CN112264024A - Environment-friendly fluidized bed alkane dehydrogenation catalyst and preparation method thereof - Google Patents
Environment-friendly fluidized bed alkane dehydrogenation catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a dehydrogenation catalyst, in particular to a fluidized bed alkane dehydrogenation catalyst and a preparation method thereof. The catalyst comprises a component A, B, C, D, E, wherein the component A is selected from one or more oxides of Fe, Ni, Co, W and Mo, the component B is selected from one or more oxides of Ge, Sb, In and Te, the component C is selected from one or more oxides of Zn, Cu, Ga and Mn, the component D is selected from one or more oxides of Ba, Ca, Mg, K and Na, and the component E is a carrier. The catalyst does not contain noble metal Pt, does not contain Cr and V which pollute the environment, and is a catalyst with low price and environmental protection. The catalyst has high alkane conversion rate and high olefin selectivity, and can be used for a fluidized bed reaction device.
Description
Technical Field
The invention relates to a dehydrogenation catalyst, in particular to a fluidized bed alkane dehydrogenation catalyst and a preparation method of the catalyst.
Background
The alkane dehydrogenation technology has been industrialized, and the catalysts used at present mainly have two types: pt-based catalysts and CrOx-based catalysts. The Pt-based catalyst has high cost and is sensitive to sulfur, olefin and other poisons, so the requirements on raw materials are strict and the raw materials need to be pretreated. The CrOx-based catalyst is easy to coke and quickly deactivated and needs to be repeatedly regenerated; in addition, Cr6+ has strong toxicity, is a carcinogen published by the International center for anticancer research and the U.S. toxicological organization, hexavalent chromium is a first pollutant in the national industrial wastewater discharge standard, hexavalent chromium compounds are listed in the poisonous and harmful pollutant directory (first batch) at 7-24.7.2019, and serious environmental pollution can be caused in the preparation, use and subsequent recovery links of Cr-based catalysts. Therefore, there is a need to develop low cost, environmentally friendly alkane dehydrogenation catalysts.
CN111036260A and CN109939688A disclose an iron-based propane dehydrogenation catalyst respectively, but the catalyst conversion rate and selectivity are both low, and industrialization is difficult to realize. CN109382090A discloses a molybdenum-vanadium bimetallic oxide catalyst, which has very good activity, but vanadium oxide has higher toxicity and stronger carcinogenicity. CN 102451677, CN104610768 and CN105289622 provide a series of alkane dehydrogenation catalysts which take Al2O3, SiO2, ZrO2, TiO2 and MgO as carriers and a plurality of metals as active components, although better propylene yield is achieved. However, the dehydrogenation catalyst using single or composite metal oxide as a carrier has the problem that the conversion rate and the selectivity cannot be coordinated, and still has a space for optimizing and improving.
Disclosure of Invention
Aiming at the defects of the prior art, the invention develops a fluidized bed alkane dehydrogenation catalyst which is a non-noble metal environment-friendly alkane dehydrogenation catalyst. The active component of the catalyst is non-noble metal element, does not contain noble metal Pt, does not contain Cr and V which pollute the environment, and is a catalyst with low price and environmental protection; and the active components are enriched on the surface, have higher alkane conversion rate and olefin selectivity, and can be used for a fluidized bed reaction device.
It is a further object of the present invention to provide a process for the preparation of the above-described catalyst.
In order to achieve the above purpose, the specific technical scheme of the invention is as follows:
a fluidized bed alkane dehydrogenation catalyst comprises a component A, B, C, D, E, wherein a component A is selected from one or more oxides of Fe, Ni, Co, W and Mo, a component B is selected from one or more oxides of Ge, Sb, In and Te, a component C is selected from one or more oxides of Zn, Cu, Ga and Mn, a component D is selected from one or more oxides of Ba, Ca, Mg, K and Na, and a component E is a carrier.
As a better preferable mode of the method, the content of the oxide of the component A in the catalyst is 1-15% by mass percentage; the content of the oxide of the component B in the catalyst is 0.01-1.5%; the content of the oxide of the component C in the catalyst is 0.1-15%; the oxide of the component D accounts for 0.1-5% of the catalyst; the content of the component E accounts for 65-95% of the catalyst, and the sum of the total mass percentage is 100%.
