CN107983402B - Propane aromatization catalyst and preparation method and application thereof - Google Patents
Propane aromatization catalyst and preparation method and application thereof Download PDFInfo
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
A propane aromatization catalyst comprises metal oxide and a ZSM-5 molecular sieve carrier, and the mass percent of the catalyst is as follows: 1-2% of zinc oxide, 0.1-0.5% of gallium oxide, 2-5% of molybdenum oxide, 2-4% of iron oxide, 0.3-1% of rare earth mixed metal oxide, 0.2-0.7% of noble metal mixed oxide, 0.6-1.5% of other transition metal mixed oxides and the balance of ZSM-5 molecular sieve carrier.
Description
Technical Field
The invention belongs to a catalyst and a preparation method and application thereof, and particularly relates to a propane aromatization catalyst and a preparation method and application thereof.
Background
Propane is a byproduct obtained during catalytic cracking and thermal cracking of crude oil, has high yield and relatively low price, but has few chemical utilization ways, and is mostly only used as industrial and civil fuel. The aromatic hydrocarbon synthesized by adopting propane as a raw material has good economic value and is a hot field of chemical research.
The molecular sieve can catalyze the aromatization reaction of propane, wherein the ZSM-5 molecular sieve has better catalytic performance and more related researches. Adding metal components Zn (Ono Y, Catal Rev-Sci Eng,1992,34(3):179), Pt (Minache v Kh M, real Kinet Catal Letter,1987,85(1-2):195) or Ni (Qianjin, Ind Rng Res,1987,28(4):647) in a ZSM-5 molecular sieve catalyst by means of ion exchange or loading, can increase the conversion rate of molecular sieve propane and improve the selectivity of aromatic hydrocarbon; the catalyst activity and selectivity can be further improved by continuing the addition of the second metal components Ga (Lubango L M, Appl Catal A,2002,235:265), La (Seire S, React Kinet Catal Letter,1989,40(2):39), Fe (Popova Z, React Kinet Catal Letter,1990,41(2):369) and the like. It can be seen that the addition of the metal element auxiliary agent in the ZSM-5 molecular sieve is a feasible path for improving the aromatization performance of the catalyst propane; the synergistic addition of 2 or even more metal promoters can achieve further optimization of catalyst performance. However, the existing catalyst for propane aromatization generates a large amount of methane and ethane by-products through reaction, and the catalyst is easy to form carbon and is quick in inactivation, so that the types and the contents of the metal auxiliary agents and the preparation method need to be deeply researched and comprehensively optimized.
Disclosure of Invention
The invention aims to provide a propane aromatization catalyst with good propane aromatization activity and high selectivity as well as a preparation method and application thereof.
The catalyst consists of metal oxide and a ZSM-5 molecular sieve carrier, and comprises the following components in percentage by mass: 1-2% of zinc oxide, 0.1-0.5% of gallium oxide, 2-5% of molybdenum oxide, 2-4% of iron oxide, 0.3-1% of rare earth mixed metal oxide, 0.2-0.7% of noble metal mixed oxide, 0.6-1.5% of other transition metal mixed oxides and the balance of ZSM-5 molecular sieve carrier.
The rare earth mixed metal oxide as described above is a mixture of lanthanum oxide, cerium oxide, yttrium oxide and europium oxide, each oxide component constituting at least 0.05% by mass of the total mass of the catalyst.
The noble metal mixed oxide as described above is a mixture of platinum oxide, palladium oxide and ruthenium oxide, and each oxide component accounts for at least 0.05% of the total mass of the catalyst.
Other transition metal mixed oxides as described above are mixtures of nickel oxide, cobalt oxide, manganese oxide, bismuth oxide. Each oxide component accounts for at least 0.1 percent of the total mass of the catalyst.
