CN115634696A - Ethane dehydrogenation catalyst and method for simultaneously preparing ethylene and hydrogen by ethane dehydrogenation - Google Patents
Ethane dehydrogenation catalyst and method for simultaneously preparing ethylene and hydrogen by ethane dehydrogenation Download PDFInfo
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- CN115634696A CN115634696A CN202211278054.5A CN202211278054A CN115634696A CN 115634696 A CN115634696 A CN 115634696A CN 202211278054 A CN202211278054 A CN 202211278054A CN 115634696 A CN115634696 A CN 115634696A
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Abstract
The invention provides an ethane dehydrogenation catalyst and a method for simultaneously preparing ethylene and hydrogen by ethane dehydrogenation. The ethane dehydrogenation catalyst adopts non-noble metal as an active component; the first metal component is selected from the combination of more than two of Fe, zn and Ga elements, and the second metal component is selected from one or more of alkali metal, alkaline earth metal, rare earth metal, cu and Mn elements; the third metal component is one or more of compounds containing V, mo, W, ni and Zr elements; and the mass content of the first metal component in the active component is not less than 50%, the content of the second metal component in the active component is 0-30%, and the content of the third metal component in the active component is 0-20% calculated by metal oxide; the mass content of the active component in the ethane dehydrogenation catalyst is not less than 1%. The ethane dehydrogenation catalyst has high selectivity to hydrogen and ethylene, low price, safety and environmental protection when being used for ethane dehydrogenation reaction.
Description
Technical Field
The invention relates to an ethane dehydrogenation conversion technology, in particular to an ethane dehydrogenation catalyst and a method for preparing ethylene and hydrogen by ethane dehydrogenation.
Background
Ethylene is used as an important olefin product and a downstream production raw material, ethane dehydrogenation is one of the paths used in the industry, and the mature method applied in the technology for preparing ethylene by ethane dehydrogenation is mainly an ethane steam cracking method, the temperature of a furnace tube of the steam cracking method needs high temperature of 1000-1200 ℃, and the process has very high energy consumption. Therefore, a feasible catalyst is selected and utilized to perform catalytic dehydrogenation on ethane, reduce the reaction temperature and realize high-efficiency and low-energy consumption production of ethylene, and a lot of research reports are provided, including the design of the catalyst and the selection of process route conditions. The design and definition of a specific catalyst is also a key factor in achieving the goal, in order to have a better effect both in terms of conversion of the ethane feed and selectivity and yield of the ethylene product. On the one hand, even if a catalytic similar feedstock, such as a lower alkane dehydrogenation catalyst, is used for different lower alkane feedstocks, the reaction paths that ethane and propane and/or butane undergo will vary, and as a result substantial differences may occur; on the other hand, different catalytic effects can be brought by selecting corresponding catalysts and differences of reaction systems and process conditions.
At present, the catalyst for preparing low-carbon olefin by oxidative dehydrogenation of low-carbon alkane with carbon dioxide mainly collectsIn the case of Pt-based and CrOx-based catalysts, for example, CN201610134338.5 discloses a modified chromium oxide catalyst with a special pore structure for catalyzing the dehydrogenation of carbon dioxide to prepare ethylene by oxidizing ethane, although a higher ethylene yield is claimed to be obtained, the catalyst has a limited improvement on the ethylene selectivity in the reaction process. In addition, cr in CrOx is expensive as Pt metal 6+ Has carcinostatic property, seriously affects the health and environment of human body, and Cr is also a noble metal. The development of these two noble metal-based catalysts has been greatly limited for a number of reasons. The development of a metal active component catalyst which has high activity (good specificity), low price, safety and environmental protection is particularly important in alkane dehydrogenation reaction and industrial application.
Patent CN105727978B discloses a method for preparing a catalyst for preparing ethylene by oxidative dehydrogenation of ethane, in order to improve the conversion rate of ethane and the selectivity of ethylene, the main active component of the catalyst is Ni, the carrier is alumina, but the catalyst preparation needs to perform reduction treatment on the catalyst precursor, and when the catalyst is used for catalyzing the dehydrogenation of ethane, the composition of the dehydrogenation reaction raw material gas needs to include ethane/oxygen with a 1:1 molar ratio.
Patent CN106984297a discloses a method for preparing ethylene by dehydrogenation of ethane in carbon dioxide atmosphere. Aiming at the problems of the gallium catalyst in the prior art, the used catalyst is a supported catalyst which takes titanium oxide doped with 1.0-20.0% of silicon oxide as a carrier and gallium oxide as an active component.
Patent CN111013563A discloses a spinel catalyst for preparing ethylene by ethane dehydrogenation under carbon dioxide atmosphere and a preparation method thereof. The catalyst is magnesia-alumina spinel doped with gallium oxide, and the general formula of the catalyst is as follows: mgGa x Al 2-x O 4 And x =0.5 to 2, and the doping amount of gallium oxide is preferably 50% or more. The catalyst is used for preparing ethylene by catalytic dehydrogenation of ethane under the atmosphere of carbon dioxide, solves the problem of stability of the catalyst in production, and has high ethane conversion rate and ethylene selectivity.
Compared with the currently researched and disclosed ethane catalytic dehydrogenation technology, more ethane catalytic dehydrogenation technologies can simultaneously meet the requirements of ethane conversion rate and ethylene selectivityThe consensus is that an oxidizing agent (e.g. CO) is used 2 ) The catalytic dehydrogenation of the ethane is assisted, the deep oxidation of the ethane can be inhibited through the adjustment of reaction conditions, the selectivity of an ethylene product is favorably ensured, and therefore, related research is also based on the requirement to research and design a special catalyst and match corresponding reaction conditions. On the other hand, hydrogen generated in the dehydrogenation reaction process is also a hydrogen resource, but the use of the oxidant easily causes part of hydrogen generated in ethane dehydrogenation to be converted into useless water, and precious hydrogen resources are wasted.
