CN112958103B - Catalyst for catalyzing propylene to be oxidized and synthesized into acrolein and preparation method thereof - Google Patents
Catalyst for catalyzing propylene to be oxidized and synthesized into acrolein and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a catalyst for catalyzing propylene to oxidize and synthesize acraldehyde and a preparation method thereof, wherein the catalyst comprises a carrier and active components, and the active components comprise Mo, bi, fe, co, X, Y and Z; the molar ratio of Bi to Mo is (0.1-10): 12; the molar ratio of Fe to Mo is (0.05-9): 12; the molar ratio of Co to Mo is (0.2-5): 12; the molar ratio of X to Mo is (0.08-10): 12; the molar ratio of Y to Mo is (0.01-9): 12; the molar ratio of Z to Mo is (0.1-3.2): 12; x is one or more of Mg, ca, be, cu, zn and Mn; y is Ti and/or Zr; z is one or more of Li, na, K and Cs; the carrier includes an Si element and an Al element. The catalyst has the advantages of high activity, high stability and long service life in catalyzing the oxidation of propylene to synthesize the acrolein.
Description
Technical Field
The invention belongs to the technical field of catalytic synthesis, and particularly relates to a catalyst for catalyzing propylene to be oxidized and synthesized into acrolein and a preparation method thereof.
Background
Acrolein (H) 2 C = CH-CH = O) is the simplest α, β unsaturated aldehyde, and is generally colorless or pale yellow, transparent, liquid that can volatilize pungent odor under normal temperature and pressure, and acrolein is easily soluble in water and various organic solvents. Because of containing carbon-carbon double bond and aldehyde group, the acrolein has high reactivity and is mainly used as an organic chemical synthesis intermediate for producing acrylic acid and methionine.
The current major industrial production of acrolein is the direct oxidation of propylene. Mixing propylene, air and steam according to a specific proportion, reacting at 290-380 ℃ and 200-300kPa in the presence of a certain catalyst, and washing, absorbing, stripping and rectifying the reacted system to obtain the final product acrolein. The method has the advantages of convenient and easily obtained raw materials, low energy consumption, low equipment requirement and investment, good acrolein product quality, less discharge of industrial three wastes and the like. The most common catalyst used in the present direct propylene oxidation process is a Mo-Bi multi-component catalyst. The catalytic reaction mechanism of the Mo-Bi multi-component catalyst is mostly Mars-van Krevelen mechanism, namely: the lattice oxygen with nucleophilic nature is the oxidant of the reaction, the lattice oxygen ions migrate, and oxygen in the gas phase replenishes the lattice oxygen consumed in the catalytic process, so that the oxygen in acrolein is derived from the lattice oxygen of the catalyst itself.
The research on the acrolein preparation by propylene oxidation is wide at home and abroad. ZL201210412591 discloses a catalyst which adopts a molybdenum-bismuth system, the once-through yield of acrolein reaches over 75 percent, and the once-through yield of the acrolein is lower; CN103739467A provides a method for obtaining acrolein and acrylic acid simultaneously, in which acrolein and acrylic acid obtained by the molybdenum bismuth based catalyst are obtained in yields of 92% or more, but effective separation of olefine aldehyde and acrylic acid is not achieved. ZL201410096092.8 adopts a Mo-Bi catalyst, introduces Mn, fe and Co elements, adjusts the pH value by adding ammonia water, and is prepared by adopting a blending one-step combustion method, so that the activity of the catalyst is improved to a certain extent, but the defect of low mechanical strength of the catalyst is overcome. The catalytic activity and the service life of the acrolein catalyst obtained by the above technology need to be further improved.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a catalyst for catalyzing propylene to be oxidized and synthesized into acrolein and a preparation method thereof, aiming at the defects of the prior art. The invention provides a catalyst for catalyzing propylene to be oxidized and synthesized into acrolein, which comprises a carrier and an active component, wherein the active component comprises Mo, bi, fe, co, X, Y and Z, the carrier is a mixture containing a Si element and an Al element, and the active component is combined with the carrier element to form Mo 12 Bi a Fe b Co c X d Y e Z f Si g Al h O i The structure has the advantages of high activity, stability and long service life in catalyzing the synthesis of acrolein by propylene oxidation.
In order to solve the technical problems, the invention adopts the technical scheme that: the catalyst for catalyzing propylene to be oxidized and synthesized into acrolein is characterized by comprising a carrier and active components, wherein the active components comprise Mo, bi, fe, co, X, Y and Z;
in the active components, the molar ratio of Bi to Mo is (0.1-10): 12; the molar ratio of Fe to Mo is (0.05-9): 12; the molar ratio of Co to Mo is (0.2-5): 12; the molar ratio of X to Mo is (0.08-10): 12; the molar ratio of Y to Mo is (0.01-9): 12; the molar ratio of Z to Mo is (0.1-3.2): 12;
x is one or more of Mg, ca, be, cu, zn and Mn; the Y is one or two of Ti and Zr; z is one or more of Li, na, K and Cs;
the mass percentage of the carrier in the catalyst is 5-50%, the carrier comprises Si element and Al element, and the molar ratio of the Si element to the Al element in the carrier is (0.2-15): (0.05-15).
The catalyst for catalyzing propylene to oxidize and synthesize the acrolein is characterized in that X is one or more of Mg, ca, zn and Mn; z is one or more of Na, K and Cs; the mass percentage of the carrier in the catalyst is 15-50%, and the molar ratio of Si element to Al element in the carrier is (3-5): (2 to 9).
In addition, the invention also provides a method for preparing the catalyst for catalyzing the propylene to be oxidized and synthesized into the acrolein, which is characterized by comprising the following steps:
step one, preparing a first catalytic precursor; the first catalytic precursor comprises a carrier containing Si element, mo, bi, fe and Co;
step two, preparing a second catalytic precursor; the second catalytic precursor comprises a support comprising an aluminum element, X, Y and Z;
and step three, mixing and grinding the first catalytic precursor in the step one and the second catalytic precursor in the step two, extruding and forming, and roasting at the temperature of 150-600 ℃ for 0.5-12 h to obtain the catalyst for synthesizing acrolein by catalyzing the oxidation of propylene.
