Each section was charged with 20mL of catalyst, and after conversion with nitrogen, the carbon four fraction was mixed with hydrogen and fed into the reactor. The metered carbon four-fraction raw material is mixed with metered hydrogen, and enters the section I and the section II reactor from the lower part of the reactor in sequence. The reaction product flows out of the top of the reactor into a product storage tank. The catalyst was replaced with nitrogen before the reaction and reduced with hydrogen at 150 ℃ for 2 hours. The composition of the carbon four fraction is shown in table 1. The reaction time was evaluated to be 100 hours, and the reaction conditions and test results are shown in Table 2. The content of each component in the carbon four fraction and the hydrogenation product was determined by gas chromatography.
TABLE 1 composition of the carbon four fraction
| Component (A) | Content (vol%) | Component (A) | Content (vol%) |
| Isobutane | 2.35 | 1, 2-Butadiene | 0.17 |
| N-butane | 4.73 | 1, 3-Butadiene | 48.56 |
| Trans-2-butene | 4.49 | Methyl acetylene | 0.08 |
| 1-Butene | 13.9 | Ethylacetylene | 0.14 |
| Isobutene (i-butene) | 21.31 | Vinyl acetylene | 0.73 |
| Cis-2-butene | 3.36 |
TABLE 2 reaction conditions and reaction results for the removal of alkynes by hydrogenation of the C4 fraction
The results of comparative examples 1 and 2, comparative examples 2 and 5, and comparative examples 3 and 6 can be seen: compared with the comparative example, the catalyst has better catalysis effect when the catalyst is used for removing the alkyne in the carbon four fraction. It can also be seen from Table 2 that the use of the catalysts of examples 1-6 of the present invention effectively removes acetylenes from the four carbon fraction while ensuring that the loss of butadiene is less than 3%. The results fully demonstrate that the catalyst prepared by the carbon-modified alumina carrier of the invention has better effect.
In addition, it can be seen from comparison of comparative example 4 with examples 1 and 5 that Cu and Pd in the catalyst of the present invention have a synergistic effect, and the effect of the catalyst can be further improved.
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (11)
1. An alumina supported catalyst of large specific surface area, characterized in that: the alumina-supported catalyst with large specific surface area comprises a carbon-modified alumina carrier and an active component supported on the carbon-modified alumina carrier;
the active component comprises a first metal active component and optionally a second metal active component;
The first metal active component comprises Cu;
The second metal active component is selected from at least one of Ni, co, pt, pd, rh, ru, mn, co and Ag;
The specific surface area of the carbon-modified alumina carrier is more than or equal to 300m 2/g, preferably more than or equal to 320-460m 2/g.
2. The large specific surface area alumina supported catalyst of claim 1, wherein:
Based on the weight of the carbon-modified alumina carrier as 100%,
The carbon content is 0.01-10wt%; preferably 0.1 to 1wt%.
3. The large specific surface area alumina supported catalyst of claim 1, wherein:
Based on 100% by weight of the catalyst,
The content of the first metal active component is 1 to 40wt%, preferably 10 to 30wt%, further preferably 14 to 27wt%;
When the second metal active component is contained, the content of the second metal active component is 0.001 to 0.5wt%, preferably 0.001 to 0.2wt%, and more preferably 0.05 to 0.15wt%.
4. A method for preparing a large specific surface area alumina supported catalyst according to any one of claims 1 to 3, comprising the steps of:
(1) Adding boehmite into a nitrogen-containing high polymer solution to react to obtain the boehmite modified by the nitrogen-containing high polymer;
(2) Roasting the nitrogenous high polymer modified boehmite in a protective atmosphere to obtain a carbon modified alumina carrier;
(3) And (3) contacting the carbon-modified alumina carrier with an active component precursor solution, carrying out aftertreatment, and roasting in a protective atmosphere to obtain the alumina supported catalyst with large specific surface area.
5. The method for preparing an alumina-supported catalyst having a large specific surface area according to claim 4, wherein:
in the step (1), the preparation method of the boehmite comprises the following steps:
(1-1) dropwise adding the sodium metaaluminate solution into the aluminum sulfate solution until the mixed solution is alkaline, and fully mixing to obtain a boehmite precursor;
(1-2) crystallizing the boehmite precursor, and performing post-treatment to obtain the boehmite.
6. The method for preparing an alumina-supported catalyst having a large specific surface area according to claim 5, wherein:
step (1-1),
The concentration of aluminum ions in the sodium metaaluminate solution is 0.1-0.8mol/L; and/or the number of the groups of groups,
The concentration of the aluminum sulfate solution is 0.1-0.7mol/L; and/or the number of the groups of groups,
The pH range corresponding to alkalinity is 8-11; and/or the number of the groups of groups,
The mixing mode is stirring, preferably stirring time is 10-60min; and/or the number of the groups of groups,
Step (1-2),
The crystallization treatment temperature is 70-120 ℃; and/or the number of the groups of groups,
The crystallization treatment time is 5-24 hours; and/or the number of the groups of groups,
The mode of post-treatment comprises at least one of filtration and washing;
Preferably, the crystallization treatment is a hydrothermal crystallization treatment.