Disclosure of Invention
The invention provides an ethane dehydrogenation catalyst, which adopts non-noble metal as an active component, can meet the requirement of ethane conversion rate when used for ethane dehydrogenation reaction, has higher selectivity on hydrogen and ethylene, has the advantages of low price, safety and environmental protection, and is suitable for wide popularization and application.
The invention provides a method for preparing ethylene and hydrogen by ethane catalytic dehydrogenation, which uses the ethane dehydrogenation catalyst and is matched with corresponding process conditions, so that the high-efficiency conversion of ethane to ethylene can be realized, and hydrogen is co-produced.
The invention provides an ethane dehydrogenation catalyst, which adopts non-noble metal as an active component and comprises a first metal component, a second metal component and a third metal component; the first metal component is selected from the combination of more than two of Fe, zn and Ga elements, and the second metal component is selected from one or more of alkali metal, alkaline earth metal, rare earth metal, cu and Mn elements; the third metal component is one or more of compounds containing V, mo, W, ni and Zr elements; and the content of the metal oxide is calculated as the metal oxide,
the mass content of the first metal component in the active component is not less than 50%, the content of the second metal component in the active component is 0-30%, and the content of the third metal component in the active component is 0-20%;
the mass content of the active component in the ethane dehydrogenation catalyst is not less than 1%.
The ethane dehydrogenation catalyst as described above, wherein the first stepA metal component from ZnFe 2 O 4 、ZnGa 2 O 4 、Fe 2 O 3 And ZnO or any combination thereof.
The ethane dehydrogenation catalyst as described above, wherein the contents of the second metal component and the third metal component in the active component are respectively not less than 1%.
The ethane dehydrogenation catalyst as described above, wherein the active component is derived from ZnFe 2 O 4 、ZnGa 2 O 4 、Fe 2 O 3 And ZnO or any combination thereof, and is prepared by coprecipitation, hydrothermal synthesis, a sol-gel method or a roasting method.
The ethane dehydrogenation catalyst is obtained by processing and molding an active component precursor; or the ethane dehydrogenation catalyst is a mixture of an active component and a catalyst carrier, or is loaded on the catalyst carrier and is obtained by processing and molding.
The ethane dehydrogenation catalyst as described above, wherein the catalyst support is selected from one or more of silicon-based molecular sieves, silicon-aluminum molecular sieves, aluminum oxide and silicon oxide.
The invention provides a method for preparing ethylene and hydrogen by catalytic dehydrogenation of ethane, which comprises the following steps:
carrying out dehydrogenation reaction on ethane by using the ethane dehydrogenation catalyst, wherein steam or/and nitrogen is used as a diluent gas, and the percentage of the diluent gas in the total feed by mass is not less than 3%;
controlling the condition of ethane dehydrogenation reaction to be 650-750 ℃ and 200-10000 mL/(g.h) of reaction space velocity;
and respectively recovering ethylene and hydrogen.
The process as described above, wherein the proportion of the diluent gas in the total feed is from 10 to 50%.
The process as described above, wherein the pressure of the dehydrogenation reaction system is controlled to be 0.1 to 3MPa.
The method is characterized in that the dehydrogenation reaction space velocity is controlled to be 500-6000 mL/(g.h).
The invention provides an ethane dehydrogenation catalyst, which uses cheap non-noble metals as active components, has higher selectivity on hydrogen and ethylene when used in ethane dehydrogenation reaction, has the advantages of safety and environmental protection, and is suitable for wide popularization and application.
The invention provides a method for preparing ethylene and hydrogen by ethane catalytic dehydrogenation, which uses the ethane dehydrogenation catalyst, can realize high-efficiency conversion of ethane to ethylene at lower temperature and coproduce hydrogen, and has excellent economic benefit.
Detailed Description
In order to make the aforementioned objects, features and advantages of the embodiments of the present invention more comprehensible, embodiments of the present invention will be described in detail. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides an ethane dehydrogenation catalyst, which adopts non-noble metal as an active component. In some embodiments, the active component may be present in the ethane dehydrogenation catalyst in an amount of from 1 to 20% by weight, for example, such that the active component is present in the ethane dehydrogenation catalyst in an amount of from 1 to 10% by weight.
The active component of the ethane dehydrogenation catalyst at least comprises a first metal component, and also can comprise a second metal component and a third metal component, and based on the total mass of the active components, the mass percentage content of the first metal component is not less than 50%, the mass percentage content of the second metal component is not more than 30%, and the mass percentage content of the third metal component is not more than 30%. Wherein, the first metal component is selected from the combination of more than two of Fe, zn and Ga elements, and the second metal component is selected from one or more of alkali metal, alkaline earth metal, rare earth metal, cu and Mn elements; the third metal component is one or more of compounds containing V, mo, W, ni and Zr elements; and calculated as the metal oxide. It will be appreciated that the ethane dehydrogenation catalyst of the present invention also includes catalyst auxiliaries commonly used in the art.
The ethane dehydrogenation catalyst is used for ethane dehydrogenation reaction by selecting the non-noble metal active component with specific type and content, has higher selectivity on hydrogen and ethylene, and is low in price, safe and environment-friendly.
In the present invention, the sources of the first metal component, the second metal component and the third metal component are not particularly limited, and may be at least one of an oxysalt, an oxysalt and a partial acid salt of the metal.
In some embodiments of the invention, the first metal component is derived from ZnFe 2 O 4 、ZnGa 2 O 4 、Fe 2 O 3 And ZnO, or any combination thereof; the first metal component was found to be from Fe 2 O 3 And/or ZnO, the ethane dehydrogenation catalyst can also have excellent recyclability.
In some embodiments, the second metal component may be selected from at least one of Li, na, K, mg, ca, sr, ba, la, ce, pr, nd, ti.