The preparation method comprises the following steps:
(1) preparation of a ZSM-5 molecular sieve carrier:
preparing an aqueous solution A by adopting concentrated sulfuric acid and aluminum sulfate, wherein the mass ratio of water to concentrated sulfuric acid is 1:0.035-0.038, the mass ratio of water to aluminum sulfate is 1:0.011-0.014, preparing an aqueous solution B by adopting water glass, n-butylamine and sodium hydroxide, wherein the mass ratio of water to water glass is 1:0.457-0.459, the mass ratio of water to n-butylamine is 1:0.045-0.048, and the mass ratio of water to sodium hydroxide is 1:0.008-0.012, dropwise adding the solution A with the same volume into the solution B under the stirring condition, continuously stirring at room temperature for 24-36h, heating to 170-190 ℃ under the closed condition, and stirring for 36-48 h. Filtering, washing to neutrality, oven drying, and soaking in 6-9 g/ml-1Standing the ammonium nitrate aqueous solution for 4-10h under the closed condition of 110-130 ℃ for ion exchange, taking out and drying, and roasting at the temperature of 500-600 ℃ for 4-6h to obtain the hydrogen type ZSM-5 molecular sieve carrier;
(2) the metal oxide component is loaded by a stepwise impregnation method
First impregnation: preparing a mixed solution of zinc nitrate and gallium nitrate with the cation concentration of 0.5-1.3 g/ml according to the composition of a catalyst, adding 60-100 meshes of hydrogen type ZSM-5 molecular sieve carrier powder into the mixed solution, dipping for 6-24 hours under the stirring condition, heating and concentrating the suspension liquid under the water bath condition of 60-90 ℃ after dipping, roasting for 6-12 hours at 350-550 ℃, and grinding the roasted first catalyst precursor to 60-100 meshes;
second impregnation: preparing a mixed solution of nickel nitrate, cobalt nitrate, manganese nitrate and bismuth nitrate with the cation concentration of 0.5-1.3 g/ml according to the composition of a catalyst, adding 60-100 meshes of first catalyst precursor powder into the solution, dipping for 6-24 h under the stirring condition, heating and concentrating the suspension at the temperature of 60-90 ℃ in a water bath after dipping, roasting for 6-12 h at the temperature of 350-550 ℃, and grinding the roasted second catalyst precursor to 60-100 meshes;
and (3) third impregnation: preparing a mixed solution of ammonium molybdate, ferric nitrate, lanthanum nitrate, cerium nitrate, yttrium nitrate and europium nitrate with the cation concentration of 0.5-1.3 g/ml according to the composition of a catalyst, adding 60-100 meshes of secondary catalyst precursor powder into the mixed solution, soaking for 6-24 hours under the stirring condition, heating and concentrating the suspension at the temperature of 60-90 ℃ in a water bath condition after soaking is finished, roasting for 6-12 hours at the temperature of 350-550 ℃, and grinding the roasted third catalyst precursor to 60-100 meshes;
fourth impregnation: preparing a platinum nitrate, palladium nitrate and ruthenium nitrate mixed solution with the cation concentration of 0.5-1.3 g/ml according to the composition of the catalyst, adding 60-100 meshes of third catalyst precursor powder into the solution, dipping for 6-24 h under the stirring condition, heating and concentrating the suspension at the temperature of 60-90 ℃ in a water bath after dipping, roasting for 6-12 h at the temperature of 350-550 ℃, and grinding the roasted catalyst to 60-100 meshes to obtain the catalyst product.
The catalyst is used for fixed bed propane aromatization reaction, and the mass space velocity is 1-10 h-1The reaction pressure is 0.5-3 MPa, and the reaction temperature is 400-600 ℃.
The technical advantages of the invention are as follows:
the invention discloses a molecular sieve propane aromatization catalyst containing multiple metal oxide auxiliaries. Compared with the existing propane aromatization catalyst, the invention has the substantive characteristics and the progress that:
(1) the synergistic effect of several metal oxides is utilized to raise the aromatization activity and selectivity of propane catalyst.
(2) The distribution and the placement of various metal elements in the catalyst are controlled by adopting a step-by-step impregnation method, so that the optimization of the metal synergistic effect is realized.
(3) The aromatization performance of the catalyst is improved by screening the types and the contents of the metal oxides and regulating the electronic effect and the structural effect of the catalyst.
Detailed Description
The following provides a more detailed description of embodiments of the present invention by way of specific examples.
Example 1
Preparing an aqueous solution A by adopting concentrated sulfuric acid and aluminum sulfate, wherein the mass ratio of water to concentrated sulfuric acid is 1:0.037, the mass ratio of water to aluminum sulfate is 1:0.014, and preparing an aqueous solution B by adopting water glass, n-butylamine and sodium hydroxide, wherein the mass ratio of water to water glass is 1:0.457, the mass ratio of water to n-butylamine is 1:0.046, and the mass ratio of water to sodium hydroxide is 1: 0.012. The mass of water taken is 100g, the mass of concentrated sulfuric acid is 3.7g, the mass of aluminum sulfate is 1.4g, the mass of water glass is 45.7g, the mass of n-butylamine is 4.6g, and the mass of sodium hydroxide is 1.2 g. Dropwise adding the solution A with the same volume into the solution B under the stirring condition, continuously stirring for 30h at room temperature, heating to 190 ℃ under the closed condition, and stirring for 38 h. The product was filtered, washed to neutrality, dried and then immersed in a solution of 8g/ml-1And standing the ammonium nitrate aqueous solution at 115 ℃ for 5 hours under a closed condition for ion exchange, taking out and drying the ammonium nitrate aqueous solution, and roasting the ammonium nitrate aqueous solution at 540 ℃ for 5.5 hours to obtain the hydrogen type ZSM-5 molecular sieve.
