CN114984941B - Transition metal-based low-carbon alkane dehydrogenation catalyst and preparation method and application thereof - Google Patents
Transition metal-based low-carbon alkane dehydrogenation catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a transition metal-based low-carbon alkane dehydrogenation catalyst and a preparation method and application thereof, and belongs to the technical field of petrochemical industry. The catalyst takes at least one of transition metal element V, co, ni, zn and Fe as an active center and at least one of non-metal element N, P and B as an auxiliary agent, and is prepared by immersing a carrier in a solution containing the transition metal element and the auxiliary agent and then roasting at 300-900 ℃ for 1-4 hours. The catalyst has the characteristics of high conversion rate of low-carbon alkane, high selectivity of low-carbon olefin, strong anti-sintering capability, good stability and the like, and solves the problems of unfriendly environment and high price of the existing dehydrogenation catalyst.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry, and particularly relates to a transition metal-based low-carbon alkane dehydrogenation catalyst, and a preparation method and application thereof.
Background
With the rapid development of the international petrochemical industry, the demand for lower olefins is also increasing. The existing main ways for obtaining the low-carbon olefin are a catalytic cracking technology and a steam cracking technology, but the two technologies have the defects of high energy consumption, low olefin yield and the like; the low-carbon olefin obtained by the coal-to-olefin technology and the methanol-to-olefin technology has high cost and high energy consumption, and is difficult to be industrially applied. Through market research, the investment cost of equipment of a direct dehydrogenation technology of low-carbon alkane is 2/3 of the investment cost of steam cracking, and the cost of the low-carbon alkane serving as a raw material of the technology accounts for more than 70% of the total production cost of the alkene, and the technology can be directly used for continuously producing downstream derivatives of the low-carbon alkane, so that the direct dehydrogenation reaction is the most effective means for obtaining the low-carbon alkane.
The direct dehydrogenation reaction is a thermodynamically limited highly endothermic reaction, and the activation of the C-H bond of the lower alkane is a key step in determining the dehydrogenation catalytic performance. However, the C-H bonds of lower alkanes are highly stable and therefore require higher reaction temperatures (550-700 ℃) to effect C-H bond cleavage. However, at high temperatures, the C-C bonds are more easily broken than the C-H bonds, and side reactions such as cracking, deep dehydrogenation or polymerization are easily caused, resulting in low selectivity and coking.
The direct dehydrogenation processes have been commercialized as Oleflex (Honeywell UOP) and Catofin (ABB Lummus) processes, using Pt and Cr-based catalysts, respectively, the high cost of platinum, the toxicity of chromium, and the rapid deactivation of both pose economic and environmental problems.
CN108654596a is a propane dehydrogenation catalyst and its preparation method, which discloses a method using V as an auxiliary agent, but because the disclosed invention is a chromium dehydrogenation catalyst, on the one hand, the problems of environmental pollution and human body hazard are designed, and on the other hand, the above patent does not break through the limitation of the traditional chromium dehydrogenation catalyst.
CN103785388a also discloses a method for using V as an auxiliary agent of a platinum-series dehydrogenation catalyst, which improves the performance of the catalyst by introducing V, but the technology has no significant breakthrough due to the high cost of the platinum-based catalyst.
In view of the above, in order to break through the limitations of the conventional chromium-based and platinum-based dehydrogenation catalysts, it is imperative to develop a novel non-chromium non-noble metal dehydrogenation catalyst.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a transition metal-based low-carbon alkane dehydrogenation catalyst, a preparation method and application thereof, wherein the catalyst has the characteristics of high low-carbon alkane conversion rate, high low-carbon alkene selectivity, strong sintering resistance, good stability and the like, and solves the problems of environment unfriendly and high price existing in the conventional dehydrogenation catalyst.
The invention is realized by the following technical scheme:
In a first aspect, the invention provides a transition metal-based low-carbon alkane dehydrogenation catalyst, which is prepared by taking at least one of transition metal elements V, co, ni, zn and Fe as an active center and at least one of nonmetallic elements N, P and B as an auxiliary agent, and roasting a carrier in a solution containing the transition metal elements and the auxiliary agent at 300-900 ℃ for 1-4 hours after soaking the carrier in the solution.