Further, in order to further improve the selectivity of hydrogen and ethylene in the ethane dehydrogenation reaction of the ethane dehydrogenation catalyst, the contents of the second metal component and the third metal component may be selected, and in some embodiments, the contents of the second metal component and the third metal component in the total metal components are respectively not less than 1%.
In some embodiments of the invention, the active component of the ethane dehydrogenation catalyst is derived from ZnFe 2 O 4 、ZnGa 2 O 4 、Fe 2 O 3 And ZnO, or any combination thereof, and is prepared by coprecipitation, hydrothermal synthesis, a sol-gel method, a firing method, or the like.
In some embodiments of the invention, the ethane dehydrogenation catalyst is obtained by processing and shaping an active component precursor; or the ethane dehydrogenation catalyst is a mixture of an active component and a catalyst carrier, or is loaded on the catalyst carrier and is obtained by processing and molding.
In the invention, the active component precursor can be a simple substance or a compound containing active components, and more than two active components can be provided by the same active component precursor or can be respectively from the corresponding active component precursors; for example, zinc ferrite can be used directly, and iron and zinc salts can also be used to obtain a catalyst containing an Fe-Zn active component.
In the present invention, the ethane dehydrogenation catalyst containing an active component can be obtained by processing and molding the active component precursor. That is, a carrier may not be required. Illustratively, the compound containing the active component is compounded and then tableted to obtain the ethane dehydrogenation catalyst, or the compound containing the active component is directly used as the ethane dehydrogenation catalyst in the form of powder mixture. Specific preparation methods include, but are not limited to, the following: the method for producing the catalyst for ethane dehydrogenation includes dissolving a compound containing an active metal (for example, an active metal acid salt) in water or ethanol to obtain a solution, evaporating the solvent in the solution to obtain a mixed system, and drying the mixed system to obtain the ethane dehydrogenation catalyst, or tabletting the mixed system to obtain the ethane dehydrogenation catalyst. The drying temperature is 50-200 deg.C, and the drying time is 1-72h. In some embodiments, the drying may be followed by calcination at 300-800 deg.C for 1-72h, and the calcination atmosphere is not particularly limited in the present invention, and may be, for example, an oxidizing atmosphere or a reducing atmosphere.
In the present invention, the active component may also be mixed with a catalyst support to obtain an ethane dehydrogenation catalyst containing the active component.
The invention can also load the active component on the catalyst carrier, and the ethane dehydrogenation catalyst containing the active component is obtained by processing and shaping. The ethane dehydrogenation catalyst of the invention can be a product in which active components are sequentially loaded on a catalyst carrier, or a product in which each active component is loaded on a catalyst carrier respectively and then compounded. In some embodiments, the ethane dehydrogenation catalyst can be obtained by dissolving a compound containing an active metal (e.g., an active metal acid salt) in water or ethanol to obtain a solution, adding a part or all of the carrier to the solution to obtain a mixed system, subjecting the mixed system to a shaping treatment to obtain an ethane dehydrogenation catalyst precursor, and drying and calcining the ethane dehydrogenation catalyst precursor. The carrier comprises a binder which is taken as a component of the carrier, such as one or more of sol, silica sol, nitric acid, hydrochloric acid peptization and partially peptized pseudo-boehmite; the forming process includes, but is not limited to, at least one of extrusion, spray forming, tablet forming, oil column forming, or ball forming.
In other embodiments, the carrier (including the binder) may be molded, dried and calcined to obtain a molded carrier; then dissolving a compound containing an active metal (such as an active metal acid salt) in water or ethanol to obtain a solution, loading the solution on a formed carrier, and drying and roasting the impregnated carrier to obtain the formed ethane dehydrogenation catalyst, wherein the loading method comprises one or more of an excess solution impregnation method, an equal volume impregnation method, a multiple impregnation method, an ion exchange method, a high-temperature and high-pressure impregnation method, a direct mixing method, an impregnation precipitation method, a fluidized bed spraying impregnation method and a solid grinding method, and the formed carrier and/or the formed ethane dehydrogenation catalyst comprises but is not limited to strip-shaped, spherical, microspherical, regular or irregular particles.
The mass percentage of the catalyst carrier in the ethane dehydrogenation catalyst is not particularly limited, and in some embodiments, the mass percentage of the catalyst carrier is 0 to 99% based on the total mass of the ethane dehydrogenation catalyst, and further, the mass percentage of the catalyst carrier in the ethane dehydrogenation catalyst is 50 to 90%. Further, when the catalyst carrier is contained in the ethane dehydrogenation catalyst in an amount of 80 to 99% by mass, the ethane dehydrogenation catalyst has more excellent catalyst efficiency.
The catalyst support is not particularly limited, and in some embodiments, the catalyst support may be selected from one or more combinations of silica-based molecular sieves, silicoaluminophosphate molecular sieves, alumina, and silica.
In the invention, the catalyst carrier can be prepared by taking a pure molecular sieve as a raw material. The catalyst carrier can also be prepared by taking a molecular sieve and a non-molecular sieve as raw materials together. When the catalyst carrier is prepared by taking a molecular sieve and a non-molecular sieve as raw materials together, the mass ratio of the molecular sieve to the non-molecular sieve is 4: (0 to 3) is advantageous in that the ethane dehydrogenation catalyst has excellent catalytic activity and mechanical properties. In some embodiments, the mass ratio between the molecular sieve and non-molecular sieve support may be 4:1 or 4:3.
in the invention, the molecular sieve can be selected from one or more of MCM-41, SBA-15, ZSM-5, ZSM-11, ZSM-35, ZSM-22, ZSM-23, IM-5, Y and the like, and the molecular sieve can be an H type molecular sieve subjected to ion exchange, and can also be Na type and K type molecular sieves which are not subjected to ion exchange.