First impregnation: preparing a zinc nitrate and gallium nitrate mixed solution with the cation concentration of 1.0g/ml, and respectively weighing 0.233g of zinc oxide and 0.109g of gallium nitrate as precursors, wherein the mass ratio of the zinc nitrate to the gallium nitrate is 2.13: 1. Adding 60-100 mesh hydrogen type ZSM-5 molecular sieve carrier powder into the solution according to the composition of the catalyst, dipping for 20h under the stirring condition, heating and concentrating the suspension in a water bath condition at 90 ℃ after dipping, then roasting for 11h at 350 ℃, and grinding the roasted first catalyst precursor to 60-100 mesh.
Second impregnation: preparing a mixed solution of nickel nitrate, cobalt nitrate, manganese nitrate and bismuth nitrate with the cation concentration of 0.8g/ml, and respectively weighing 0.024g of nickel nitrate, 0.110g of cobalt nitrate, 0.050g of manganese nitrate and 0.017g of bismuth nitrate as precursors, wherein the mass ratio of the nickel nitrate to the cobalt nitrate to the manganese nitrate to the bismuth nitrate is 1.44:6.51:2.98: 1. Adding 60-100 mesh first catalyst precursor powder into the solution according to the composition of the catalyst, dipping for 6h under the stirring condition, heating and concentrating the suspension in a water bath condition at 80 ℃ after dipping, then roasting for 6h at 500 ℃, and grinding the roasted second catalyst precursor to 60-100 mesh.
And (3) third impregnation: and preparing a mixed solution of ammonium molybdate, ferric nitrate, lanthanum nitrate, cerium nitrate, yttrium nitrate and europium nitrate with the cation concentration of 0.6 g/ml. 0.462g of ammonium molybdate, 0.909g of ferric nitrate, 0.020g of lanthanum nitrate, 0.009g of cerium nitrate, 0.012g of yttrium nitrate and 0.019g of europium nitrate are respectively weighed as precursors, and the mass ratio of the ammonium molybdate, the ferric nitrate, the lanthanum nitrate, the cerium nitrate, the yttrium nitrate and the europium nitrate is 24.05:47.35:1.04:0.49:0.63: 1. Adding 60-100 meshes of second catalyst precursor powder into the solution according to the composition of the catalyst, dipping for 20h under the stirring condition, heating and concentrating the suspension in 70 ℃ water bath after dipping, roasting for 8h at 350 ℃, and grinding the roasted third catalyst precursor to 60-100 meshes.
Fourth impregnation: a mixed solution of platinum nitrate, palladium nitrate and ruthenium nitrate having a cation concentration of 0.8g/ml was prepared. 0.014g of platinum nitrate, 0.009g of palladium nitrate and 0.009g of ruthenium nitrate are respectively weighed as precursors, and the mass ratio of the platinum nitrate to the palladium nitrate to the ruthenium nitrate is 1.62:1.09: 1. Adding 60-100 meshes of third catalyst precursor powder into the solution according to the composition of the catalyst, dipping for 6 hours under the stirring condition, heating and concentrating the suspension in a water bath condition at 60 ℃ after dipping is finished, roasting for 6 hours at 450 ℃, and grinding to 60-100 meshes to obtain the catalyst product.
The catalyst comprises the following components in percentage by mass: 1% of zinc oxide, 0.4% of gallium oxide, 0.1% of nickel oxide, 0.5% of cobalt oxide, 0.2% of manganese oxide, 0.1% of bismuth oxide, 4% of molybdenum oxide, 3% of iron oxide, 0.1% of lanthanum oxide, 0.05% of cerium oxide, 0.05% of yttrium oxide, 0.1% of europium oxide, 0.1% of platinum oxide, 0.05% of palladium oxide, 0.05% of ruthenium oxide and 90.2% of ZSM-5 molecular sieve.
The catalyst is used for fixed bed propane aromatization reaction, and has mass space velocityIs 5h-1The reaction pressure is 3MPa, and the reaction temperature is 450 ℃. In the reaction, the conversion rate of propane is 14% and the selectivity of aromatic hydrocarbon is 35%.