Further, in the preferred embodiment of the invention, the mass percentage of the transition metal element is 0.01-30%, the mass percentage of the auxiliary agent is 0.1-10% and the rest is the carrier based on the total mass of the catalyst dry basis.
Further, in a preferred embodiment of the present invention, the carrier is alumina, zinc aluminate or molecular sieve having a hierarchical pore structure.
Further, in a preferred embodiment of the present invention, the specific surface area of the carrier is 50m 2/g～500m2/g, and the pore diameter is in the range of 3nm to 40nm.
Further, in a preferred embodiment of the present invention, the precursor of the transition metal element is one or more of an oxide, an inorganic salt and a complex of the transition metal element.
Further, in a preferred embodiment of the present invention, the precursor of the nitrogen element in the auxiliary agent is at least one of nitric acid, ammonium hydroxide, ammonium nitrate, ammonium chloride, melamine, dopamine hydrochloride and urea;
preferably, the precursor of the boron element in the auxiliary agent is at least one of elemental boron, boric acid, anhydrous boric acid, sodium metaborate, potassium metaborate and borax decahydrate;
preferably, the precursor of the phosphorus element in the auxiliary agent is at least one of phytic acid, phosphoric acid, diammonium hydrogen phosphate, monoammonium hydrogen phosphate, triethyl phosphate, dipotassium hydrogen phosphate and potassium dihydrogen phosphate.
In a second aspect, the present application provides a method for preparing a transition metal-based lower alkane dehydrogenation catalyst, comprising:
mixing a solution containing transition metal elements with a solution containing an auxiliary agent to obtain an impregnating solution;
the carrier is placed in impregnating solution for impregnation, aged and dried, and then baked for 1-4 hours at 300-900 ℃.
Further, in a preferred embodiment of the present invention, the carrier is impregnated in the impregnating solution stepwise or co-impregnated in the above-mentioned impregnating process.
In a third aspect, the invention also provides an application of the transition metal-based low-carbon alkane dehydrogenation catalyst, wherein the low-carbon alkane dehydrogenation catalyst is used in a low-carbon alkane dehydrogenation reaction of a fixed bed, a moving bed or a fluidized bed, the reaction pressure is 0.01 MPa-1 MPa, the temperature is 530-660 ℃, and the mass space velocity is 0.3h -1～8h-1.
Compared with the prior art, the invention has at least the following technical effects:
The low-carbon alkane dehydrogenation catalyst provided by the invention does not contain Cr element, and has little harm to human body and environment; does not contain Pt element, and has low production cost. Breaks through the limitation of the traditional dehydrogenation chromium-based and platinum-based dehydrogenation catalysts, and thoroughly solves the industry problem of 'chromium poison platinum noble'. The catalyst takes at least one of transition metal element V, co, ni, zn and Fe as an active center, takes at least one of nonmetal element N, P and B as an auxiliary agent, and utilizes the existence state of active components improved by a plurality of elements on the surface of a carrier and the chemical state in the regulation and control reaction process, thereby greatly improving the conversion rate of low-carbon alkane, inhibiting the reaction of deep dehydrogenation of alkane to generate carbon deposition species, and improving the stability of the catalyst.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the following examples, which are to be construed as merely illustrative and not limitative of the scope of the invention, but are not intended to limit the scope of the invention to the specific conditions set forth in the examples, either as conventional or manufacturer-suggested, nor are reagents or apparatus employed to identify manufacturers as conventional products available for commercial purchase.
The technical scheme of the invention is as follows:
The embodiment provides a transition metal-based low-carbon alkane dehydrogenation catalyst, which takes at least one of transition metal element V, co, ni, zn and Fe as an active center to play a role in activating a C-H bond in propane dehydrogenation reaction; at least one of nonmetallic elements N, P and B is used as an auxiliary agent, and the auxiliary agent mainly plays a role in activating transition metal, is beneficial to improving the existing state of active components on the surface of a carrier, and regulates and controls the chemical state in the reaction process through interaction with the transition metal or the carrier.
