CN108786798B - Preparation method of low-carbon alkane dehydrogenation catalyst - Google Patents
Preparation method of low-carbon alkane dehydrogenation catalyst Download PDFInfo
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Abstract
The invention discloses a preparation method of a low-carbon alkane dehydrogenation catalyst, which comprises the following steps: (1) preparing a Pt-Sn impregnating solution: dissolving a proper amount of soluble platinum salt in deionized water, adding soluble tin salt into the solution, uniformly stirring, adding a proper amount of ethylene diamine tetraacetic acid into the solution, and uniformly stirring to prepare a Pt-Sn impregnation solution; (2) and (2) impregnating the carrier with the impregnation liquid obtained in the step (1), drying, roasting, and then loading the second auxiliary metal on the carrier to obtain the final catalyst. According to the invention, Pt and Sn are loaded on the surface of the carrier by a complex co-leaching method, so that the catalyst can still keep higher activity under higher carbon deposition amount, the one-way operation period of the catalyst is prolonged, and the operation cost of the device is reduced.
Description
Technical Field
The invention relates to a preparation method of a low-carbon alkane dehydrogenation catalyst.
Background
The development of north american shale gas has resulted in a dramatic decline in natural gas prices relative to crude oil prices, and a rapid increase in the production of large quantities of condensate (NGLs) from shale gas. Shale gas condensate is rich in ethane, propane, butane and other low-carbon alkanes, and ethane can be used as a cracking raw material to produce ethylene, so that the demand of rapid growth of propylene cannot be met only by an FCC (fluid catalytic cracking) technology. The effective way for solving the problem is to prepare the low-carbon olefin by dehydrogenating the low-carbon alkane in the natural gas (conventional natural gas, shale gas, coal bed gas, combustible ice and the like). Moreover, with the increasing shortage of petroleum resources, the production of propylene has been shifted from a technical route which simply depends on petroleum as raw material to a technical route which has diversified raw material sources, and the trend is gradually changed. In recent years, the technology for producing propylene by propane dehydrogenation has been greatly developed, and especially the technology for producing propylene by Propane Dehydrogenation (PDH) has been developed rapidly and has become the third method for producing large propylene.
At present, the dehydrogenation technology of low-carbon alkane mainly comprises the following steps: anaerobic dehydrogenation and aerobic dehydrogenation. The oxygen-free dehydrogenation technology mainly comprises a Pt-based noble metal dehydrogenation technology and a Cr-based dehydrogenation technology. The major anaerobic dehydrogenation technologies in the world include: oleflex process by UOP, Catofin process by ABB rum, Star process by Conphyra (Uhde), FBD-4 process by Snamprogetti/Yarsintz, PDH process by Linde/Basofu, etc. In which the Catofin and Oleflex technologies have become the dominant process technologies used in new installations. The catalyst used in the Oleflex process is a Pt-based noble metal catalyst, and the catalyst used in the Catafin process is a Cr-based dehydrogenation catalyst. Aerobic dehydrogenation technology has no industrialized example.
In the course of the research on noble metal dehydrogenation catalysts, it has long been found that small amounts of Pt, Ir, Ru and Re are dispersed in Al having a high specific surface area2O3、SiO2The dehydrogenation activity is higher. These catalysts have high initial activity, but quickly lose carbon deposition, have poor reaction selectivity and have more side reactions such as hydrogenolysis and the like. The main causes of Pt catalyst deactivation are carbon deposition and sintering. Carbon deposition can be suppressed by reducing the amount of carrier acid, and sintering of Pt particles is avoided by introducing Sn component. Through years of research, people conclude that Pt-Sn/Al2O3Function of Sn component in catalyst: (1) the Pt particle size on the surface of the catalyst is reduced through a geometric effect, so that the dispersion of Pt is promoted; (2) pt charges on the surface of the catalyst are enriched through an electronic effect so as to promote the desorption of the carbon deposition precursor; (3) the carbon on the surface of the catalyst is favorably transferred from a metal position to a carrier position; (4) altering the interaction between the metal and the support; (5) promoting the occurrence of hydrogen overflow so as to maintain the activity of the catalyst and improve the carbon elimination capability of the catalyst; (6) modulating the acidity of the surface of the catalyst; (7) facilitates anchoring of Pt on SnOX and formation of Pt-SnOX-Al2O3A "sandwich" structure.