Examples 2 to 6
The synthesis conditions of the ZSM-5 molecular sieve are shown in table 1, the first to fourth impregnation conditions are shown in tables 2-5, the catalyst composition is shown in table 6, and the propane aromatization reaction conditions and the reaction results are shown in table 7. The specific procedure is as shown in example 1.
Comparative example 1
Preparing an aqueous solution A by adopting concentrated sulfuric acid and aluminum sulfate, wherein the mass ratio of water to concentrated sulfuric acid is 1:0.037, the mass ratio of water to aluminum sulfate is 1:0.012, preparing an aqueous solution B by adopting water glass, n-butylamine and sodium hydroxide, wherein the mass ratio of water to water glass is 1:0.459, the mass ratio of water to n-butylamine is 1:0.047, and the mass ratio of water to sodium hydroxide is 1:0.012, dropwise adding the solution A with the same volume into the solution B under the stirring condition, continuously stirring at room temperature for 32 hours, heating to 170 ℃ under the sealing condition, and stirring for 44 hours. The product was filtered, washed to neutrality, dried and then immersed in a solution having a concentration of 7 g/ml-1And standing the ammonium nitrate aqueous solution at 115 ℃ for 6 hours under a closed condition for ion exchange, taking out and drying the ammonium nitrate aqueous solution, and roasting the ammonium nitrate aqueous solution at 590 ℃ for 5 hours to obtain the hydrogen type ZSM-5 molecular sieve.
Preparing a mixed solution of zinc nitrate and gallium nitrate with the cation concentration of 0.5g/ml, adding carrier powder of 60-100 meshes into the solution according to the composition of the catalyst, dipping for 18h under the stirring condition, heating and concentrating the suspension in a water bath condition at 80 ℃ after dipping, roasting for 10h at 500 ℃, and grinding the roasted catalyst precursor to 60-100 meshes.
The catalyst comprises the following components: 1.4 percent of zinc oxide, 0.3 percent of gallium oxide and 98.3 percent of ZSM-5 molecular sieve.
The catalyst is used for fixed bed propane aromatization reaction, and the mass space velocity is 4h-1The reaction pressure is 2.5MPa, and the reaction temperature is 400 ℃. In the reaction, the conversion rate of propane is 8%, and the selectivity of aromatic hydrocarbon is 21%.
Comparative example 2
Preparing aqueous solution A from concentrated sulfuric acid and aluminum sulfate, which isThe mass ratio of the water to the concentrated sulfuric acid is 1:0.037, the mass ratio of the water to the aluminum sulfate is 1:0.012, the water glass, the n-butylamine and the sodium hydroxide are adopted to prepare an aqueous solution B, the mass ratio of the water to the water glass is 1:0.459, the mass ratio of the water to the n-butylamine is 1:0.047, and the mass ratio of the water to the sodium hydroxide is 1:0.012, the solution A with the same volume is dripped into the solution B under the stirring condition, the stirring is continuously carried out at room temperature for 32 hours, the temperature is raised to 170 ℃ under the sealing condition, and the stirring is carried out for 44 hours. The product was filtered, washed to neutrality, dried and then immersed in a solution having a concentration of 7 g/ml-1And standing the ammonium nitrate aqueous solution at 115 ℃ for 6 hours under a closed condition for ion exchange, taking out and drying the ammonium nitrate aqueous solution, and roasting the ammonium nitrate aqueous solution at 590 ℃ for 5 hours to obtain the hydrogen type ZSM-5 molecular sieve.
The molecular sieve is directly used as a catalyst for fixed bed propane aromatization reaction, and the mass space velocity is 4h-1The reaction pressure is 2.5MPa, and the reaction temperature is 400 ℃. In the reaction, the conversion rate of propane is 5% and the selectivity of aromatic hydrocarbon is 19%.