As a better preferable mode of the method, the content of the oxide of the component A in the catalyst is 2-12% by mass percentage; the content of the oxide of the component B in the catalyst is 0.05-0.7%; the content of the oxide of the component C in the catalyst is 4-12%; the content of the oxide of the component D in the catalyst is 0.1-1.5%; the content of the component E in the catalyst is 65-95%, and the sum of the total mass percentage is 100%.
In a preferred embodiment of the present invention, component E is an alumina support.
As a preferred mode of the present application, the A, C, D component and the precursor are preferably nitrates.
The component B can generate a synergistic effect with the component A, and can promote the surface enrichment of the component A, so that the component A is more exposed on the surface, and the activity of the catalyst is enhanced.
The component C can effectively disperse the component A, so that the component A cannot form a metal cluster, the hydrogenolysis activity is inhibited, and the olefin selectivity is improved.
As a better preferred mode of the application, the component D interacts with the carrier, so that the acid-base property of the carrier is effectively controlled, the strong acid sites of the carrier are reduced, the cracking activity is reduced, and the selectivity is improved.
As a preferred mode of the present invention, the alkane includes an alkane having 2 to 4 carbon atoms.
As a preferred mode of the present application, the preparation method of the catalyst comprises the following steps:
1) preparation of the support
Adding macroporous pseudo-boehmite into water, stirring uniformly, adding weak acid to form colloid, spray drying, and roasting to obtain alumina microspheres with the average particle size of 10-30 mu m for later use;
adding the small-pore pseudo-boehmite into water, uniformly stirring, adding strong acid to form gel, adding the component B and the roasted alumina microspheres, uniformly stirring, and then performing spray drying and roasting to obtain the alumina microspheres with the average particle size of 20-150 mu m.
The carrier obtained at the moment is of an internal and external double-layer structure, the inner layer is the macroporous pseudo-boehmite subjected to high-temperature roasting treatment, the aperture is larger, the diffusion of reaction products is facilitated, the acidity is lower, the activity is smaller, the secondary reaction of propylene product cannot occur, and the improvement of selectivity is facilitated. The outer layer is the small-hole pseudo-boehmite processed at a lower temperature, has moderate acidity, is matched with active components, and is beneficial to the generation of dehydrogenation reaction.
2) Preparation of the catalyst
Weighing the component A, the component C and the component D according to the proportion, introducing the component A, the component C and the component D into the alumina microspheres serving as the carrier by adopting a dipping method, and then drying and roasting to obtain the catalyst.
As a preferred mode of the present application, the weak acid is formic acid, acetic acid, citric acid or tartaric acid; the temperature for gelling the weak acid is 60-80 ℃, and the roasting temperature is 800-1100 ℃.
As a better preferred mode of the application, the strong acid is hydrochloric acid or nitric acid, and the gelling temperature is 60-80 ℃; the roasting temperature is 500-700 ℃.
As a preferable mode of the present application, the drying is performed for 1 to 24 hours at 60 to 150 ℃, and the baking is performed for 2 to 8 hours at 400 to 800 ℃.
Compared with the prior art, the positive effects of the invention are as follows:
the active component of the saturated alkane dehydrogenation catalyst provided by the invention is a non-noble metal element, does not contain noble metal Pt, Cr and V which pollute the environment, does not pollute the environment, and is a catalyst with low price and environmental protection. The catalyst has enriched surface of active component, high alkane converting rate and high olefin selectivity, and may be used in fluidized bed reactor.