The method described above, wherein the first method for preparing the first catalytic precursor specifically comprises:
step 101, mixing Mo-containing soluble salt, bi-containing soluble salt, fe-containing soluble salt and Co-containing soluble salt with water to obtain solution A; in the solution A, the molar concentration of Mo element is 1.0-10.0 mol/L;
102, stirring and precipitating the solution A obtained in the step 101 for 0.5 to 6 hours under the conditions that the pH value is 3.0 to 10.5 and the temperature is 25 to 80 ℃ to obtain slurry A; the reagent for adjusting the pH is a sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 0.2-3.0 mol/L;
103, adding silicon dioxide into the slurry A obtained in the step 102, and continuously stirring and precipitating for 0.5-6 h under the conditions that the pH is 3.0-10.5 and the temperature is 25-80 ℃ to obtain slurry B;
and step 104, carrying out hydrothermal treatment on the slurry B obtained in the step 103 at the temperature of 60-110 ℃ for 3-10 h, carrying out suction filtration, drying the trapped substance at the temperature of 60-150 ℃ for 5-24 h, and grinding to obtain the first catalytic precursor.
The method described above, wherein the second catalytic precursor preparation method specifically includes:
step 201, mixing soluble salt containing X, soluble salt containing Y, soluble salt containing Z, soluble salt containing Al and water to obtain solution B; in the solution B, the molar concentration of the X element is 0.01-6.0 mol/L;
202, stirring and precipitating the solution B obtained in the step 201 for 0.5-3 h under the conditions that the pH value is 3.0-8.5 and the temperature is 25-80 ℃ to obtain slurry C; the reagent for adjusting the pH is a sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 0.2-3.0 mol/L;
and 203, carrying out hydrothermal treatment on the slurry C obtained in the step 202 at the temperature of 60-110 ℃ for 3-10 h, carrying out suction filtration, drying the retentate obtained by suction filtration at the temperature of 60-150 ℃ for 5-24 h, and grinding to obtain a second catalytic precursor.
The method as described above, wherein the second catalytic precursor includes a carrier containing a silicon element and an aluminum element, mo, bi, fe, co, X, Y, and Z.
The method described above, characterized in that the preparation of the first catalytic precursor in the first step specifically comprises:
step 101, mixing Mo-containing soluble salt, bi-containing soluble salt, fe-containing soluble salt and Co-containing soluble salt with water to obtain solution A; in the solution A, the molar concentration of the Mo element is 1.0-10.0 mol/L;
102, stirring and precipitating the solution A obtained in the step 101 for 0.5-6 hours under the conditions that the pH is 3.0-10.5 and the temperature is 25-80 ℃ to obtain slurry A; the reagent for adjusting the pH is a sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 0.2-3.0 mol/L;
103, adding silicon dioxide into the slurry A obtained in the step 102, and continuously stirring and precipitating for 0.5-6 h under the conditions that the pH is 3.0-10.5 and the temperature is 25-80 ℃ to obtain slurry B;
104, dividing the slurry B in the step 103 into two parts, wherein the mass of the first part accounts for 1/5-1/3 of the total mass of the slurry B, carrying out hydrothermal treatment on the first part at 60-110 ℃ for 3-10 h, carrying out suction filtration, drying the trapped substance at 60-150 ℃ for 5-24 h, and grinding to obtain a first catalytic precursor;
step two preparation of the second catalytic precursor specifically comprises:
step 201, mixing soluble salt containing X, soluble salt containing Y, soluble salt containing Z, soluble salt containing Al and water to obtain solution B; in the solution B, the molar concentration of the X element is 0.01-6.0 mol/L;
step 202, mixing the second part of slurry B in the step 104 with the solution B in the step 201 to obtain a mixed system;
step 203, stirring and precipitating the mixed system obtained in the step 202 for 0.5-3 h under the conditions that the pH value is 3.0-8.5 and the temperature is 25-80 ℃ to obtain slurry C; the reagent for adjusting the pH is a sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 0.2-3.0 mol/L;
and 204, carrying out hydrothermal treatment on the slurry C obtained in the step 203 at the temperature of 60-110 ℃ for 3-10 h, carrying out suction filtration, drying the retentate obtained by suction filtration at the temperature of 60-150 ℃ for 5-24 h, and grinding to obtain a second catalytic precursor.
The method is characterized in that the temperature rise rate of the roasting in the third step is 1-10 ℃/min.
The method described above, wherein the pH in step 102 and step 103 is 3.0 to 8.5.
The method is characterized in that the silicon dioxide in step 103 is modified silicon dioxide, and the preparation method of the modified silicon dioxide comprises the steps of soaking powder silicon dioxide in ammonia water for 1-12 h, filtering and drying to obtain modified silicon dioxide; the ammonia water comprises 20-30% by mass of ammonia based on the mass of the silicon dioxide powder which can be immersed.
Compared with the prior art, the invention has the following advantages:
1. the invention provides a catalyst for catalyzing propylene to be oxidized and synthesized into acrolein, which comprises a carrier and an active component, wherein the active component comprises Mo, bi, fe, co, X, Y and Z, the carrier is a mixture containing a Si element and an Al element, and the active component is combined with the carrier element to form Mo 12 Bi a Fe b Co c X d Y e Z f Si g Al h O i The structure has the advantages of high activity, stability and long service life in catalyzing the synthesis of acrolein by propylene oxidation.
2. The invention provides a method for preparing a catalyst for catalyzing propylene to be oxidized and synthesized into acrolein, which comprises the steps of preparing a carrier containing Si element and a first catalytic precursor of first active components Mo, bi, fe and Co, preparing a second catalytic precursor of the carrier containing the aluminum element and second active components X, Y and Z, mixing, grinding and roasting the first catalytic precursor and the second catalytic precursor, forming by roasting, and loading specific active components on different carriers respectively and then mixing, grinding and roasting.
3. The method for preparing the catalyst for synthesizing the acrolein by catalyzing the oxidation of the propylene comprises the steps of preparing the first catalytic precursor and the second catalytic precursor, wherein the method for preparing the first catalytic precursor and the second catalytic precursor comprises the steps of mixing, dissolving, stirring, precipitating and carrying out hydrothermal treatment, and the catalytic performance of active components on corresponding carriers can be exerted to the maximum extent.