As described above, based on the framework structure of the molecular sieve, the catalyst carrier of the present invention may use a silica-based molecular sieve or a silica-alumina molecular sieve, and in some embodiments, when the silica-alumina molecular sieve is used as the carrier, the silica-alumina ratio of the molecular sieve may be 1 to 600, and further, the silica-alumina ratio of the molecular sieve may be 1 to 200. The silicon to aluminum ratio refers to the molar ratio between silicon oxide and aluminum oxide, i.e., n (SiO) 2 )/n(Al 2 O 3 )。
The second aspect of the present invention provides a method for preparing ethylene and hydrogen by catalytic dehydrogenation of ethane, which comprises the following processes:
the ethane dehydrogenation catalyst is adopted to carry out dehydrogenation reaction on ethane, water vapor or/and nitrogen are/is used as diluent gas, and the percentage of the diluent gas in the total feed by mass is not less than 3%;
the condition of ethane dehydrogenation reaction is controlled, the reaction temperature is 650-750 ℃, and the reaction space velocity is 200-10000 mL/(g.h).
In the invention, ethane and diluent gas are mixed as feed materials, or the ethane and the diluent gas are respectively fed and are contacted with a catalyst in a reaction zone to carry out dehydrogenation reaction on ethane, and reaction products of ethylene and hydrogen are collected. Furthermore, the diluent gas can be water vapor with low cost.
According to embodiments of the present invention, the ethane catalytic dehydrogenation operation may be accomplished in conventional reactors, such as fixed bed, fluidized bed, fixed fluidized bed, slurry bed, ebullating bed, circulating fluidized bed, moving bed reactors, and the like. The ethane and diluent feed are contacted with the catalyst in the reactor, and the reaction temperature and space velocity (ethane feed space velocity) and the reactor internal pressure are regulated to enable the ethane dehydrogenation reaction to proceed with the expected effect.
The conditions under which the ethane dehydrogenation reaction is carried out according to the process of the present invention can be suitably adjusted and matched within the aforementioned ranges depending on the specific choice of the reactor and the catalyst. The reaction temperature is 650-750 ℃, the ethane feeding airspeed is 200-10000 mL/(g.h), the percentage of the diluting gas in the total feeding is not less than 3%, and the proper pressure of the reaction system can be controlled to be 0.1-3 Mpa; in a specific embodiment, the space velocity can be controlled to be 500-6000 mL/(g.h), the proportion of the diluent gas in the total feed is 10-50%, and the efficiency of the catalyst can be ensured while the dehydrogenation reaction process is satisfied.
According to the method for preparing the ethylene and the hydrogen through the catalytic dehydrogenation of the ethane, the ethane dehydrogenation catalyst with the non-noble metal as the active component is used for carrying out the dehydrogenation reaction on the ethane, so that the non-noble metal is low in cost and is beneficial to saving the cost; in the dehydrogenation reaction, an oxidant is not used, and the hydrogen can be co-produced while the ethylene is prepared; meanwhile, the dehydrogenation reaction of the invention also has excellent ethane conversion rate (more than 33 percent), ethylene selectivity (more than 83 percent), hydrogen selectivity (more than 4 percent) and ethylene yield (more than 30 percent). It is worth mentioning that the ethane dehydrogenation catalyst of the invention can be directly used for catalyzing ethane to generate dehydrogenation reaction without reduction pretreatment, which is beneficial to saving operation steps and production cost. Therefore, the method for preparing the ethylene and the hydrogen by the catalytic dehydrogenation of the ethane has the advantages of excellent catalytic effect, simple process and controllable conditions, and is convenient for practical industrial implementation and popularization.
Hereinafter, the technical solution of the present invention will be described in detail by specific examples.
In the embodiment and the comparative example of the invention, the silicon-aluminum ratio of the ZSM-5 molecular sieve is 46; the silicon-aluminum ratio of the MCM-22 molecular sieve is 40; the silicon-aluminum ratio of the IM-5 molecular sieve is 50; MCM-41 has a specific surface area of 1180m 2 (ii)/g; the specific surface area of the pseudo-boehmite is 382m 2 Per g, pore volume 0.91cm 3 /g。
Example 1
The ethane dehydrogenation catalyst of this example was prepared by a process comprising the steps of:
1) 1g of zinc ferrite is dissolved in 10mL of deionized water to prepare a steeping fluid;
2) Weighing pseudoboehmite with corresponding mass, and adding a certain amount of sesbania powder, citric acid and nitric acid (sesbania powder =6wt% multiplied by Al) 2 O 3 Citric acid =6wt% × Al 2 O 3 Nitric acid =6wt% x Al 2 O 3 ) And deionized water (corresponding water absorption capacity), extruding, naturally airing at room temperature, drying at 120 ℃ for 6h, and roasting at 500 ℃ for 4h to obtain a catalyst carrier;
3) Dropwise adding the impregnation liquid in the step 1) to 10g of the catalyst carrier in the step 2) to obtain a catalyst semi-finished product;
4) Standing the semi-finished product of the catalyst in the step 3) in the air for 2 hours, drying in a drying oven at 120 ℃, then heating at the speed of 4 ℃/min, roasting at 500 ℃ for 4 hours in the air atmosphere, and crushing to 40-60 meshes to obtain the ethane dehydrogenation catalyst 1A # ZnFe 2 O 4 /Al 2 O 3 。
The process for the catalytic dehydrogenation of ethane to produce ethylene and hydrogen of this example comprises the following steps:
weighing 5g of 1A # ethane dehydrogenation catalyst, loading the catalyst into a fixed fluidized bed reactor, controlling the pressure in the reactor to be 0.1Mpa, heating the reactor to 680 ℃, feeding ethane and water vapor, wherein the water vapor accounts for 20wt% of the total feeding materials, the space velocity of the ethane is 1200 mL/(g.h), the reaction temperature is 680 ℃, after dehydrogenation reaction is carried out for 2 hours, keeping the temperature of a connecting pipeline between the fixed bed reactor and a chromatogram at 220 ℃, and enabling a gas phase product after the dehydrogenation reaction to flow into a gas chromatograph (Agilent 7890B) provided with a double detector through a six-way valve for on-line analysis, wherein the analysis result is shown in Table 1.