Preferably, the catalyst uses any one of transition metal element V, co, ni, zn and Fe as an active center and any one of nonmetallic element N, P and B as an auxiliary agent. More preferably, transition metal element V, co or Ni is used as active center, and N or P is used as auxiliary agent.
Further, based on the total mass of the catalyst dry basis, the mass percent of the transition metal element is 0.01-30%, the mass percent of the auxiliary agent is 0.1-10%, and the rest is the carrier. Preferably, the mass percentage of the transition metal element is 5% -25%, and the mass percentage of the auxiliary agent is 2% -8%; more preferably, the mass percentage of the transition metal element is 10% -20% and the mass percentage of the auxiliary agent is 3% -7%. The mass percentage of transition metal elements in the catalyst is controlled to be 0.01-30%, which is beneficial to the dehydrogenation reaction; beyond this range, the influence of metal agglomeration may occur. The mass percentage of the auxiliary agent in the catalyst is controlled to be 0.1-10%, which is helpful for the activation of the active components; beyond this range, the active site may be covered, inhibiting the progress of the dehydrogenation reaction.
Wherein the precursor of the transition metal element is one or more of oxide, inorganic salt and complex of the transition metal element. The precursor of nitrogen element in the auxiliary agent is at least one of nitric acid, ammonium hydroxide, ammonium nitrate, ammonium chloride, melamine, dopamine hydrochloride and urea; the precursor of boron element in the auxiliary agent is at least one of elemental boron, boric acid, anhydrous boric acid, sodium metaborate, potassium metaborate and borax decahydrate; the precursor of the phosphorus element in the auxiliary agent is at least one of phytic acid, phosphoric acid, diammonium phosphate, monoammonium phosphate, triethyl phosphate, dipotassium phosphate and potassium dihydrogen phosphate. Further, the carrier is alumina, zinc aluminate or molecular sieve with a multistage pore structure.
Preferably, an alumina support is employed; the specific surface area of the carrier is 50m 2/g～500m2/g and the pore diameter is in the range of 3nm to 40nm, and preferably, the carrier is used in a fixed bed reaction. The alumina carrier used in the application has a multistage pore structure, and is prepared by a gel sol method. Compared with commercial alpha-phase alumina, the alumina has the advantages of large specific surface area, large mechanical strength and the like.
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
Example 1
The embodiment provides a transition metal-based light alkane dehydrogenation catalyst, and the preparation method thereof comprises the following steps:
the alumina carrier was placed in an oven for use, the specific surface area of the alumina being 200m 2/g and the pore size range being 30nm.
Weighing 2.11g of vanadyl oxalate, placing in a beaker, adding 60ml of deionized water to form a solution, and stirring for 10min for dissolution; 0.2g of phosphoric acid is weighed and added into the solution, and the solution is stirred for 20min until the solution is dissolved; 14.475g of dried aluminum oxide is weighed and poured into the solution, stirred for 2 hours, put into an oven for drying, and then baked for 3 hours at 600 ℃ in an air atmosphere.
Example 2
The embodiment provides a transition metal-based light alkane dehydrogenation catalyst, and the preparation method thereof comprises the following steps:
the alumina carrier was placed in an oven for use, the specific surface area of the alumina being 200m 2/g and the pore size range being 30nm.
49G of nickel nitrate and 0.2g of phosphoric acid are weighed and placed in a beaker, 60ml of deionized water is added to form a solution, and the solution is stirred for 10 minutes to dissolve; 14.475g of dried aluminum oxide is weighed and poured into the solution, stirred for 2 hours, put into an oven for drying, and then baked for 3 hours at 600 ℃ in an air atmosphere.
Example 3
The embodiment provides a transition metal-based light alkane dehydrogenation catalyst, and the preparation method thereof comprises the following steps:
the alumina carrier was placed in an oven for use, the specific surface area of the alumina being 200m 2/g and the pore size range being 30nm.
Weighing 50g of cobalt nitrate and 0.33g of nitric acid, placing the cobalt nitrate and the nitric acid in a beaker, adding 60ml of deionized water to form a solution, and stirring for 10min to dissolve; 14.475g of dried aluminum oxide is weighed and poured into the solution, stirred for 2 hours, put into an oven for drying, and then baked for 3 hours at 600 ℃ in an air atmosphere.