4. The other method for preparing the first catalytic precursor and the second catalytic precursor further comprises the steps of dividing the slurry A into two parts, carrying out hydrothermal treatment on the first part of the slurry A to obtain the first catalytic precursor, mixing the second part of the slurry A with the solution B, and carrying out stirring, precipitation and hydrothermal treatment on the mixture to obtain the second catalytic precursor.
The technical solution of the present invention is further described in detail with reference to the following examples.
Detailed Description
Example 1
The embodiment provides a catalyst for catalyzing propylene to be oxidized and synthesized into acrolein, which comprises a carrier and active components, wherein the active components comprise Mo, bi, fe, co, mg, ti and Na;
in the active component, the active component is selected from,
the molar ratio of Bi to Mo is 2:12;
the molar ratio of Fe to Mo is 3:12;
the molar ratio of Co to Mo is 2:12;
the molar ratio of Mg to Mo is 3:12;
the molar ratio of Ti to Mo is 2:12;
the molar ratio of Na to Mo is 2:12;
the mass of the carrier is 20% of the mass of the catalyst, the carrier comprises Si and Al, and the molar ratio of the Si to the Al in the carrier is 3:2;
the embodiment provides a method for preparing the catalyst for catalyzing propylene to be oxidized and synthesized into the acrolein, which comprises the following steps:
step one, preparing a first catalytic precursor; the method of preparing the first catalytic precursor may comprise:
step 101, mixing 24.5g of ammonium molybdate, 3.78g of bismuth nitrate, 12.96g of ferric nitrate and 6.21g of cobalt nitrate with water at the temperature of 60-70 ℃, and stirring to uniformly mix to obtain a solution A; in the solution A, the molar concentration of the Mo element is 1.0mol/L;
102, stirring and precipitating the solution A obtained in the step 101 for 6 hours under the conditions that the pH value is 3.0 and the temperature is 25 ℃ to obtain slurry A; the reagent for adjusting the pH is a sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 0.2mol/L;
103, adding 430g of silicon dioxide into the slurry A obtained in the step 102, and continuously stirring and precipitating for 6 hours under the conditions that the pH value is 3.0 and the temperature is 25 ℃ to obtain slurry B; the silicon dioxide is modified silicon dioxide, and the preparation method of the modified silicon dioxide comprises the steps of soaking powder silicon dioxide in ammonia water for 1 hour, filtering and drying to obtain modified silicon dioxide; the mass of the ammonia water is based on the fact that the powdery silicon dioxide can be immersed, and the mass percentage of the ammonia in the ammonia water is 30%;
step 104, carrying out hydrothermal treatment on the slurry B obtained in the step 103 at 60 ℃ for 10 hours, carrying out suction filtration, drying the retentate at 60 ℃ for 24 hours, and grinding to obtain a first catalytic precursor;
step two, preparing a second catalytic precursor; the preparation method for preparing the second catalytic precursor may comprise:
step 201, under the temperature condition of 60-70 ℃, mixing 18.54g of magnesium nitrate, 7.93g of titanium chloride, 7.39g of sodium nitrate, 1791g of aluminum nitrate nonahydrate and water, and stirring to uniformly mix to obtain a solution B; in the solution B, the molar concentration of Mg element is 6.0mol/L;
step 202, stirring and precipitating the solution B obtained in the step 201 for 3 hours under the conditions that the pH value is 6 and the temperature is 25 ℃ to obtain slurry C; the reagent for adjusting the pH is a sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 3.0mol/L;
step 203, carrying out hydrothermal treatment on the slurry C obtained in the step 202 at the temperature of 60 ℃ for 10 hours, carrying out suction filtration, drying the retentate obtained by suction filtration at the temperature of 60 ℃ for 24 hours, and grinding to obtain a second catalytic precursor;
step three, mixing and grinding the first catalytic precursor in the step 104 and the second catalytic precursor in the step 203, extruding and forming, and roasting at 150 ℃ for 12 hours to obtain a catalyst for synthesizing acrolein by catalyzing propylene oxidation; the heating rate of the roasting is 1 ℃/min.
Example 2
The embodiment provides a catalyst for synthesizing acrolein by catalyzing propylene oxidation, which comprises a carrier and active components, wherein the active components comprise Mo, bi, fe, co, zn, zr and Na;
among the active components, the active components are,
the molar ratio of Bi to Mo is 2:12;
the molar ratio of Fe to Mo is 3:12;
the molar ratio of Co to Mo is 2:12;
the molar ratio of Zn to Mo is 3:12;
the molar ratio of Zr to Mo is 2:12;
the molar ratio of Na to Mo is 2:12;
the mass of the carrier is 50% of that of the catalyst, the carrier comprises Si and Al, and the molar ratio of the Si to the Al in the carrier is 4:9;
the embodiment provides a method for preparing the catalyst for synthesizing the acrolein by catalyzing the propylene oxidation, which comprises the following steps:
step one, preparing a first catalytic precursor; the method of preparing the first catalytic precursor may comprise:
step 101, mixing 24.5g of ammonium molybdate, 3.78g of bismuth nitrate, 12.96g of ferric nitrate and 6.21g of cobalt nitrate with water at the temperature of 60-70 ℃, and stirring to uniformly mix to obtain a solution A; in the solution A, the molar concentration of the Mo element is 10.0mol/L;
102, stirring and precipitating the solution A obtained in the step 101 for 0.5h under the conditions that the pH value is 8.5 and the temperature is 80 ℃ to obtain slurry A; the reagent for adjusting the pH is a sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 3.0mol/L;
103, adding 996g of silicon dioxide into the slurry A obtained in the step 102, and continuously stirring and precipitating for 0.5h under the conditions that the pH value is 8.5 and the temperature is 80 ℃ to obtain slurry B; the silicon dioxide is modified silicon dioxide, and the preparation method of the modified silicon dioxide comprises the steps of soaking powder silicon dioxide in ammonia water for 12 hours, filtering and drying to obtain the modified silicon dioxide; the mass of the ammonia water is based on the fact that the powdery silicon dioxide can be immersed, and the mass percentage of ammonia in the ammonia water is 20%;
step 104, carrying out hydrothermal treatment on the slurry B obtained in the step 103 at 110 ℃ for 3h, carrying out suction filtration, drying the retentate at 150 ℃ for 5h, and grinding to obtain a first catalytic precursor;
step two, preparing a second catalytic precursor; the preparation method for preparing the second catalytic precursor may comprise:
step 201, under the temperature condition of 60-70 ℃, 8.69g of zinc nitrate, 9.44g of zirconium nitrate, 7.39g of sodium nitrate, 14007g of aluminum nitrate nonahydrate and water are mixed and stirred to be uniformly mixed, so as to obtain a solution B; in the solution B, the molar concentration of Zn element is 0.01mol/L;
step 202, stirring and precipitating the solution B obtained in the step 201 for 0.5h under the conditions that the pH value is 8.5 and the temperature is 80 ℃ to obtain slurry C; the reagent for adjusting the pH is a sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 0.2mol/L;
step 203, carrying out hydrothermal treatment on the slurry C obtained in the step 202 at the temperature of 110 ℃ for 3 hours, carrying out suction filtration, drying the retentate obtained by suction filtration at the temperature of 150 ℃ for 5 hours, and grinding to obtain a second catalytic precursor;
step three, mixing and grinding the first catalytic precursor in the step 104 and the second catalytic precursor in the step 203, extruding and forming, and roasting at 600 ℃ for 0.5h to obtain a catalyst for synthesizing acrolein by catalyzing propylene oxidation; the heating rate of the roasting is 10 ℃/min.