Secondly, the active components and the auxiliary agent interact with each other, and the hydrogenolysis reaction is inhibited; the assistant interacts with the carrier, so that strong acid sites are reduced, and the cracking reaction is reduced; the carrier has unique pore size distribution, which is favorable for the diffusion of products, reduces the secondary reaction of olefin and improves the selectivity of the catalyst.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The test conditions for the catalysts prepared in the following examples were: system for making100g of catalyst was prepared and evaluated for performance on a continuous fluidized bed apparatus. Reaction conditions are as follows: pure propane is taken as raw material, normal pressure is achieved, the reaction temperature is 600 ℃, and the alkane mass space velocity is 3h-1. The product was analyzed by HP-5890 gas chromatograph (HP-AL/S capillary column, 50 m.times.0.53 mm.times.15 μm; FID detector)
Example 1:
adding 40g of macroporous pseudo-boehmite into water, uniformly stirring, adding a proper amount of formic acid, adjusting the pH value to be about 4-5, gelatinizing at 60 ℃, spray-drying, and roasting at 800 ℃ for 4 hours to obtain the alumina microspheres with the average particle size of 18 microns.
Adding 80g of small-hole pseudo-boehmite into water, stirring uniformly, adding a proper amount of nitric acid to form colloid at the temperature of 60-80 ℃, and adding 1.2g of GeO2And mixing the alumina microspheres prepared above, uniformly stirring, spray drying, and roasting at 500 ℃ to obtain the alumina microspheres with the particle size of 20-150 mu m. 25.25g of ferric nitrate nonahydrate, 9.14g of zinc nitrate hexahydrate and 1.70g of barium nitrate are weighed and dissolved in 200g of water, the solution is soaked on alumina microspheres, and then the alumina microspheres are dried at 60 ℃ for 15h and roasted at 500 ℃ for 4h to obtain the catalyst. The catalyst evaluation showed that the propane conversion was 35.08% and the selectivity was 85.25%.
Example 2:
adding 33g of macroporous pseudo-boehmite into water, uniformly stirring, adding a proper amount of acetic acid, adjusting the pH value to be about 4-5, gelatinizing at 70 ℃, spray-drying, and roasting at 900 ℃ for 4 hours to obtain the alumina microspheres with the average particle size of 22 mu m.
Adding 100g of small-hole pseudoboehmite into water, stirring uniformly, adding a proper amount of hydrochloric acid to form colloid at 80 ℃, and adding 0.2g of Sb2O3And mixing the alumina microspheres prepared above, uniformly stirring, spray drying, and roasting at 600 ℃ to obtain the alumina microspheres with the particle size of 20-150 mu m. Weighing 7.78g of nickel nitrate hexahydrate, 9.72g of copper nitrate trihydrate and 6.41g of magnesium nitrate hexahydrate, dissolving in 200g of water, dipping the solution on alumina microspheres, drying at 80 ℃ for 10h, and roasting at 600 ℃ for 6h to obtain the catalyst. The catalyst evaluation results showed that the propane conversion was 34.37% and the selectivity was 85.43%.
Example 3:
adding 28g of macroporous pseudo-boehmite into water, uniformly stirring, adding a proper amount of acetic acid, adjusting the pH value to be about 4-5, gelatinizing at 80 ℃, spray-drying, and roasting at 900 ℃ for 4 hours to obtain the alumina microspheres with the average particle size of 28 microns.
Adding 86g of small-hole pseudo-boehmite into water, uniformly stirring, adding a proper amount of hydrochloric acid to form a colloid at 70 ℃, adding 0.8g of In2O3 and the prepared alumina microspheres, uniformly stirring, spray-drying, and roasting at 700 ℃ to obtain the alumina microspheres with the particle size of 20-150 mu m. Weighing 7.78g of nickel nitrate hexahydrate, 9.72g of copper nitrate trihydrate and 6.41g of magnesium nitrate hexahydrate, dissolving in 200g of water, dipping the solution on alumina microspheres, drying at 80 ℃ for 10h, and roasting at 800 ℃ for 6h to obtain the catalyst. The catalyst evaluation results showed that the propane conversion was 36.27% and the selectivity was 86.55%.
Example 4:
adding 25g of macroporous pseudo-boehmite into water, uniformly stirring, adding a proper amount of acetic acid, adjusting the pH value to be about 4-5, gelatinizing at 80 ℃, spray-drying, and roasting at 1000 ℃ for 4 hours to obtain the alumina microspheres with the average particle size of 15 microns.