Example 2
The ethane dehydrogenation catalyst of this example was prepared in substantially the same manner as in the examples, except that: replacing zinc ferrite in the step 1) with zinc gallate; the ethane dehydrogenation catalyst 2A # -ZnGa is obtained in the step 4) 2 O 4 /Al 2 O 3 。
The process for the catalytic dehydrogenation of ethane to produce ethylene and hydrogen of this example is essentially the same as example 1 except that a 2A # ethane dehydrogenation catalyst is used in place of the 1A # ethane dehydrogenation catalyst.
Example 3
The ethane dehydrogenation catalyst of this example was prepared by a process comprising the steps of:
1) Weighing 4.04g of ferric nitrate and 1.48g of zinc nitrate, dissolving in 250mL of distilled water, and adjusting the pH to 9 by using NaOH to obtain a mixed solution;
2) Stirring the mixed solution for 10 hours by using a magnetic stirrer until the mixed solution is obviously layered;
3) Separating the layered mixed solution by using a centrifuge, washing by using deionized water, drying the obtained precipitate at 120 ℃ for 6h, and roasting at 500 ℃ for 4h in an air atmosphere to obtain an ethane dehydrogenation catalyst, namely, 3A # ZnFe 2 O 4 。
The process for the catalytic dehydrogenation of ethane to produce ethylene and hydrogen of this example is essentially the same as example 1 except that a 3A # ethane dehydrogenation catalyst is used in place of the 1A # ethane dehydrogenation catalyst.
Example 4
The preparation method of the ethane dehydrogenation catalyst of this example is substantially the same as that of example 1 except that:
in the step 1), 2.04g of ferric nitrate is dissolved in 10mL of deionized water to prepare a first impregnation liquid; dissolving 1.48g of zinc nitrate in the first impregnation liquid to prepare an impregnation liquid;
in the step 4), the ethane dehydrogenation catalyst 4A # Fe is obtained 2 O 3 -ZnO/Al 2 O 3 。
The process for the catalytic dehydrogenation of ethane to produce ethylene and hydrogen of this example is essentially the same as example 1 except that a 4A # ethane dehydrogenation catalyst is used in place of the 1A # ethane dehydrogenation catalyst.
Example 5
The ethane dehydrogenation catalyst of this example was the 4A # ethane dehydrogenation catalyst of example 4.
The process for the catalytic dehydrogenation of ethane to produce ethylene and hydrogen in this example was substantially the same as in example 4 except that the temperature was raised to 660 ℃ and the reaction temperature was 660 ℃.
Example 6
The ethane dehydrogenation catalyst of this example was the 4A # ethane dehydrogenation catalyst of example 4.
The process for the catalytic dehydrogenation of ethane to produce ethylene and hydrogen in this example was substantially the same as in example 4 except that the temperature was raised to 690 ℃ and the reaction temperature was 690 ℃.
Example 7
The ethane dehydrogenation catalyst of this example was the 4A # ethane dehydrogenation catalyst of example 4.
The process for the catalytic dehydrogenation of ethane to produce ethylene and hydrogen in this example was substantially the same as in example 4 except that the temperature was raised to 700 c and the reaction temperature was 700 c.
Example 8
The ethane dehydrogenation catalyst of this example was the 4A # ethane dehydrogenation catalyst of example 4.
The process for the catalytic dehydrogenation of ethane to produce ethylene and hydrogen in this example was substantially the same as example 4 except that the temperature was raised to 710 c and the reaction temperature was 710 c.
Example 9
The ethane dehydrogenation catalyst of this example was the 4A # ethane dehydrogenation catalyst of example 4.
The process for the catalytic dehydrogenation of ethane to produce ethylene and hydrogen in this example was substantially the same as in example 4 except that the temperature was raised to 720 ℃ and the reaction temperature was 720 ℃.
Example 10
The ethane dehydrogenation catalyst of this example was the 4A # ethane dehydrogenation catalyst of example 4.
The process for the catalytic dehydrogenation of ethane to produce ethylene and hydrogen in this example was substantially the same as in example 4 except that the temperature was raised to 740 c and the reaction temperature was 740 c.
Example 11
The ethane dehydrogenation catalyst of this example was prepared by a process comprising the steps of:
1) 0.41g of ZnFe 2 O 4 Dissolving in 10mL of deionized water to prepare a first impregnation solution; dissolving 0.27g of zinc nitrate in 10mL of deionized water to prepare a second impregnation solution;
2) According to the molecular sieve ZSM-5: pseudo-boehmite =4:1 (dry basis ratio), weighing ZSM-5 molecular sieve and pseudoboehmite with corresponding mass, adding a certain amount of sesbania powder, citric acid and nitric acid (sesbania powder =6wt% multiplied by Al) 2 O 3 Citric acid =6wt% × Al 2 O 3 Nitric acid =6wt% x Al 2 O 3 ) And deionized water (corresponding water absorption), extruding, naturally airing at room temperature, drying at 120 ℃ for 6h, and roasting at 500 ℃ for 4h to obtain a catalyst carrier;
3) Dropwise adding the first impregnation liquid obtained in the step 1) to 10g of the catalyst carrier obtained in the step 2) to obtain a first catalyst semi-finished product; dropwise adding the second impregnation liquid obtained in the step 1) to 10g of the catalyst carrier obtained in the step 2) to obtain a second catalyst semi-finished product;
4) Mixing the first catalyst semi-finished product and the second catalyst semi-finished product in the step 3) in a ratio of 1:1, standing in the air for 10 hours, drying in a baking oven at 120 ℃, heating at the speed of 4 ℃/min, roasting at 500 ℃ for 4 hours in the air atmosphere, crushing to 40-60 meshes to obtain the ethane dehydrogenation catalysts 11A # ZnO/ZSM-5 and ZnFe 2 O 4 a/ZSM-5 composite catalyst.