Example 3
The embodiment provides a catalyst for catalyzing propylene to be oxidized and synthesized into acrolein, which comprises a carrier and active components, wherein the active components comprise Mo, bi, fe, co, ca, ti and Cs;
among the active components, the active components are,
the molar ratio of Bi to Mo is 2:12;
the molar ratio of Fe to Mo is 3:12;
the molar ratio of Co to Mo is 2:12;
the molar ratio of Ca to Mo is 3:12;
the molar ratio of Ti to Mo is 2:12;
the molar ratio of Cs to Mo is 2:12;
the mass of the carrier is 15% of that of the catalyst, the carrier comprises Si and Al, and the molar ratio of the Si to the Al in the carrier is 5:7;
the embodiment provides a method for preparing the catalyst for catalyzing propylene to be oxidized and synthesized into the acrolein, which comprises the following steps:
step one, preparing a first catalytic precursor; the method of preparing the first catalytic precursor may comprise:
step 101, mixing 24.5g of ammonium molybdate, 3.78g of bismuth nitrate, 12.96g of ferric nitrate and 6.21g of cobalt nitrate with water at the temperature of 60-70 ℃, and stirring to uniformly mix to obtain a solution A; in the solution A, the molar concentration of the Mo element is 5.0mol/L;
102, stirring and precipitating the solution A obtained in the step 101 for 3 hours under the conditions that the pH value is 6 and the temperature is 60 ℃ to obtain slurry A; the reagent for adjusting the pH is a sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 2.0mol/L;
103, adding 261g of silicon dioxide into the slurry A obtained in the step 102, and continuously stirring and precipitating for 3 hours under the conditions that the pH value is 6 and the temperature is 50 ℃ to obtain slurry B; the silicon dioxide is modified silicon dioxide, and the preparation method of the modified silicon dioxide comprises the steps of soaking powder silicon dioxide in ammonia water for 6 hours, filtering and drying to obtain the modified silicon dioxide; the mass of the ammonia water is based on the fact that the powdery silicon dioxide can be immersed, and the mass percentage of the ammonia in the ammonia water is 24%;
step 104, carrying out hydrothermal treatment on the slurry B obtained in the step 103 at 90 ℃ for 6 hours, carrying out suction filtration, drying the retentate at 100 ℃ for 18 hours, and grinding to obtain a first catalytic precursor;
step two, preparing a second catalytic precursor; the preparation method for preparing the second catalytic precursor may comprise:
step 201, mixing 12.31g of calcium nitrate, 7.93g of titanium chloride, 2.93g of cesium nitrate, 2286g of aluminum nitrate nonahydrate and water at the temperature of 60-70 ℃, and stirring to uniformly mix to obtain a solution B; in the solution B, the molar concentration of Ca element is 2mol/L;
step 202, stirring and precipitating the solution B obtained in the step 201 for 2 hours under the conditions that the pH value is 3.0 and the temperature is 60 ℃ to obtain slurry C; the reagent for adjusting the pH is a sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 1.5mol/L;
step 203, carrying out hydrothermal treatment on the slurry C obtained in the step 202 at the temperature of 90 ℃ for 6 hours, carrying out suction filtration, drying the retentate obtained by the suction filtration at the temperature of 120 ℃ for 16 hours, and grinding to obtain a second catalytic precursor;
step three, mixing and grinding the first catalytic precursor in the step 104 and the second catalytic precursor in the step 203, extruding and forming, and roasting at 300 ℃ for 6 hours to obtain a catalyst for synthesizing acrolein by catalyzing propylene oxidation; the heating rate of the roasting is 5 ℃/min.
Example 4
This example is the same as example 1 except that the pH was 9.0 in both step 102 and step 103.
Example 5
This example is the same as example 1 except that the pH was 10.5 in both step 102 and step 103.
Example 6
The embodiment provides a catalyst for synthesizing acrolein by catalyzing propylene oxidation, which comprises a carrier and active components, wherein the active components comprise Mo, bi, fe, co, ca, zr and Na;
in the active component, the active component is selected from,
the molar ratio of Bi to Mo is 10:12;
the molar ratio of Fe to Mo is 0.05:12;
the molar ratio of Co to Mo is 3:12;
the molar ratio of Ca to Mo is 10:12;
the molar ratio of Zr to Mo is 9:12;
the molar ratio of Na to Mo is 3.2:12;
the mass of the carrier is 5% of that of the catalyst, the carrier comprises Si and Al, and the molar ratio of the Si to the Al in the carrier is 2:0.5;
the catalyst of this example was prepared by the same method as in example 1.