As for the manner of introduction of the Sn component, there are various ways. The conventional method is to prepare a soluble precursor of the Sn component into a solution, impregnate and load the solution on a carrier, and load the solution independently or together with the Pt component and the like, such as Chinese patents CN96117222.3, CN98114083.1 and the like. Journal of catalysis (1987, Vol. 8, No. 4) "Pt-Sn/Al2O3The influence of the presence state of Sn in the catalyst on the propane dehydrogenation "mention is made of a complex-type dehydrogenation catalyst which exhibits excellent performance in the propane dehydrogenation. The dehydrogenation catalysts mentioned in CN87101513A and CN200910011770.5, CN200910011771.x, CN200910011772.4 are introduced by introducing the Sn component during gelling of the supported alumina. CN201410841699.4 discloses a method for preparing a dehydrogenation catalyst, which comprises adding a precursor of Sn into Pt nano sol, mixing thoroughly, reducing with sodium borohydride to obtain Sn-containing Pt nano sol, adding other additives into the sol, and impregnating the carrier. In the prior art, the interaction and position between Pt, Sn and the support are mostly not elucidated. How to form a better position relationship between Pt, Sn and a carrier so as to improve the carbon deposit resistance of a catalyst and reduce the influence of carbon deposit on the catalytic activity is a technical problem to be solved all the time.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the preparation method of the low-carbon alkane dehydrogenation catalyst, and Pt and Sn are loaded on the surface of the carrier by a complex co-immersion method, so that the catalyst can still keep higher activity under higher carbon deposition amount, the one-way operation period of the catalyst is prolonged, and the operation cost of the device is reduced.
The preparation method of the low-carbon alkane dehydrogenation catalyst comprises the following steps:
(1) preparing a Pt-Sn impregnating solution: dissolving a proper amount of soluble salt of platinum in deionized water, adding soluble salt of tin into the solution, uniformly stirring, adding a proper amount of Ethylene Diamine Tetraacetic Acid (EDTA) into the solution, and uniformly stirring to obtain the Pt-Sn impregnation solution.
(2) And (2) impregnating the carrier with the impregnation liquid obtained in the step (1), drying, roasting, and then loading the second auxiliary metal on the carrier to obtain the final catalyst.
In the method, the mass concentration of Pt in the Pt-Sn impregnating solution is 0.001-0.8%, preferably 0.025-0.5%; the mass concentration of Sn is 0.001-4%, preferably 0.05-2%; the mass concentration of the EDTA is 0.003-5%, preferably 0.01-4.5%.
In the method, the platinum-containing compound can be one or more of chloroplatinic acid, chloroplatinic acid or platinum nitrate, preferably chloroplatinic acid; the soluble salt of tin can be one or more of tin tetrachloride, tin oxalate or stannous sulfate, and tin tetrachloride is preferred.
In the method, the mass ratio of the impregnation liquid to the carrier is 2: 1-4: 1; the dipping time is 1-20 hours, preferably 3-10 hours;
in the method of the invention, the carrier is active Al2O3The crystal form can be gamma, delta or theta. The carrier can be in a proper shape such as a sphere, a strip, a microsphere or a special shape, the equivalent diameter of the particles is generally 0.2-4 mm, and the preferred particle size is 0.5-2 mm.
In the method, the drying temperature is 100-130 ℃, and the drying time is 10-24 hours; the roasting temperature is 450-550 ℃, and preferably 480-520 ℃; the roasting time is 3-12 hours, preferably 4-6 hours.
In the method of the present invention, the process of loading the second auxiliary agent is well known to those skilled in the art, and a conventional impregnation method may be adopted, and after impregnation, drying and roasting are performed to complete loading; the second promoter precursor may be a soluble nitrate, chloride or sulphate thereof.
The low-carbon alkane dehydrogenation catalyst has the following properties: active alumina is taken as a carrier, Pt is taken as an active component, Sn is taken as a first auxiliary agent, and a metal selected from Li, Na, K, Fe, Ni, Cu, Zn, Ga, Mn, Ce, Mg and V is taken as a second auxiliary agent; based on the weight of the catalyst, 0.1-1% of Pt calculated by element, 0.1-5% of Sn calculated by element, 0.5-4% of second auxiliary agent calculated by element, and the balance of carrier.