The process for the catalytic dehydrogenation of ethane to produce ethylene and hydrogen of this example is essentially the same as example 1 except that an 11A # ethane dehydrogenation catalyst is used in place of the 1A # ethane dehydrogenation catalyst.
Example 12
The ethane dehydrogenation catalyst of this example was prepared in substantially the same manner as in example 11, except that:
in the step 2), replacing the ZSM-5 molecular sieve with the IM-5 molecular sieve; the ethane dehydrogenation catalyst 12A # -ZnO/IM-5 and ZnFe obtained in the step 4) 2 O 4 The composite catalyst of/IM-5.
The process for the catalytic dehydrogenation of ethane to produce ethylene and hydrogen of this example is essentially the same as example 1 except that a 12A # ethane dehydrogenation catalyst is used in place of the 1A # ethane dehydrogenation catalyst.
Example 13
The ethane dehydrogenation catalyst of this example was prepared in substantially the same manner as in example 11, except that:
in the step 2), replacing a ZSM-5 molecular sieve with an MCM-41 molecular sieve; the ethane dehydrogenation catalyst 13A ZnO/MCM-41 and ZnFe obtained in the step 4) 2 O 4 The composite catalyst of/MCM-41.
The process for the catalytic dehydrogenation of ethane to produce ethylene and hydrogen of this example is essentially the same as example 1 except that a 13A # ethane dehydrogenation catalyst is used in place of the 1A # ethane dehydrogenation catalyst.
Example 14
The ethane dehydrogenation catalyst of this example was prepared in substantially the same manner as in example 11, except that:
in step 2), siO is used 2 Replacing the ZSM-5 molecular sieve; the ethane dehydrogenation catalyst 14A # -ZnO/SiO obtained in the step 4) 2 And ZnFe 2 O 4 /SiO 2 The composite catalyst of (4).
The process for the catalytic dehydrogenation of ethane to produce ethylene and hydrogen of this example is substantially the same as example 1 except that a 14A # ethane dehydrogenation catalyst is used in place of the 1A # ethane dehydrogenation catalyst.
Example 15
The ethane dehydrogenation catalyst of this example was prepared by a process comprising the steps of:
1) 0.41g of ZnFe 2 O 4 Dissolving in 10mL of deionized water to prepare intermediate impregnation liquid; dissolving 0.24g of potassium nitrate in the intermediate impregnation liquid to prepare an impregnation liquid;
2) According to MCM-41 molecular sieve: pseudoboehmite =4:3 (dry basis ratio), weighing MCM-41 molecular sieve and pseudo-boehmite with corresponding mass, adding a certain amount of sesbania powder, citric acid and nitric acid (sesbania powder =6wt% multiplied by Al) 2 O 3 Citric acid =6wt% × Al 2 O 3 Nitric acid =6wt% x Al 2 O 3 ) And deionized water (corresponding water absorption), extruding, naturally airing at room temperature, drying at 120 ℃ for 6h, and roasting at 500 ℃ for 4h to obtain a catalyst carrier;
3) Dropwise adding the impregnation liquid in the step 1) to 10g of the catalyst carrier in the step 2) to obtain a catalyst semi-finished product;
4) Standing the semi-finished product of the catalyst in the step 3) in the air for 7 hours, drying the semi-finished product in an oven at the temperature of 120 ℃, then heating the semi-finished product at the speed of 4 ℃/min, roasting the semi-finished product for 4 hours in the air atmosphere at the temperature of 500 ℃, and crushing the semi-finished product to 40-60 meshes to obtain the ethane dehydrogenation catalyst 15A # ZnFe 2 O 4 -K/MCM-41。
The process for the catalytic dehydrogenation of ethane to produce ethylene and hydrogen of this example is essentially the same as example 1 except that a 15A # ethane dehydrogenation catalyst is used in place of the 1A # ethane dehydrogenation catalyst.
Example 16
The ethane dehydrogenation catalyst of this example was prepared in substantially the same manner as in example 15, except that:
in the step 1), 0.13g of calcium nitrate is used to replace 0.24g of potassium nitrate; the ethane dehydrogenation catalyst 16980 ZnFe obtained in the step 4) 2 O 4 -Ca/MCM-41。
The process for the catalytic dehydrogenation of ethane to produce ethylene and hydrogen of this example is essentially the same as example 1 except that a 16A # ethane dehydrogenation catalyst is used in place of the 1A # ethane dehydrogenation catalyst.
Example 17
The ethane dehydrogenation catalyst of this example was prepared essentially as in example 15, except that:
in the step 1), 0.18g of sodium nitrate is used to replace 0.24g of potassium nitrate; the ethane dehydrogenation catalyst 17A # ZnFe is obtained in the step 4) 2 O 4 -Na/MCM-41。
The process for the catalytic dehydrogenation of ethane to produce ethylene and hydrogen of this example is essentially the same as example 1 except that a 17A # ethane dehydrogenation catalyst is used in place of the 1A # ethane dehydrogenation catalyst.
Example 18
The ethane dehydrogenation catalyst of this example was the 4A # ethane dehydrogenation catalyst of example 4.
The process for the catalytic dehydrogenation of ethane to produce ethylene and hydrogen in this example is essentially the same as in example 4, except that steam comprises 10wt% of the total feed.
Example 19
The ethane dehydrogenation catalyst of this example was the 4A # ethane dehydrogenation catalyst of example 4.
The process for the catalytic dehydrogenation of ethane to produce ethylene and hydrogen in this example is essentially the same as in example 4, except that the feeds are ethane and nitrogen, with the nitrogen comprising 10wt% of the total feed.
Example 20
The ethane dehydrogenation catalyst of this example was the 4A # ethane dehydrogenation catalyst of example 4.
The process for the dehydrogenation of ethane to produce ethylene and hydrogen in this example is essentially the same as in example 4, except that the feeds are ethane and nitrogen, with the nitrogen comprising 20wt% of the total feed.