Example 7
The embodiment provides a catalyst for synthesizing acrolein by catalyzing propylene oxidation, which comprises a carrier and active components, wherein the active components comprise Mo, bi, fe, co, mg, zr and K;
in the active component, the active component is selected from,
the molar ratio of Bi to Mo is 5:12;
the molar ratio of Fe to Mo is 9:12;
the molar ratio of Co to Mo is 0.2:12;
the molar ratio of Mg to Mo is 5:12;
the molar ratio of Zr to Mo is 6:12;
the molar ratio of K to Mo is 3:12;
the mass of the carrier is 50% of that of the catalyst, the carrier comprises Si and Al, and the molar ratio of the Si to the Al in the carrier is 1;
the catalyst of this example was prepared by the same method as in example 1.
Example 8
The embodiment provides a catalyst for synthesizing acrolein by catalyzing propylene oxidation, which comprises a carrier and active components, wherein the active components comprise Mo, bi, fe, co, zn, zr and Cs;
in the active component, the active component is selected from,
the molar ratio of Bi to Mo is 0.1:12;
the molar ratio of Fe to Mo is 2:12;
the molar ratio of Co to Mo is 5:12;
the molar ratio of Zn to Mo is 0.08:12;
the molar ratio of Zr to Mo is 0.01:12;
the molar ratio of Cs to Mo is 2:12;
the mass of the carrier is 25% of the mass of the catalyst, the carrier comprises Si and Al, and the molar ratio of the Si to the Al in the carrier is 3:7;
the catalyst of this example was prepared by the same method as in example 1.
Example 9
The embodiment provides a catalyst for catalyzing propylene to be oxidized and synthesized into acrolein, which comprises a carrier and active components, wherein the active components comprise Mo, bi, fe, co, mn, ti, na, K and Cs;
among the active components, the active components are,
the molar ratio of Bi to Mo is 5:12;
the molar ratio of Fe to Mo is 9:12;
the molar ratio of Co to Mo is 0.2:12;
the molar ratio of Mn to Mo is 5:12;
the molar ratio of Ti to Mo is 5:12;
the molar ratio of Na to Mo is 0.02, the molar ratio of K to Mo is 0.02, and the molar ratio of Cs to Mo is 0.06;
the mass of the carrier is 25% of that of the catalyst, the carrier comprises Si and Al, and the molar ratio of the Si to the Al in the carrier is 1:1.
the catalyst of this example was prepared by the same method as in example 1.
Example 10
The embodiment provides a catalyst for catalyzing propylene to be oxidized and synthesized into acrolein, which comprises a carrier and active components, wherein the active components comprise Mo, bi, fe, co, mg, ca, zn, mn, ti, na and K;
in the active component, the active component is selected from,
the molar ratio of Bi to Mo is 0.1:12;
the molar ratio of Fe to Mo is 2:12;
the molar ratio of Co to Mo is 5:12;
the molar ratio of Mg to Mo is 1:12;
the molar ratio of Ca to Mo is 3:12;
the molar ratio of Zn to Mo is 1.5:12;
the molar ratio of Mn to Mo is 0.5:12;
the molar ratio of Ti to Mo is 4:12;
the molar ratio of Na to Mo is 1:12, the molar ratio of K to Mo is 2.2:12;
the mass of the carrier is 5% of that of the catalyst, the carrier comprises Si and Al, and the molar ratio of the Si to the Al in the carrier is 3:10.
the catalyst of this example was prepared by the same method as in example 1.
Example 11
The embodiment provides a catalyst for synthesizing acrolein by catalyzing propylene oxidation, which comprises a carrier and active components, wherein the active components comprise Mo, bi, fe, co, mg, ca, zn, zr, na and Cs;
in the active component, the active component is selected from,
the molar ratio of Bi to Mo is 10:12;
the molar ratio of Fe to Mo is 0.5:12;
the molar ratio of Co to Mo is 3:12;
the molar ratio of Mg to Mo is 3:12;
the molar ratio of Ca to Mo is 3:12;
the molar ratio of Zn to Mo is 4:12;
the molar ratio of Zr to Mo is 0.01:12;
the molar ratio of Na to Mo is 1.5:12;
the molar ratio of Cs to Mo is 1.5:12;
the mass of the carrier is 15% of that of the catalyst, the carrier comprises Si and Al, and the molar ratio of the Si to the Al in the carrier is 1:5;
the catalyst of this example was prepared by the same method as in example 1.
Example 12
The embodiment provides a catalyst for catalyzing propylene to Be oxidized and synthesized into acrolein, which comprises a carrier and active components, wherein the active components comprise Mo, bi, fe, co, be, ti and Li;
in the active component, the active component is selected from,
the molar ratio of Bi to Mo is 0.1:12;
the molar ratio of Fe to Mo is 2:12;
the molar ratio of Co to Mo is 5:12;
the mole ratio of Be to Mo is 0.08:12;
the molar ratio of Ti to Mo is 0.01:12;
the molar ratio of Li to Mo is 0.1:12;
the mass of the carrier is 20% of that of the catalyst, the carrier comprises Si and Al, and the molar ratio of the Si to the Al in the carrier is 1;
the catalyst of this example was prepared by the same method as in example 1.
Example 13
The embodiment provides a catalyst for catalyzing propylene to be oxidized and synthesized into acrolein, which comprises a carrier and active components, wherein the active components comprise Mo, bi, fe, co, cu, ti, zr, li and Na;
among the active components, the active components are,
the molar ratio of Bi to Mo is 10:12;
the molar ratio of Fe to Mo is 0.05:12;
the molar ratio of Co to Mo is 3:12;
the molar ratio of Cu to Mo is 0.1:12;
the molar ratio of Ti to Mo is 4:12;
the molar ratio of Zr to Mo is 5:12;
the molar ratio of Li to Mo is 0.5:12;
the molar ratio of Na to Mo is 0.5:12;
the mass of the carrier is 50% of that of the catalyst, the carrier comprises Si and Al, and the molar ratio of the Si to the Al in the carrier is 1;
the catalyst of this example was prepared by the same method as in example 1.