In the method, Pt and Sn species form macromolecular active component precursor groups in the impregnation liquid by taking EDTA as a ligand, so that the phenomenon that the Pt species are deep into a pore canal with narrow gaps and exist in the pore canal with large pore diameters in a large amount when the Pt and Sn species are impregnated and loaded with active components can be avoided. The pore channel with larger pore diameter can play a role of higher carbon capacity, even if the catalyst is rapidly deposited with a large amount of carbon in high-temperature reaction, the pore channel of the catalyst leading to the dehydrogenation active component is not blocked by the deposited carbon, and reactants and products can still freely enter and exit, so that the catalyst can still keep higher activity under higher carbon deposition amount, the one-way operation period of the catalyst is prolonged, and the operation cost of the device is reduced. Meanwhile, atom clusters of Pt and Sn close to each other are formed on the surface of the carrier by the active component precursor groups of macromolecules, so that a synergistic catalytic effect is generated, and the alkane conversion rate and the alkene selectivity are more excellent.
Detailed Description
The following examples are given to illustrate the technical aspects of the present invention in detail, but the present invention is not limited to the following examples.
Example 1
Preparing a Pt-Sn impregnating solution: 0.68g of chloroplatinic acid was dissolved in 100ml of deionized water, and 0.74g of crystalline tin tetrachloride was added to the solution and stirred to dissolve it. Then, 3g of EDTA was added to the solution, and the mixture was sufficiently stirred to prepare a Pt-Sn impregnation solution.
Weighing 50g of spherical gamma-Al2O3The support was placed in a rotary evaporator and evacuated for 60 min. And (4) sucking the impregnation liquid into a rotary evaporator, closing a vacuum pump, and impregnating for 6 hours at normal temperature and normal pressure.
The temperature of the water bath was then raised to 80 ℃, the catalyst was vacuum dried and transferred to a beaker and dried in an oven at 110 ℃ for 15 hours. The catalyst was then transferred to a muffle furnace and calcined at 500 ℃ for 5 hours. And then, soaking the catalyst in an aqueous solution of potassium nitrate, and drying and roasting to obtain the final catalyst.
The catalyst comprises the following metal simple substances in percentage by weight of a carrier: pt 0.5wt%, Sn 0.5wt%, K0.8 wt%, and the catalyst is designated A.
Comparative example 1
The dehydrogenation catalyst was prepared according to the method disclosed in patent CN 87101513A. The catalyst comprises the following metal simple substances in percentage by weight of a carrier: pt 0.5wt%, Sn 0.5wt%, K0.8 wt%, and this catalyst is denoted as B1.
Comparative example 2
0.68g of chloroplatinic acid was dissolved in 100ml of deionized water, and 0.74g of crystalline tin tetrachloride was added to the solution and stirred to dissolve it, thereby obtaining a Pt-Sn mixed impregnation solution.
Weighing 50g of spherical gamma-Al2O3The support was placed in a rotary evaporator and evacuated for 60 min. And (4) sucking the impregnation liquid into a rotary evaporator, closing a vacuum pump, and impregnating for 6 hours at normal temperature and normal pressure.
The temperature of the water bath was then raised to 80 ℃, the catalyst was vacuum dried and transferred to a beaker and dried in an oven at 110 ℃ for 15 hours. The catalyst was then transferred to a muffle furnace and calcined at 500 ℃ for 5 hours. And then, soaking the catalyst in an aqueous solution of potassium nitrate, and drying and roasting to obtain the final catalyst.
The catalyst comprises the following metal simple substances in percentage by weight of a carrier: pt 0.5wt%, Sn 0.5wt%, K0.8 wt%, and this catalyst is denoted as B2.
Comparative example 3
Preparation of Sn-containing gamma-Al2O3Carrier: mixing a certain amount of 0.98M aluminum trichloride solution and 0.01M stannic chloride solution, adding a certain amount of 8% ammonia water, uniformly mixing in a neutralization tank at 60-80 ℃, controlling the pH value to be 7.0-9.0, filtering, washing, acidifying, pressurizing into an oil ammonia column to form balls, drying, aging, and roasting at 650-750 ℃ for 4 hours to obtain the spherical aluminum oxide with the particle size of 1.5mm and the content of Sn of 0.5 wt%.