Example 4
The embodiment provides a transition metal-based light alkane dehydrogenation catalyst, and the preparation method thereof comprises the following steps:
The alumina carrier with specific surface area of 200m 2/g and pore size of 15nm is placed in an oven for standby.
Weighing 1.053 ammonium metavanadate and 0.12g boric acid, placing in a beaker, adding 60ml deionized water to form a solution, and stirring for 10min for dissolution; 14.475g of dried aluminum oxide is weighed and poured into the solution, stirred for 2 hours, put into an oven for drying, and then baked for 3 hours at 600 ℃ in an air atmosphere.
Example 5
The embodiment provides a transition metal-based light alkane dehydrogenation catalyst, and the preparation method thereof comprises the following steps:
The alumina carrier with specific surface area of 200m 2/g and pore size of 15nm is placed in an oven for standby.
2.11G of vanadyl oxalate and 0.22 diammonium hydrogen phosphate are weighed and placed in a beaker, 60ml of deionized water is added to form a solution, and the solution is stirred for 10min for dissolution; 14.475g of dried aluminum oxide is weighed and poured into the solution, stirred for 2 hours, put into an oven for drying, and then baked for 3 hours at 600 ℃ in an air atmosphere.
Example 6
The embodiment provides a transition metal-based light alkane dehydrogenation catalyst, and the preparation method thereof comprises the following steps:
The alumina carrier was placed in an oven for use, the specific surface area of the alumina being 400m 2/g and the pore size range being 27nm.
Weighing 1.93 ferric nitrate and 0.2g phosphoric acid, placing in a beaker, adding 60ml deionized water to form a solution, and stirring for 10min for dissolution; 14.475g of dried aluminum oxide is weighed and poured into the solution, stirred for 2 hours, put into an oven for drying, and then baked for 3 hours at 600 ℃ in an air atmosphere.
Example 7
The embodiment provides a transition metal-based light alkane dehydrogenation catalyst, and the preparation method thereof comprises the following steps:
The carrier molecular sieve is placed in an oven for standby, the specific surface area of the molecular sieve is 500m 2/g, and the pore diameter range is 40nm.
2.11G of vanadyl oxalate and 0.22 diammonium hydrogen phosphate are weighed and placed in a beaker, 60ml of deionized water is added to form a solution, and the solution is stirred for 10min for dissolution; 14.475g of dried molecular sieve is weighed and poured into the solution, stirred for 2 hours, put into an oven for drying, and then baked for 3 hours at 600 ℃ in an air atmosphere.
Example 8
The embodiment provides a transition metal-based light alkane dehydrogenation catalyst, and the preparation method thereof comprises the following steps:
The alumina carrier was placed in an oven for use, the specific surface area of the alumina being 400m 2/g and the pore size range being 27nm.
Weighing 32g of zinc sulfate and 10g of boric acid, placing in a beaker, adding 60ml of deionized water to form a solution, and stirring for 10min for dissolution; 102g of dried alumina is weighed, poured into the solution, stirred for 2 hours, put into an oven for drying, and then baked for 3 hours at 600 ℃ in an air atmosphere.
Example 9
The embodiment provides a transition metal-based light alkane dehydrogenation catalyst, and the preparation method thereof comprises the following steps:
the carrier zinc aluminate is put into an oven for standby, the specific surface area of the zinc aluminate is 50m 2/g, and the pore diameter range is 40nm.
Weighing 50g of cobalt nitrate and 0.33g of nitric acid, placing the cobalt nitrate and the nitric acid in a beaker, adding 60ml of deionized water to form a solution, and stirring for 10min to dissolve; 14.475g of dried zinc aluminate is weighed and poured into the solution, stirred for 2 hours, put into an oven for drying, and then baked for 4 hours at 300 ℃ in an air atmosphere.
Example 10
The embodiment provides a transition metal-based light alkane dehydrogenation catalyst, and the preparation method thereof comprises the following steps:
The carrier molecular sieve is placed in an oven for standby, the specific surface area of the molecular sieve is 500m 2/g, and the pore diameter range is 3nm.