Example 14
The embodiment provides a catalyst for synthesizing acrolein by catalyzing propylene oxidation, which comprises a carrier and active components, wherein the active components comprise Mo, bi, fe, co, mg, ca, be, cu, zn, mn, ti, li, na, K and Cs;
among the active components, the active components are,
the molar ratio of Bi to Mo is 5:12;
the molar ratio of Fe to Mo is 9:12;
the molar ratio of Co to Mo is 0.2:12;
the molar ratio of Mg to Mo is 1:12;
the molar ratio of Ca to Mo is 2:12;
the mole ratio of Be to Mo is 1.2:12;
the molar ratio of Cu to Mo is 1.8:12;
the molar ratio of Zn to Mo is 2:12;
the molar ratio of Mn to Mo is 2:12;
the molar ratio of Ti to Mo is 4:12;
the molar ratio of Li to Mo is 0.2:12;
the molar ratio of Na to Mo is 1.6:12;
the molar ratio of K to Mo is 1:12;
the molar ratio of Cs to Mo is 0.4:12;
the mass of the carrier is 20% of that of the catalyst, the carrier comprises Si and Al, and the molar ratio of the Si to the Al in the carrier is 1;
the catalyst of this example was prepared by the same method as in example 1.
Comparative example 1
This comparative example is the same as example 1 except that the silica is not modified in step 103.
Comparative example 2
This comparative example is the same as example 1 except that the temperature of the hydrothermal treatment in step 104 is 120 ℃; the temperature of the hydrothermal treatment in step 203 is 120 ℃.
Comparative example 3
This comparative example provides a catalyst that is the same as the catalyst of example 1 except that the support does not contain the Si element.
The comparative example was prepared by the same method as example 1, except that:
no silica is added in step 103.
The mass of aluminum nitrate nonahydrate added in step 201 was 4952g.
Comparative example 4
This comparative example is the same as example 1, except that,
step 104, directly drying the slurry B in the step 103 at 60 ℃ for 24 hours, and grinding to obtain a first catalytic precursor;
step 203, directly drying the slurry C obtained in the step 202 at 60 ℃ for 24 hours, and grinding to obtain a second catalytic precursor.
Comparative example 5
This comparative example is the same as example 1, except that,
stirring and mixing in the step 101 to obtain a solution A and stirring and mixing in the step 201 to obtain a solution B are both carried out at normal temperature; the normal temperature is 20-25 ℃.
Comparative example 6
This comparative example provides a catalyst that is the same as the catalyst of example 1 except that the support is a mixture containing Ti element and Al element, and the molar ratio of Ti element to Al element in the support is 3:2.
the comparative example was prepared in the same manner as example 1 except that:
473g of titanium dioxide were added to the slurry A from step 102 in step 103.
The mass of aluminum nitrate nonahydrate added in step 201 was 1477g.
Comparative example 7
The catalyst of this comparative example was the same as example 1.
The preparation method of the catalyst of the comparative example comprises the following steps:
step one, mixing 24.5g of ammonium molybdate, 3.78g of bismuth nitrate, 12.96g of ferric nitrate and 6.21g of cobalt nitrate with water at the temperature of 60-70 ℃, and stirring to uniformly mix to obtain a solution A; in the solution A, the molar concentration of the Mo element is 1.0mol/L;
step two, mixing the solution A, 18.54g of magnesium nitrate, 7.93g of titanium chloride, 7.39g of sodium nitrate, 1791g of aluminum nitrate nonahydrate, 430g of silicon dioxide and water at the temperature of 60-70 ℃, stirring, and then carrying out stirring precipitation for 3 hours at the pH of 6 and the temperature of 25 ℃ to obtain slurry; the reagent for adjusting the pH is sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 3.0mol/L;
step three, drying the slurry obtained in the step two at 60 ℃ for 24 hours, grinding, and roasting at 150 ℃ for 12 hours to obtain a catalyst for synthesizing acrolein by catalyzing propylene oxidation; the heating rate of the roasting is 1 ℃/min.
Example 15
This example provides a catalyst for catalytic oxidation of propylene to acrolein, the catalyst being the same as the catalyst of example 1;
the embodiment provides a method for preparing the catalyst for synthesizing the acrolein by catalyzing the propylene oxidation, which comprises the following steps:
step one, preparing a first catalytic precursor; the method of preparing the first catalytic precursor may comprise:
step 101, mixing 24.5g of ammonium molybdate, 3.78g of bismuth nitrate, 12.96g of ferric nitrate and 6.21g of cobalt nitrate with water at the temperature of 60-70 ℃, and stirring to uniformly mix to obtain a solution A; in the solution A, the molar concentration of Mo element is 1.0mol/L;
102, stirring and precipitating the solution A obtained in the step 101 for 6 hours under the conditions that the pH is 3.0 and the temperature is 25 ℃ to obtain slurry A; the reagent for adjusting the pH is a sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 0.2mol/L;
103, adding 430g of silicon dioxide into the slurry A obtained in the step 102, and continuously stirring and precipitating for 6 hours under the conditions that the pH value is 3.0 and the temperature is 25 ℃ to obtain slurry B; the preparation method of the modified silicon dioxide comprises the steps of soaking powder silicon dioxide in ammonia water for 1 hour, filtering and drying to obtain the modified silicon dioxide; the mass of the ammonia water is based on the fact that the powdery silicon dioxide can be immersed, and the mass percentage of the ammonia in the ammonia water is 30%;
104, dividing the slurry B in the step 103 into two parts, wherein the mass of the first part accounts for 1/5 of the total mass of the slurry B, carrying out hydrothermal treatment on the first part at 60 ℃ for 10 hours, carrying out suction filtration, drying the retentate at 60 ℃ for 24 hours, and grinding to obtain a first catalytic precursor;
step two, preparing a second catalytic precursor; the preparation method for preparing the second catalytic precursor may comprise:
step 201, under the temperature condition of 60-70 ℃, mixing 18.54g of magnesium nitrate, 7.93g of titanium chloride, 7.39g of sodium nitrate, 1791g of aluminum nitrate nonahydrate and water, and stirring to uniformly mix to obtain a solution B; in the solution B, the molar concentration of Mg element is 6.0mol/L;
step 202, mixing the second part of slurry B in the step 104 with the solution B in the step 201 to obtain a mixed system;
step 203, stirring and precipitating the mixed system obtained in the step 202 for 3 hours under the conditions that the pH value is 6 and the temperature is 25 ℃ to obtain slurry C; the reagent for adjusting the pH is sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 3.0mol/L;
step 204, carrying out hydrothermal treatment on the slurry C obtained in the step 203 at the temperature of 60 ℃ for 10 hours, carrying out suction filtration, drying the retentate obtained by suction filtration at the temperature of 60 ℃ for 24 hours, and grinding to obtain a second catalytic precursor;
step three, mixing and grinding the first catalytic precursor in the step 104 and the second catalytic precursor in the step 204, extruding and forming, and roasting at 150 ℃ for 12 hours to obtain a catalyst for synthesizing acrolein by catalyzing propylene oxidation; the heating rate of the roasting is 1 ℃/min.