Adding 100g of small-hole pseudoboehmite into water, stirring uniformly, adding a proper amount of nitric acid to form colloid at 80 ℃, and adding 1.2g of TeO2And mixing the alumina microspheres prepared above, uniformly stirring, spray drying, and roasting at 500 ℃ to obtain the alumina microspheres with the particle size of 20-150 mu m. 29.13g of cobalt nitrate hexahydrate, 6.24g of gallium nitrate nonahydrate and 5.86g of calcium nitrate are weighed and dissolved in 200g of water, the solution is soaked on alumina microspheres, and then the alumina microspheres are dried at 90 ℃ for 4 hours and calcined at 400 ℃ for 8 hours to obtain the catalyst. The catalyst evaluation results showed that the propane conversion was 30.56% and the selectivity was 87.94%.
Example 5:
adding 18g of macroporous pseudo-boehmite into water, uniformly stirring, adding a proper amount of citric acid, adjusting the pH value to be 4-5, gelatinizing at 80 ℃, spray-drying, and roasting at 1000 ℃ for 4 hours to obtain the alumina microspheres with the average particle size of 19 microns.
Adding 97g of small-hole pseudo-boehmite into water, uniformly stirring, adding a proper amount of nitric acid to form colloid at 80 ℃, adding 0.05g of TeO2 and the prepared alumina microspheres, uniformly stirring, spray-drying, and roasting at 500 ℃ to obtain the alumina microspheres with the particle size of 20-150 mu m. 12.83g of ammonium metatungstate, 21.26g of copper nitrate trihydrate and 2.74g of sodium nitrate are weighed and dissolved in 200g of water, the solution is impregnated on alumina microspheres, and then the alumina microspheres are dried at 120 ℃ for 2h and calcined at 800 ℃ for 2h to obtain the catalyst. The catalyst evaluation showed that the propane conversion was 36.42% and the selectivity was 83.65%.
Example 6:
adding 31g of macroporous pseudo-boehmite into water, uniformly stirring, adding a proper amount of tartaric acid, adjusting the pH value to be 4-5, gelatinizing at 80 ℃, spray-drying, and roasting at 1100 ℃ for 8 hours to obtain the alumina microspheres with the average particle size of 25 mu m.
Adding 100g of small-hole pseudoboehmite into water, stirring uniformly, adding a proper amount of nitric acid to form colloid at 70 ℃, and adding 0.70gSb2O3And mixing the alumina microspheres prepared above, uniformly stirring, spray drying, and roasting at 700 ℃ for 4 hours to obtain the alumina microspheres with the particle size of 20-150 mu m. 2.70g of ammonium heptamolybdate, 1.65g of manganese nitrate and 30.77g of magnesium nitrate hexahydrate are weighed and dissolved in 200g of water, the solution is soaked on alumina microspheres, and then the alumina microspheres are dried at 150 ℃ for 1h and calcined at 400 ℃ for 8h to obtain the catalyst. The catalyst evaluation showed that the propane conversion was 30.28% and the selectivity was 91.62%.
Example 7:
adding 33g of macroporous pseudo-boehmite into water, uniformly stirring, adding a proper amount of tartaric acid, adjusting the pH value to be 4-5, gelatinizing at 70 ℃, spray-drying, and roasting at 800 ℃ for 8 hours to obtain the alumina microspheres with the average particle size of 12 microns.
Adding 100g of small-hole pseudo-boehmite into water, uniformly stirring, adding a proper amount of nitric acid to form colloid at 60 ℃, adding 1.20g of GeO2 and the prepared alumina microspheres, uniformly stirring, spray-drying, and roasting at 500 ℃ for 7 hours to obtain the alumina microspheres with the particle size of 20-150 mu m. Weighing 4.28g of nickel nitrate hexahydrate, 4.29g of ammonium heptamolybdate, 2.05g of zinc nitrate hexahydrate and 1.41g of calcium nitrate, dissolving in 200g of water, soaking the solution on alumina microspheres, drying at 80 ℃ for 5h, and roasting at 800 ℃ for 2h to obtain the catalyst. The catalyst evaluation results showed that the propane conversion was 37.26% and the selectivity was 86.85%.