Weighing 1.93 ferric nitrate and 0.2g phosphoric acid, placing in a beaker, adding 60ml deionized water to form a solution, and stirring for 10min for dissolution; 14.475g of dried aluminum oxide is weighed and poured into the solution, stirred for 2 hours, put into an oven for drying, and then baked for 1 hour at 900 ℃ in an air atmosphere.
Comparative example 1
This comparative example provides a catalyst, the preparation method of which comprises:
Placing commercial alpha-phase alumina in an oven for use; the specific surface area of the alumina is 15m 2/g, and the pore diameter range is 30nm.
Weighing 2.11g of vanadyl oxalate, placing in a beaker, adding 60ml of deionized water to form a solution, and stirring for 10min for dissolution; 14.55g of dried alumina is weighed, poured into the solution, stirred for 2 hours, put into an oven for drying, and then baked for 3 hours at 600 ℃ in an air atmosphere.
Comparative example 2
This comparative example provides a catalyst, the preparation method of which comprises:
commercial alpha phase alumina having a specific surface area of 15m 2/g and a pore size in the range of 30nm was placed in an oven for use.
2.11G of vanadyl oxalate and 0.2g of phosphoric acid are weighed and placed in a beaker, 60ml of deionized water is added to form a solution, and the solution is stirred for 10min for dissolution; 14.475g of dried aluminum oxide is weighed and poured into the solution, stirred for 2 hours, put into an oven for drying, and then baked for 3 hours at 600 ℃ in an air atmosphere.
Comparative example 3
This comparative example provides a catalyst, the preparation method of which comprises:
the alumina, having a specific surface area of 100m 2/g and a pore size in the range of 18nm, was placed in an oven for use.
Weighing 2.11g of vanadyl oxalate, placing in a beaker, adding 60ml of deionized water to form a solution, and stirring for 10min for dissolution; 14.55g of dried alumina is weighed, poured into the solution, stirred for 2 hours, put into an oven for drying, and then baked for 3 hours at 600 ℃ in an air atmosphere.
Comparative example 4
This comparative example provides a catalyst, the preparation method of which comprises:
The alumina carrier is put into an oven for standby, the specific surface area of the alumina is 50m 2/g～500m2/g, and the aperture range is 3 nm-40 nm.
49G of nickel nitrate is weighed and placed in a beaker, 60ml of deionized water is added to form a solution, and the solution is stirred for 10 minutes to dissolve; 14.475g of dried aluminum oxide is weighed and poured into the solution, stirred for 2 hours, put into an oven for drying, and then baked for 3 hours at 600 ℃ in an air atmosphere.
To further illustrate the performance of the catalysts provided by the present invention, the following experiments were performed:
1. propane dehydrogenation test
The fixed bed catalysts obtained in examples 1 to 10 were compared with the fixed bed comparative agents in comparative examples 1 to 4, and propane dehydrogenation tests were performed, respectively, with the conventional chromium-based dehydrogenation catalysts and platinum-based dehydrogenation catalysts as the comparison.
The adopted process flow is the existing process flow, and the embodiment is not described in detail, and the control parameters in the process flow are as follows: the space velocity of propane is 1h -1, a proper amount of nitrogen is introduced, the partial pressure of propane is kept to be 50kPa, and the total pressure of a reaction system is normal pressure; the temperature of the bed layer is 550-600 ℃; the results are shown in Table 1.
TABLE 1 propane dehydrogenation Performance of the catalysts
As can be seen from the above table, the alumina transition metal catalyst prepared by us has good advantage of propane dehydrogenation reaction.
2. Propane dehydrogenation test
The catalyst provided in example 3 was subjected to propane dehydrogenation test performance study by controlling the bed temperature of different fixed beds in the reaction process, and the test results are shown in table 2;
TABLE 2 study of propane catalytic Performance of catalysts obtained at different calcination temperatures
As can be seen from Table 3, in the range of 570-600 ℃, the catalyst provided in example 3 of the present application all exhibited excellent catalytic performance for propane dehydrogenation, with 600 ℃ being the most preferred.