Example 16
This example provides a catalyst for the catalytic oxidation of propylene to acrolein, which is the same as the catalyst of example 2;
the embodiment provides a method for preparing the catalyst for synthesizing the acrolein by catalyzing the propylene oxidation, which comprises the following steps:
step one, preparing a first catalytic precursor; the method of preparing the first catalytic precursor may comprise:
step 101, mixing 24.5g of ammonium molybdate, 3.78g of bismuth nitrate, 12.96g of ferric nitrate and 6.21g of cobalt nitrate with water at the temperature of 60-70 ℃, and stirring to uniformly mix to obtain a solution A; in the solution A, the molar concentration of the Mo element is 10.0mol/L;
102, stirring and precipitating the solution A obtained in the step 101 for 0.5h under the conditions that the pH value is 8.5 and the temperature is 80 ℃ to obtain slurry A; the reagent for adjusting the pH is a sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 3.0mol/L;
step 103, adding 996g of silicon dioxide into the slurry A obtained in the step 102, and continuously stirring and precipitating for 0.5h under the conditions that the pH is 8.5 and the temperature is 80 ℃ to obtain slurry B; the silicon dioxide is modified silicon dioxide, and the preparation method of the modified silicon dioxide comprises the steps of soaking powder silicon dioxide in ammonia water for 12 hours, filtering and drying to obtain the modified silicon dioxide; the mass of the ammonia water is based on the fact that the powdery silicon dioxide can be immersed, and the mass percentage of ammonia in the ammonia water is 20%;
104, dividing the slurry B in the step 103 into two parts, wherein the mass of the first part accounts for 1/3 of the total mass of the slurry B, carrying out hydrothermal treatment on the first part at 110 ℃ for 3 hours, carrying out suction filtration, drying the intercepted matters at 150 ℃ for 5 hours, and grinding to obtain a first catalytic precursor;
step two, preparing a second catalytic precursor; the preparation method for preparing the second catalytic precursor may comprise:
step 201, under the temperature condition of 60-70 ℃, 8.69g of zinc nitrate, 9.44g of zirconium nitrate, 7.39g of sodium nitrate, 14007g of aluminum nitrate nonahydrate and water are mixed and stirred to be uniformly mixed, so as to obtain a solution B; in the solution B, the molar concentration of Zn element is 0.01mol/L;
step 202, mixing the second part of slurry B in the step 104 with the solution B in the step 201 to obtain a mixed system;
step 203, stirring and precipitating the mixed system obtained in the step 202 for 0.5h under the conditions that the pH value is 8.5 and the temperature is 80 ℃ to obtain slurry C; the reagent for adjusting the pH is a sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 0.2mol/L;
step 204, carrying out hydrothermal treatment on the slurry C obtained in the step 203 at the temperature of 110 ℃ for 3 hours, carrying out suction filtration, drying the retentate obtained by suction filtration at the temperature of 150 ℃ for 5 hours, and grinding to obtain a second catalytic precursor;
step three, mixing and grinding the first catalytic precursor in the step 104 and the second catalytic precursor in the step 204, carrying out extrusion forming, and roasting at 600 ℃ for 0.5h to obtain a catalyst for synthesizing acrolein by catalyzing propylene oxidation; the heating rate of the roasting is 10 ℃/min.
Example 17
This example provides a catalyst for the catalytic oxidation of propylene to acrolein, which is the same as the catalyst of example 3;
the embodiment provides a method for preparing the catalyst for synthesizing the acrolein by catalyzing the propylene oxidation, which comprises the following steps:
step one, preparing a first catalytic precursor; the method of preparing the first catalytic precursor may comprise:
step 101, mixing 24.5g of ammonium molybdate, 3.78g of bismuth nitrate, 12.96g of ferric nitrate and 6.21g of cobalt nitrate with water at the temperature of 60-70 ℃, and stirring to uniformly mix to obtain a solution A; in the solution A, the molar concentration of the Mo element is 5.0mol/L;
102, stirring and precipitating the solution A obtained in the step 101 for 3 hours under the conditions that the pH value is 6 and the temperature is 60 ℃ to obtain slurry A; the reagent for adjusting the pH is a sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 2.0mol/L;
103, adding 261g of silicon dioxide into the slurry A obtained in the step 102, and continuously stirring and precipitating for 3 hours under the conditions that the pH value is 6 and the temperature is 50 ℃ to obtain slurry B; the silicon dioxide is modified silicon dioxide, and the preparation method of the modified silicon dioxide comprises the steps of soaking powder silicon dioxide in ammonia water for 6 hours, filtering and drying to obtain modified silicon dioxide; the mass of the ammonia water is based on the fact that the powdery silicon dioxide can be immersed, and the mass percentage of the ammonia in the ammonia water is 24%;
104, dividing the slurry B in the step 103 into two parts, wherein the mass of the first part accounts for 1/4 of the total mass of the slurry B, carrying out hydrothermal treatment on the first part at 90 ℃ for 6 hours, carrying out suction filtration, drying the retentate at 100 ℃ for 18 hours, and grinding to obtain a first catalytic precursor;
step two, preparing a second catalytic precursor; the preparation method for preparing the second catalytic precursor may comprise:
step 201, under the temperature condition of 60-70 ℃, mixing 12.31g of calcium nitrate, 7.93g of titanium chloride, 2.93g of cesium nitrate, 2286g of aluminum nitrate nonahydrate and water, and stirring to uniformly mix to obtain a solution B; in the solution B, the molar concentration of Ca element is 2mol/L;
step 202, mixing the second part of slurry B in the step 104 with the solution B in the step 201 to obtain a mixed system;
step 203, stirring and precipitating the mixed system obtained in the step 202 for 2 hours under the conditions that the pH value is 3.0 and the temperature is 60 ℃ to obtain slurry C; the reagent for adjusting the pH is a sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 1.5mol/L;
step 204, carrying out hydrothermal treatment on the slurry C obtained in the step 203 at the temperature of 90 ℃ for 6 hours, carrying out suction filtration, drying the retentate obtained by the suction filtration at the temperature of 120 ℃ for 16 hours, and grinding to obtain a second catalytic precursor;
step three, mixing and grinding the first catalytic precursor in the step 104 and the second catalytic precursor in the step 204, extruding and forming, and roasting at 300 ℃ for 6 hours to obtain a catalyst for synthesizing acrolein by catalyzing propylene oxidation; the heating rate of the roasting is 5 ℃/min.