Example 21
The ethane dehydrogenation catalyst of this example was prepared in substantially the same manner as in example 15, except that:
in the step 1), 3.53g of ferric nitrate is dissolved in 10mL of deionized water to prepare an intermediate impregnation liquid; dissolving 0.51g of zinc nitrate in the intermediate impregnation liquid to prepare an impregnation liquid; the ethane dehydrogenation catalyst 21A # Fe obtained in the step 4) 2 O 3 -ZnO/MCM-41。
The process for the catalytic dehydrogenation of ethane to produce ethylene and hydrogen of this example is essentially the same as example 1 except that a 21A # ethane dehydrogenation catalyst is used in place of the 1A # ethane dehydrogenation catalyst.
Example 22
The ethane dehydrogenation catalyst of this example was prepared essentially as in example 15, except that:
in the step 1), 3.53g of ferric nitrate is dissolved in 10mL of deionized water to prepare a first intermediate impregnation liquid; dissolving 0.51g of zinc nitrate in the first intermediate impregnation liquid to prepare a second intermediate impregnation liquid; dissolving 0.04g of ammonium molybdate in the second intermediate impregnation liquid to obtain an impregnation liquid;
the ethane dehydrogenation catalyst 22A # Fe obtained in the step 4) 2 O 3 -ZnO-MoO 3 /MCM-41。
The process for the catalytic dehydrogenation of ethane to produce ethylene and hydrogen of this example is essentially the same as example 1 except that a 22A # ethane dehydrogenation catalyst is used in place of the 1A # ethane dehydrogenation catalyst.
Example 23
The ethane dehydrogenation catalyst of this example was prepared essentially as in example 22, except that:
in the step 1), 0.03g of nickel nitrate is used for replacing 0.04g of ammonium molybdate;
the ethane dehydrogenation catalyst 23A # Fe obtained in the step 4) 2 O 3 -ZnO-NiO/MCM-41。
The process for the catalytic dehydrogenation of ethane to produce ethylene and hydrogen of this example is substantially the same as example 1 except that a 23A # ethane dehydrogenation catalyst is used in place of the 1A # ethane dehydrogenation catalyst.
Example 24
The ethane dehydrogenation catalyst of this example was prepared essentially as in example 22, except that:
in step 1), 0.02g of zirconium nitrate was used instead of 0.04g of ammonium molybdate;
the ethane dehydrogenation catalyst 24A # Fe obtained in the step 4) 2 O 3 -ZnO-ZrO 2 /MCM-41。
The process for the catalytic dehydrogenation of ethane to produce ethylene and hydrogen of this example is essentially the same as example 1 except that a 24A # ethane dehydrogenation catalyst is used in place of the 1A # ethane dehydrogenation catalyst.
Example 25
The ethane dehydrogenation catalyst of this example was prepared essentially as in example 22, except that:
in the step 1), 0.02g of ammonium metatungstate is used for replacing 0.04g of ammonium molybdate;
the ethane dehydrogenation catalyst 25A # Fe obtained in the step 4) 2 O 3 -ZnO-WO 3 /MCM-41。
The process for the catalytic dehydrogenation of ethane to produce ethylene and hydrogen of this example is essentially the same as example 1 except that a 25A # ethane dehydrogenation catalyst is used in place of the 1A # ethane dehydrogenation catalyst.
Example 26
The ethane dehydrogenation catalyst of this example was the 4A # ethane dehydrogenation catalyst of example 4.
The process for the dehydrogenation of ethane to produce ethylene and hydrogen in this example is essentially the same as in example 4, except that the reactor is a fixed bed.
Comparative example 1
The preparation method of the ethane dehydrogenation catalyst of this comparative example was substantially the same as that of example 1 except that: replacing 1g of zinc ferrite with 0.76g of chromium nitrate in step 1); the ethane dehydrogenation catalyst 1aMc Cr/Al obtained in the step 4) 2 O 3 。
The process for the catalytic dehydrogenation of ethane to produce ethylene and hydrogen of this comparative example is substantially the same as in example 1, except that a 1A # ethane dehydrogenation catalyst is used instead of the 1A # ethane dehydrogenation catalyst.
Comparative example 2
The preparation method of the ethane dehydrogenation catalyst of this comparative example was substantially the same as that of example 1 except that:
in step 1), 1.21g of ferric nitrate is used to replace 1g of zinc ferrite; obtaining the ethane dehydrogenation catalyst 2a # Fe in the step 4) 2 O 3 /Al 2 O 3 。
The process for the catalytic dehydrogenation of ethane to produce ethylene and hydrogen of this comparative example is substantially the same as in example 1, except that a 2a # ethane dehydrogenation catalyst is used instead of the 1A # ethane dehydrogenation catalyst.
Comparative example 3
The preparation method of the ethane dehydrogenation catalyst of this comparative example was substantially the same as that of example 1 except that:
in step 1), 1.21g of zinc nitrate is used to replace 1g of zinc ferrite; znO/Al catalyst for ethane dehydrogenation obtained in step 4) 2 O 3 。
The process for the catalytic dehydrogenation of ethane to produce ethylene and hydrogen of this comparative example is essentially the same as example 1, except that the 1A # ethane dehydrogenation catalyst is replaced with the 3a # ethane dehydrogenation catalyst.
Comparative example 4
The ethane dehydrogenation catalyst of this comparative example was the 4A # ethane dehydrogenation catalyst of example 4.
The process for the dehydrogenation of ethane to produce ethylene and hydrogen of this comparative example is essentially the same as example 4, except that the feed is ethane.
Comparative example 5
The ethane dehydrogenation catalyst of this comparative example was the 4A # ethane dehydrogenation catalyst of example 4.
The process for the dehydrogenation of this comparative example to produce ethylene and hydrogen is essentially the same as in example 4, except that the feed is propane.