Example 8:
adding 22g of macroporous pseudo-boehmite into water, uniformly stirring, adding a proper amount of citric acid, adjusting the pH value to be 4-5, gelatinizing at 60 ℃, spray-drying, and roasting at 900 ℃ for 5 hours to obtain the alumina microspheres with the average particle size of 27 microns.
Adding 96g of small-hole pseudo-boehmite into water, uniformly stirring, adding a proper amount of nitric acid to form colloid at 70 ℃, adding 0.65g of TeO2 and the prepared alumina microspheres, uniformly stirring, spray-drying, and roasting at 600 ℃ for 6 hours to obtain the alumina microspheres with the particle size of 20-150 mu m. 12.12g of iron nitrate nonahydrate, 31.85g of cobalt nitrate hexahydrate, 3.66g of gallium nitrate nonahydrate, 5.10g of manganese nitrate and 0.52g of potassium nitrate were weighed and dissolved in 200g of water, and the solution was impregnated into alumina microspheres, followed by drying at 80 ℃ for 5 hours and calcining at 800 ℃ for 2 hours, to obtain a catalyst. The catalyst evaluation showed 40.56% propane conversion and 85.37% selectivity.
Example 9:
adding 22g of macroporous pseudo-boehmite into water, uniformly stirring, adding a proper amount of formic acid, adjusting the pH value to be about 4-5, gelatinizing at 60 ℃, spray-drying, and roasting at 900 ℃ for 4 hours to obtain the alumina microspheres with the average particle size of 24 microns.
Adding 96g of small-hole pseudo-boehmite into water, uniformly stirring, adding a proper amount of nitric acid to form colloid at 70 ℃, adding 0.65g of TeO2, 0.25g of Sb2O3 and the prepared alumina microspheres, uniformly stirring, spray-drying, and roasting at 700 ℃ for 4 hours to obtain the alumina microspheres with the particle size of 20-150 mu m. Weighing 18.68g of nickel nitrate hexahydrate, 7.06g of ammonium metatungstate, 1.75g of zinc nitrate hexahydrate, 5.10g of manganese nitrate and 14.74g of magnesium nitrate hexahydrate, dissolving in 200g of water, impregnating the solution on alumina microspheres, drying at 80 ℃ for 5h, and roasting at 500 ℃ for 4h to obtain the catalyst. The catalyst evaluation showed 38.74% propane conversion and 86.32% selectivity.
Example 10:
adding 22g of macroporous pseudo-boehmite into water, uniformly stirring, adding a proper amount of formic acid, adjusting the pH value to be about 4-5, gelatinizing at 60 ℃, spray-drying, and roasting at 900 ℃ for 4 hours to obtain the alumina microspheres with the average particle size of 26 microns.
Adding 96g of small-hole pseudo-boehmite into water, uniformly stirring, adding a proper amount of nitric acid to form colloid at 70 ℃, adding 0.65g of TeO2, 0.25g of Sb2O3 and the prepared alumina microspheres, uniformly stirring, spray-drying, and roasting at 700 ℃ for 4 hours to obtain the alumina microspheres with the particle size of 20-150 mu m. Weighing 18.68g of nickel nitrate hexahydrate, 7.06g of ammonium metatungstate, 1.75g of zinc nitrate hexahydrate, 5.10g of manganese nitrate and 14.74g of magnesium nitrate hexahydrate, dissolving in 200g of water, impregnating the solution on alumina microspheres, drying at 80 ℃ for 5h, and roasting at 500 ℃ for 4h to obtain the catalyst. The catalyst evaluation results showed that the propane conversion was 38.58% and the selectivity was 89.35%.
Comparative example 1:
the procedure for the preparation of the catalyst was as in example 1, except that no 1.2g of GeO was added2. The catalyst evaluation results showed that the propane conversion was 32.27% and the selectivity was 84.79%.
Comparative example 2:
the procedure for the preparation of the catalyst was as in example 3, except that no copper nitrate trihydrate was added. The catalyst evaluation results showed that the propane conversion was 37.65% and the selectivity was 80.77%.