Dissolving 0.68g of chloroplatinic acid in 100ml of deionized water, and weighing 50g of spherical gamma-Al2O3The support was placed in a rotary evaporator and evacuated for 60 min. And (3) sucking the chloroplatinic acid solution into a rotary evaporator, closing a vacuum pump, and soaking for 6 hours at normal temperature and normal pressure.
The temperature of the water bath was then raised to 80 ℃, the catalyst was vacuum dried and transferred to a beaker and dried in an oven at 110 ℃ for 15 hours. The catalyst was then transferred to a muffle furnace and calcined at 500 ℃ for 5 hours. And then, soaking the catalyst in an aqueous solution of potassium nitrate, and drying and roasting to obtain the final catalyst.
The catalyst comprises the following metal simple substances in percentage by weight of a carrier: pt 0.5wt%, Sn 0.5wt%, K0.8 wt%, and this catalyst is denoted as B3.
Comparative example 4
0.74g of crystalline tin tetrachloride was dissolved in 100mL of deionized water, and 50g of spheres were weighedForm gamma-Al2O3The support was placed in a rotary evaporator and evacuated for 60 min. And (3) sucking the chloroplatinic acid solution into a rotary evaporator, closing a vacuum pump, and soaking for 6 hours at normal temperature and normal pressure.
The temperature of the water bath was then raised to 80 ℃, the catalyst was vacuum dried and transferred to a beaker and dried in an oven at 110 ℃ for 15 hours. The catalyst was then transferred to a muffle furnace and calcined at 500 ℃ for 5 hours.
0.68g of chloroplatinic acid was dissolved in 100ml of deionized water to impregnate the above carrier. The impregnation, drying and calcination methods were the same as above. And then, soaking the catalyst in an aqueous solution of potassium nitrate, and drying and roasting to obtain the final catalyst.
The catalyst comprises the following metal simple substances in percentage by weight of a carrier: pt 0.5wt%, Sn 0.5wt%, K0.8 wt%, and this catalyst is denoted as B4.
Example 2
Preparing a Pt-Sn impregnating solution: 0.41g of chloroplatinic acid was dissolved in 100ml of deionized water, and 1.5g of crystalline tin tetrachloride was added to the solution and stirred to dissolve it. Then, 4g of EDTA was added to the solution, and the mixture was sufficiently stirred to prepare a Pt-Sn impregnation solution.
Weighing 50g of spherical theta-Al2O3The support was placed in a rotary evaporator and evacuated for 50 min. And (4) sucking the impregnation liquid into a rotary evaporator, closing a vacuum pump, and impregnating for 5 hours at normal temperature and normal pressure.
The temperature of the water bath was then raised to 70 ℃, the catalyst was vacuum dried and transferred to a beaker and dried in an oven at 120 ℃ for 11 hours. The catalyst was then transferred to a muffle furnace and calcined at 510 ℃ for 4 hours. And then, dipping the catalyst by using a zinc nitrate aqueous solution, and drying and roasting to obtain the final catalyst.
The catalyst comprises the following metal simple substances in percentage by weight of a carrier: pt 0.3wt%, Sn 1wt%, Zn 0.75wt%, and the catalyst is denoted as C.
Example 3
Preparing a Pt-Sn impregnating solution: 0.82g of chloroplatinic acid was dissolved in 100ml of deionized water, and 0.44g of crystalline tin tetrachloride was added to the solution and stirred to dissolve it. Then, 3g of EDTA was added to the solution, and the mixture was sufficiently stirred to prepare a Pt-Sn impregnation solution.
Weighing 50g of spherical gamma-Al2O3The support was placed in a rotary evaporator and evacuated for 60 min. And (4) sucking the impregnation liquid into a rotary evaporator, closing a vacuum pump, and impregnating for 7 hours at normal temperature and normal pressure.
The temperature of the water bath was then raised to 85 ℃, the catalyst was vacuum dried and transferred to a beaker and dried in an oven at 110 ℃ for 10 hours. The catalyst was then transferred to a muffle furnace and calcined at 520 ℃ for 3 hours. And then, soaking the catalyst in a gallium nitrate water solution, and drying and roasting to obtain the final catalyst.
The catalyst comprises the following metal simple substances in percentage by weight of a carrier: pt 0.7wt%, Sn 0.3wt%, Ga 0.4wt%, this catalyst is denoted as D.
Example 4
The catalysts prepared in the above examples and comparative examples were subjected to conventional hydrothermal dechlorination, and propane dehydrogenation evaluation experiments were performed in a micro-reactor.