TABLE 1 conditions for the preparation of ZSM-5 molecular sieves
TABLE 2 first impregnation conditions
TABLE 3 second impregnation conditions
TABLE 4 third impregnation conditions
TABLE 5 fourth impregnation conditions
TABLE 6 catalyst composition
TABLE 7 aromatization reaction conditions of propane and reaction results
Claims (2)
1. A propane aromatization catalyst characterized by: the catalyst consists of metal oxide and a ZSM-5 molecular sieve carrier, and the mass percentage of the catalyst is as follows: 1-2% of zinc oxide, 0.1-0.5% of gallium oxide, 2-5% of molybdenum oxide, 2-4% of iron oxide, 0.3-1% of rare earth mixed metal oxide, 0.2-0.7% of noble metal mixed oxide, 0.6-1.5% of other transition metal mixed oxide and the balance of ZSM-5 molecular sieve carrier;
the rare earth mixed metal oxide is a mixture consisting of lanthanum oxide, cerium oxide, yttrium oxide and europium oxide, and each oxide component accounts for at least 0.05 percent of the total mass of the catalyst;
the noble metal mixed oxide is a mixture consisting of platinum oxide, palladium oxide and ruthenium oxide, and each oxide component at least accounts for 0.05 percent of the total mass of the catalyst;
the other transition metal mixed oxide is a mixture consisting of nickel oxide, cobalt oxide, manganese oxide and bismuth oxide, and each oxide component at least accounts for 0.1 percent of the total mass of the catalyst;
the preparation process of the propane aromatization catalyst comprises the following steps:
(1) preparation of a ZSM-5 molecular sieve carrier:
preparing an aqueous solution A by adopting concentrated sulfuric acid and aluminum sulfate, wherein the mass ratio of water to concentrated sulfuric acid is 1:0.035-0.038, the mass ratio of water to aluminum sulfate is 1:0.011-0.014,preparing an aqueous solution B by adopting water glass, n-butylamine and sodium hydroxide, wherein the mass ratio of water to the water glass is 1:0.457-0.459, the mass ratio of the water to the n-butylamine is 1:0.045-0.048, and the mass ratio of the water to the sodium hydroxide is 1:0.008-0.012, dropwise adding the solution A with the same volume into the solution B under the stirring condition, continuously stirring at room temperature for 24-36h, heating to 170--1Standing the ammonium nitrate aqueous solution for 4-10h under the closed condition of 110-130 ℃ for ion exchange, taking out and drying, and roasting at the temperature of 500-600 ℃ for 4-6h to obtain the hydrogen type ZSM-5 molecular sieve carrier;
(2) the metal oxide component is loaded by a stepwise impregnation method
First impregnation: preparing a mixed solution of zinc nitrate and gallium nitrate with the cation concentration of 0.5-1.3 g/mL according to the composition of a catalyst, adding 60-100 meshes of hydrogen type ZSM-5 molecular sieve carrier powder into the mixed solution, dipping for 6-24 hours under the stirring condition, heating and concentrating the suspension after dipping under the water bath condition of 60-90 ℃, roasting for 6-12 hours at 350-550 ℃, and grinding the roasted first catalyst precursor to 60-100 meshes;
second impregnation: preparing a mixed solution of nickel nitrate, cobalt nitrate, manganese nitrate and bismuth nitrate with the cation concentration of 0.5-1.3 g/ml according to the composition of a catalyst, adding 60-100 meshes of first catalyst precursor powder into the solution, dipping for 6-24 h under the stirring condition, heating and concentrating the suspension at the temperature of 60-90 ℃ in a water bath after dipping, roasting for 6-12 h at the temperature of 350-550 ℃, and grinding the roasted second catalyst precursor to 60-100 meshes;
and (3) third impregnation: preparing a mixed solution of ammonium molybdate, ferric nitrate, lanthanum nitrate, cerium nitrate, yttrium nitrate and europium nitrate with the cation concentration of 0.5-1.3 g/mL according to the composition of a catalyst, adding 60-100 meshes of secondary catalyst precursor powder into the mixed solution, soaking for 6-24 hours under the stirring condition, heating and concentrating the suspension at the temperature of 60-90 ℃ in a water bath condition after soaking is finished, roasting for 6-12 hours at the temperature of 350-550 ℃, and grinding the roasted third catalyst precursor to 60-100 meshes;
fourth impregnation: preparing a platinum nitrate, palladium nitrate and ruthenium nitrate mixed solution with the cation concentration of 0.5-1.3 g/mL according to the composition of the catalyst, adding 60-100 meshes of third catalyst precursor powder into the solution, dipping for 6-24 h under the stirring condition, heating and concentrating the suspension at the temperature of 60-90 ℃ in a water bath after dipping, roasting for 6-12 h at the temperature of 350-550 ℃, and grinding the roasted catalyst to 60-100 meshes to obtain the catalyst product.
2. Use of a propane aromatization catalyst according to claim 1 comprising the steps of:
the catalyst is used for fixed bed propane aromatization reaction, and the mass space velocity is 1-10 h-1The reaction pressure is 0.5-3 MPa, and the reaction temperature is 400-600 ℃.
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