3. Isobutane dehydrogenation test
Isobutane dehydrogenation performance tests were performed at different temperatures using the catalyst provided in example 3
The adopted process flow is the existing process flow, and the embodiment is not described in detail, and the control parameters in the process flow are as follows: keeping the space velocity of the isobutane at 1h -1, introducing a proper amount of nitrogen, keeping the partial pressure of the isobutane at 50kPa, and keeping the total pressure of a reaction system at normal pressure; the bed temperature was 550-600deg.C, and the results are shown in Table 3
TABLE 3 investigation of the isobutane catalytic properties of the catalysts obtained at different calcination temperatures
As can be seen from Table 3, in the range of 570-600 ℃, the catalyst provided in example 3 of the present application all showed excellent catalytic performance for isobutane dehydrogenation, with 590-600 ℃ being the most preferred.
In summary, the light alkane dehydrogenation catalyst for the fixed bed has better dehydrogenation performance in the propane dehydrogenation reaction, the isobutane dehydrogenation reaction and the propane/isobutane mixed gas reaction, and compared with the existing traditional dehydrogenation catalyst, the light alkane dehydrogenation catalyst for the fixed bed has higher activity, selectivity and better stability, and the production raw materials are simple and easy to obtain, the preparation process is simple, the existing production line can be used for efficient, stable and economic production, and the existing traditional dehydrogenation catalyst can be effectively replaced.
Finally, it should be noted that: the foregoing description is only of the preferred embodiments of the invention and is not intended to limit the scope of the invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The transition metal-based low-carbon alkane dehydrogenation catalyst is characterized in that the catalyst takes at least one of transition metal elements V, co and Ni as an active center and at least one of nonmetallic elements N, P and B as an auxiliary agent, and is prepared by immersing a carrier in a solution containing the transition metal elements and the auxiliary agent and then roasting at 570-600 ℃ for 1-4 hours; the carrier is alumina, zinc aluminate or molecular sieve with a multistage pore structure; the specific surface area of the carrier is 50m 2/g～500m2/g, and the aperture range is 3 nm-40 nm; based on the total mass of the catalyst dry basis, the mass percentage of the transition metal element is 0.01-30%, the mass percentage of the auxiliary agent is 0.1-10%, and the rest is the carrier.
2. The transition metal-based lower alkane dehydrogenation catalyst according to claim 1, wherein the precursor of the transition metal element is one or more of an oxide, an inorganic salt, and a complex of the transition metal element.
3. The transition metal-based lower alkane dehydrogenation catalyst according to claim 1, wherein the precursor of nitrogen in the auxiliary agent is at least one of nitric acid, ammonium hydroxide, ammonium nitrate, ammonium chloride, melamine, dopamine hydrochloride, and urea.
4. The transition metal-based low-carbon alkane dehydrogenation catalyst according to claim 1, wherein the precursor of boron element in the auxiliary agent is at least one of elemental boron, boric acid, anhydrous boric acid, sodium metaborate, potassium metaborate and borax decahydrate; the precursor of the phosphorus element in the auxiliary agent is at least one of phytic acid, phosphoric acid, diammonium phosphate, monoammonium phosphate, triethyl phosphate, dipotassium phosphate and potassium dihydrogen phosphate.
5. A method for preparing the transition metal-based lower alkane dehydrogenation catalyst according to any one of claims 1 to 4, comprising:
mixing the solution containing the transition metal element with the solution containing the auxiliary agent to obtain an impregnating solution;
And (3) placing the carrier in the impregnating solution for impregnating, aging and drying, and roasting for 1-4 hours at 570-600 ℃.
6. The method for preparing a transition metal-based lower alkane dehydrogenation catalyst according to claim 5, wherein the step-wise impregnation or co-impregnation of the carrier in the impregnation liquid is performed in the impregnation process.
7. The use of the transition metal-based low-carbon alkane dehydrogenation catalyst according to any one of claims 1 to 4, wherein the low-carbon alkane dehydrogenation catalyst is used in a low-carbon alkane dehydrogenation reaction of a fixed bed, a moving bed or a fluidized bed, the reaction pressure is 0.01MPa to 1MPa, the temperature is 530 ℃ to 660 ℃, and the mass space velocity is 0.3h -1～8h-1.
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