Comparative example 3:
the procedure for the preparation of the catalyst was as in example 4, except that no calcium nitrate was added. The catalyst evaluation showed 32.64% propane conversion and 81.36% selectivity.
Comparative example 4:
the procedure is as in example 9, except that the macroporous pseudoboehmite is not used, and the support is synthesized in one step. Adding 118g of pseudo-boehmite into water, stirring uniformly, adding a proper amount of nitric acid to form colloid at 70 ℃, and adding 0.65g of TeO2、0.25g Sb2O3And mixing the alumina microspheres prepared above, uniformly stirring, spray drying, and roasting at 700 ℃ for 4 hours to obtain the alumina microspheres with the particle size of 20-150 mu m. The catalyst evaluation showed 39.26% propane conversion and 79.89% selectivity.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
1. A fluidized bed alkane dehydrogenation catalyst is characterized by comprising a component A, B, C, D, E, wherein the component A is selected from one or more oxides of Fe, Ni, Co, W and Mo, the component B is selected from one or more oxides of Ge, Sb, In and Te, the component C is selected from one or more oxides of Zn, Cu, Ga and Mn, the component D is selected from one or more oxides of Ba, Ca, Mg, K and Na, and the component E is a carrier.
2. The fluid bed alkane dehydrogenation catalyst of claim 1, wherein: the content of the oxide of the component A in the catalyst is 1-15% by mass percentage; the content of the oxide of the component B in the catalyst is 0.01-1.5%; the content of the oxide of the component C in the catalyst is 0.1-15%; the content of the oxide of the component D in the catalyst is 0.1-5%; the content of the component E in the catalyst is 65-95%, and the sum of the total mass percentage is 100%.
3. The fluid bed alkane dehydrogenation catalyst of claim 2, wherein: the content of the oxide of the component A in the catalyst is 2-12% in percentage by mass; the content of the oxide of the component B in the catalyst is 0.05-0.7%; the content of the oxide of the component C in the catalyst is 4-12%; the content of the oxide of the component D in the catalyst is 0.1-1.5%; the content of the component E in the catalyst is 65-95%, and the sum of the total mass percentage is 100%.
4. The fluid bed alkane dehydrogenation catalyst of claim 1, wherein: the carrier is alumina.
5. A process for the preparation of a fluid bed alkane dehydrogenation catalyst according to any of claims 1 to 4, characterized by comprising the steps of:
1) preparation of the support
Adding macroporous pseudo-boehmite into water, stirring uniformly, adding weak acid to form colloid, spray drying, and roasting to obtain alumina microspheres with the average particle size of 10-30 mu m for later use;
adding the small-pore pseudo-boehmite into water, uniformly stirring, adding strong acid to form gel, adding the component B and the roasted alumina microspheres, uniformly stirring, and then performing spray drying and roasting to obtain the alumina microspheres with the average particle size of 20-150 mu m;
2) preparation of the catalyst
Weighing the component A, the component C and the component D according to the proportion, introducing the component A, the component C and the component D into a carrier by adopting an impregnation method, and then drying and roasting to obtain the catalyst.
6. The process for preparing a fluidized bed alkane dehydrogenation catalyst according to claim 5, wherein: the weak acid in the step 1) is formic acid, acetic acid, citric acid or tartaric acid; the temperature for gelling the weak acid is 60-80 ℃, and the roasting temperature is 800-1100 ℃.
7. The process for preparing a fluidized bed alkane dehydrogenation catalyst according to claim 5, wherein: the strong acid in the step 1) is hydrochloric acid or nitric acid, and the gelling temperature is 60-80 ℃; the roasting temperature is 500-700 ℃.
8. The method of preparing a fluidized bed alkane dehydrogenation catalyst according to claim 5, wherein: the drying condition is 60-150 ℃ for 1-24 h, and the roasting condition is 400-800 ℃ for 2-8 h.
9. The fluidized bed alkane dehydrogenation catalyst of any of claims 1 to 4, wherein: the alkane is alkane with 2-4 carbon atoms.
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