7. The method for preparing an alumina-supported catalyst having a large specific surface area according to claim 4, wherein:
In the step (1), the step of (a),
The nitrogen-containing high molecular polymer is selected from one or a combination of polyvinyl imidazole, polyvinylpyrrolidone or polyvinyl pyridine; and/or the number of the groups of groups,
In the nitrogen-containing high polymer solution, the solvent is selected from one or a combination of methanol and ethanol; and/or the number of the groups of groups,
The mass ratio of the boehmite to the nitrogen-containing high molecular polymer is 1-100: 1, a step of; and/or the number of the groups of groups,
The reaction temperature is 100-120 ℃; and/or the number of the groups of groups,
The reaction time is 4-10 h; and/or the number of the groups of groups,
Preferably, the method comprises the steps of,
The concentration of the nitrogen-containing high molecular polymer solution is 0.1-2wt%; further preferably 0.6 to 1.8wt%.
8. The method for preparing an alumina-supported catalyst having a large specific surface area according to claim 4, wherein:
In the step (2), the step of (C),
The roasting temperature is 400-800 ℃; and/or the number of the groups of groups,
Roasting for 2-10 h; and/or the number of the groups of groups,
The protective atmosphere is selected from at least one of a nitrogen atmosphere and an inert atmosphere.
9. The method for preparing an alumina-supported catalyst having a large specific surface area according to claim 4, wherein:
In step (3), the active component precursor solution includes a soluble metal salt of a first metal active component and optionally a soluble metal salt of a second metal active component; preferably, the method comprises the steps of,
When the soluble metal salt of the second metal active component is not contained, firstly, the carbon-modified alumina carrier is contacted with a precursor solution of the first metal active component for one time, and then is subjected to aftertreatment and roasting for one time in a protective atmosphere to obtain the catalyst; or alternatively
When the soluble metal salt containing the second metal active component is contained, firstly, the carbon-modified alumina carrier is contacted with a precursor solution of the first metal active component for one time, and then is subjected to aftertreatment, and is subjected to primary roasting in a protective atmosphere to obtain a primary roasting product; and then, the primary roasting product is in secondary contact with a precursor solution of a second metal active component, after-treatment, and secondary roasting is carried out in protective atmosphere, so that the catalyst is obtained.
10. The method for preparing an alumina-supported catalyst of large specific surface area according to claim 9, characterized in that:
the soluble metal salt of the first metal active component is selected from soluble nitrates of the first metal active component; and/or the number of the groups of groups,
The soluble metal salt of the second metal active component is selected from at least one of soluble nitrate, soluble acetate and soluble chloride of the second metal active component; and/or the number of the groups of groups,
Calculated as the sum of the mass of the metal element in the soluble metal salt of the first metal active component, optionally the mass of the metal element in the soluble metal salt of the second metal active component, the carrier mass is 100%,
The mass content of the metal element in the soluble metal salt of the first metal active component is 1 to 40wt%, preferably 10 to 30wt%, further preferably 14 to 27wt%;
When the second metal active component is contained, the mass content of the metal element in the soluble metal salt of the second metal active component is 0.001 to 0.5wt%, preferably 0.001 to 0.2wt%, and more preferably 0.05 to 0.15wt%.
Preferably, the method comprises the steps of,
The concentration of the soluble metal salt of the first metal active component in the active component precursor solution is 10-66.7wt%; and/or the number of the groups of groups,
The concentration of the soluble metal salt of the second metal active component in the active component precursor solution is 4-8wt%.
11. The method for preparing an alumina-supported catalyst of large specific surface area according to claim 10, characterized in that:
in the step (3), the modes of primary contact and secondary contact are respectively and independently selected from at least one of dipping and spraying;
The temperature of the primary contact and the secondary contact is respectively 15-40 ℃; and/or the number of the groups of groups,
The time of the primary contact and the secondary contact is respectively and independently 10-60min; and/or the number of the groups of groups,
The temperature of the primary roasting and the secondary roasting is respectively and independently 400-800 ℃; and/or the number of the groups of groups,
The time of primary roasting and secondary roasting is 2-10h independently; and/or the number of the groups of groups,
The mode of the post-treatment comprises a drying treatment independently; and/or the number of the groups of groups,
The protective atmospheres are each independently selected from at least one of a nitrogen atmosphere and an inert atmosphere.
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