TABLE 1
The following can be found from table 1:
as can be seen from examples 1 to 3 and comparative example 1, the ethane dehydrogenation catalysts in the examples of the present invention have excellent ethylene selectivity as well as hydrogen selectivity.
From the results of examples 1-2 and 3, it can be seen that in the catalytic ethane dehydrogenation reaction of the catalyst of the invention, the introduction of the carrier into the catalyst is more beneficial to regulating and controlling the cracking of ethane and controlling the selectivity of methane, thereby being beneficial to reducing the generation of carbon deposition.
It can be seen from examples 1 and 4 and comparative examples 2 to 3 that the catalyst using the bimetallic composite active component has higher selectivity of ethylene and ethane yield in the reaction of catalyzing ethane dehydrogenation, and simultaneously the selectivity of hydrogen is also improved, which is believed that the reaction activity of the dehydrogenation catalyst is obviously improved due to the synergistic effect of the bimetallic active components.
From examples 4-10, it can be seen that the dehydrogenation reaction using the catalyst of the present invention has better results in both ethylene selectivity and yield in a proper temperature range, and although further increase of the reaction temperature is favorable for increasing the ethane conversion, the methane selectivity is increased, indicating that ethane is deeply cracked.
It can be seen from examples 11-14 that when the catalyst support contains a molecular sieve, the pore structure of the molecular sieve is conducive to the formation of metal active sites, and the selectivity and yield of ethylene and the yield of hydrogen are improved while the conversion rate of ethane is improved.
From examples 15-17, it can be seen that the introduction of the second metal component can improve the ethane conversion rate, ensure the ethylene yield, and have a relatively high hydrogen selectivity, and it should be assumed that the electron transfer between the metal ions has an effect on further regulating and improving the catalytic activity of the catalyst.
As can be seen from examples 4, 18-21 and comparative example 4, the catalyst of the present invention is used in ethane dehydrogenation, and the selection and use of diluent (diluent gas) is also one of the influencing factors, and has a significant influence on the improvement of ethane conversion and ethylene yield, and the presence of diluent gas is also beneficial to the suppression of methane and C3+ selectivity, thereby improving ethylene and hydrogen selectivity.
As can be seen from examples 21 to 25, the addition of the third metal component improves the selectivity and yield of ethylene while improving the conversion rate of ethane, and the selectivity of methane is also reduced, which proves that the addition of the third metal component can effectively alleviate the carbon deposition of the catalyst.
It can be seen from example 4 and example 26 that in the fixed fluidized bed reaction, the selectivity to methane is lower in the ethane dehydrogenation reaction, and the ethylene selectivity and ethylene yield are higher due to the influence of the fluidization state of the catalyst.
As can be seen from example 4 and comparative example 5, the effect of applying the ethane dehydrogenation catalyst provided by the present invention to propane catalytic dehydrogenation is significantly deteriorated, which indicates that although ethane and propane are both low-carbon alkanes, there is a substantial difference between the systems and properties thereof, and it is obvious that the desired effect cannot be achieved by simply applying the dehydrogenation catalyst, or even if the catalyst is used in different reaction systems (e.g., ethane dehydrogenation system, propane or butane dehydrogenation system) as a catalyst for low-carbon alkane dehydrogenation reaction, the effect of the catalyst cannot be simply expected.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. An ethane dehydrogenation catalyst adopts non-noble metal as an active component and comprises a first metal component, a second metal component and a third metal component; the first metal component is selected from the combination of more than two of Fe, zn and Ga elements, and the second metal component is selected from one or more of alkali metal, alkaline earth metal, rare earth metal, cu and Mn elements; the third metal component is one or more of compounds containing V, mo, W, ni and Zr elements; and the content of the metal oxide is calculated as the metal oxide,
the mass content of the first metal component in the active component is not less than 50%, the content of the second metal component in the active component is 0-30%, and the content of the third metal component in the active component is 0-20%;
the mass content of the active component in the ethane dehydrogenation catalyst is not less than 1%.
2. The ethane dehydrogenation catalyst of claim 1, wherein the first metal component is from ZnFe 2 O 4 、ZnGa 2 O 4 、Fe 2 O 3 And ZnO or any combination thereof.
3. The ethane dehydrogenation catalyst of claim 1 or 2, wherein the content of the second metal component and the third metal component in the active component is not less than 1%, respectively.
4. The ethane dehydrogenation catalyst of claim 1, wherein the active component is from ZnFe 2 O 4 、ZnGa 2 O 4 、Fe 2 O 3 And ZnO or any combination thereof, and is prepared by coprecipitation, hydrothermal synthesis, a sol-gel method or a roasting method.
5. The ethane dehydrogenation catalyst of any of claims 1-4, wherein the ethane dehydrogenation catalyst is a shaped product of an active component precursor; or the ethane dehydrogenation catalyst is a mixture of an active component and a catalyst carrier, or is loaded on the catalyst carrier and is obtained by processing and molding.
6. The ethane dehydrogenation catalyst of claim 5, wherein the catalyst support is selected from the group consisting of one or more combinations of silica-based molecular sieves, silicoaluminophosphate molecular sieves, alumina and silica.
7. A method for preparing ethylene and hydrogen by ethane catalytic dehydrogenation comprises the following steps:
dehydrogenating ethane with an ethane dehydrogenation catalyst according to any of claims 1 to 6, using steam and/or nitrogen as diluent gas, wherein the percentage of the diluent gas in the total feed is not less than 3% by mass;
the condition of ethane dehydrogenation reaction is controlled, the reaction temperature is 650-750 ℃, and the reaction space velocity is 200-10000 mL/(g.h).
8. The method of claim 7, wherein the diluent gas is present in the total feed in a proportion of 10-50%.
9. The method according to claim 7, wherein the pressure of the dehydrogenation reaction system is controlled to be 0.1 to 3MPa.
10. The method of claim 7, wherein the dehydrogenation reaction space velocity is controlled to be 500-6000 mL/(g-h).
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