Activation conditions of the catalyst: the reaction solution is kept at 500 ℃ for 2 hours by using 100% hydrogen. The volume space velocity of the reducing gas is 3000h-1。
Passivation conditions of the catalyst: the mass flow rate of the mixed gas of hydrogen sulfide and nitrogen is 1200h-1The volume ratio is 1:5, the temperature is 500 ℃, and the passivation time is 1 hour.
Evaluation conditions were as follows: the catalyst volume is 6.0ml, and the volume space velocity is 850h-1The reaction pressure is normal pressure, the reaction temperature is 620 ℃, and the volume ratio of hydrogen to propane is 1: 1. The initial catalyst and 96 hour propane per pass molar conversion and propylene selectivity are shown in table 1.
Table 1 evaluation results of catalysts of examples and comparative examples.
From the above data, it can be seen that the catalyst prepared by the process of the present invention has higher propane conversion and propylene selectivity, which is benefited by the synergistic catalytic action of the close proximity of the Pt — Sn components in the catalyst. And after the catalyst reacts for 96 hours, the activity of the catalyst is reduced less than that of the catalyst at the initial reaction stage, so that the EDTA is used as a ligand to form a macromolecular active component precursor group, and Pt-Sn species are prevented from entering carrier pore channels with narrow gaps and existing in larger pore diameter positions capable of playing a higher carbon-containing role when the catalyst is immersed and loaded with active components, and even if the catalyst is subjected to rapid and large amount of carbon deposition in high-temperature reaction, the pore channels of the catalyst leading to the dehydrogenation active component are not blocked by the carbon deposition.
Claims (10)
1. The preparation method of the low-carbon alkane dehydrogenation catalyst is characterized by comprising the following steps of: (1) preparing a Pt-Sn impregnating solution: dissolving a proper amount of soluble salt of platinum in deionized water, adding soluble salt of tin into the solution, uniformly stirring, adding a proper amount of ethylene diamine tetraacetic acid into the solution, and uniformly stirring to prepare a Pt-Sn impregnation solution; (2) impregnating an alumina carrier with the impregnation liquid obtained in the step (1), drying, roasting, and then loading a second auxiliary metal on the carrier to obtain a final catalyst;
the second additive is a metal selected from Li, Na, K, Fe, Ni, Cu, Zn, Ga, Mn, Ce, Mg and V.
2. The method of claim 1, wherein: the mass concentration of Pt in the Pt-Sn impregnating solution is 0.001% -0.8%; the mass concentration of Sn is 0.001% -4%; the mass concentration of the ethylene diamine tetraacetic acid is 0.003-5%.
3. The method of claim 1, wherein: the mass concentration of Pt in the Pt-Sn impregnating solution is 0.025% -0.5%; the mass concentration of Sn is 0.05% -2%; the mass concentration of the ethylene diamine tetraacetic acid is 0.01-4.5%.
4. The method of claim 1, wherein: the soluble salt of the platinum is one or more of chloroplatinic acid, chloroplatinic acid or platinum nitrate.
5. The method of claim 1, wherein: the soluble salt of tin is one or more of stannic chloride, stannic oxalate or stannous sulfate.
6. The method of claim 1, wherein: the mass ratio of the impregnation liquid to the carrier is 2: 1-4: 1; the dipping time is 1-20 hours.
7. The method of claim 1, wherein: the carrier is active Al2O3The crystal form is gamma, delta or theta; the equivalent diameter of the particles is 0.2-4 mm.
8. The method of claim 1, wherein: the drying temperature is 100-130 ℃, and the drying time is 10-24 hours.
9. The method of claim 1, wherein: the roasting temperature is 450-550 ℃, and the roasting time is 3-12 hours.
10. The dehydrogenation catalyst for light alkanes prepared by the method of any one of claims 1 to 9, wherein: active alumina is taken as a carrier, Pt is taken as an active component, Sn is taken as a first auxiliary agent, and a metal selected from Li, Na, K, Fe, Ni, Cu, Zn, Ga, Mn, Ce, Mg and V is taken as a second auxiliary agent; based on the weight of the catalyst, 0.1-1% of Pt calculated by element, 0.1-5% of Sn calculated by element, 0.5-4% of second auxiliary agent calculated by element, and the balance of carrier.
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