Example 18
This example provides a catalyst for the catalytic oxidation of propylene to acrolein, which is the same as the catalyst of example 1;
this example provides a process for preparing the above catalyst for catalytic oxidation of propylene to acrolein, which is the same as that of example 15, except that: the pH was 9.0 in both step 102 and step 103.
Example 19
This example provides a catalyst for the catalytic oxidation of propylene to acrolein, which is the same as the catalyst of example 1;
this example provides a process for preparing the above catalyst for the catalytic oxidation of propylene to acrolein, which is the same as that of example 15 except that: the pH in both step 102 and step 103 was 10.5.
Examples 20 to 28
The compositions of the active components of the catalysts of the examples 20 to 28 and the mass percentage of the carrier in the catalysts are the same as those of the examples 6 to 14, and the preparation methods of the catalysts of the examples 20 to 28 are the same as those of the example 15.
Comparative example 8
This comparative example is the same as example 15 except that the silica is not modified in step 103.
Comparative example 9
This comparative example is the same as example 15 except that the temperature of the hydrothermal treatment in step 104 is 120 ℃; the temperature of the hydrothermal treatment in step 204 is 120 ℃.
Comparative example 10
This comparative example provides a catalyst that is the same as the catalyst of example 15 except that the support does not contain the Si element.
This comparative example was prepared in the same manner as example 15 except that:
no silica is added in step 103.
The mass of aluminum nitrate nonahydrate added in step 201 was 4952g.
Comparative example 11
This comparative example is the same as example 15, except that,
step 104, dividing the slurry B in the step 103 into two parts, wherein the mass of the first part accounts for 1/5 of the total mass of the slurry B, drying the first part at 60 ℃ for 24 hours, and grinding to obtain a first catalytic precursor;
step 204 is to directly dry the slurry C obtained in the step 203 at 60 ℃ for 24 hours, and grind to obtain a second catalytic precursor.
Comparative example 12
This comparative example is the same as example 15, except that,
stirring and mixing in the step 101 to obtain a solution A and stirring and mixing in the step 201 to obtain a solution B are both carried out at normal temperature; the normal temperature is 20-25 ℃.
Comparative example 13
This comparative example provides a catalyst that is the same as the catalyst of example 15 except that the support is a mixture containing Ti element and Al element, and the molar ratio of Ti element to Al element in the support is 3:2.
this comparative example was prepared in the same manner as example 15 except that:
473g of titanium dioxide were added to the slurry A from step 102 in step 103.
The mass of aluminum nitrate nonahydrate added in step 201 was 1477g.
Performance evaluation:
350g of each of the catalysts of examples 1 to 28 and comparative examples 1 to 13 was placed in a fixed bed single-tube reactor (inner diameter 25.4mm, length 2000 mm) at a reaction temperature of 370 ℃ in the presence of a catalyst prepared from the following raw material, propylene: air: the volume ratio of water vapor is 10:75:15, the reaction space velocity is 1300h -1 The reaction was carried out to obtain a propylene conversion and an acrolein single pass yield as shown in Table 1.
Wherein,
propylene conversion (%) = total moles of propylene reacted/total moles of propylene in the feedstock × 100%;
acrolein single pass yield (%) = moles of propylene converted to acrolein/total moles of propylene supplied × 100%.
Table 1 shows the propylene conversion and acrolein single-pass yield for examples 1 to 28 and comparative examples 1 to 13
According to Table 1, the catalysts of examples 1-28 have high reaction performance, corresponding to a propylene conversion rate of not less than 90%, and up to 98.9%, and a single-pass yield of acrolein of not less than 90%, and up to 94.3%.
And (3) testing the stability:
the stability test of the catalyst for synthesizing acrolein by catalyzing propylene oxidation in example 3 is carried out for 4000 hours continuously, the test conditions are the same as the performance test conditions, the conversion rate of propylene is 97.9%, the once-through yield of acrolein is 93.1%, and compared with the conversion rate of propylene of 98.6% corresponding to a fresh catalyst, the once-through yield of acrolein is 93.5%, and the reaction performance of the catalyst is basically unchanged, so that the catalyst has the characteristics of high stability and stable performance.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (8)
1. The catalyst for synthesizing acrolein by catalyzing propylene oxidation is characterized by comprising a carrier and active components, wherein the active components comprise Mo, bi, fe, co, X, Y and Z;
in the active component, the molar ratio of Bi to Mo is (0.1 to 10): 12; the molar ratio of Fe to Mo is (0.05-9): 12; the molar ratio of Co to Mo is (0.2 to 5): 12; the molar ratio of X to Mo is (0.08-10): 12; the molar ratio of Y to Mo is (0.01-9): 12; the molar ratio of Z to Mo is (0.1 to 3.2): 12;
x is one or more of Mg, ca, be, cu, zn and Mn; the Y is one or two of Ti and Zr; z is one or more of Li, na, K and Cs;
the catalyst comprises 5-50% of a carrier by mass, wherein the carrier comprises a Si element and an Al element, and the molar ratio of the Si element to the Al element in the carrier is (0.2-15): (0.05 to 15);
the catalyst for catalyzing propylene to be oxidized and synthesized into the acrolein is prepared by the following method, and the method comprises the following steps of:
step one, preparing a first catalytic precursor; the first catalytic precursor comprises a carrier containing Si element, mo, bi, fe and Co;
step two, preparing a second catalytic precursor; the second catalytic precursor comprises a support comprising an aluminum element, X, Y and Z;
step three, mixing and grinding the first catalytic precursor in the step one and the second catalytic precursor in the step two, carrying out extrusion forming, and roasting at the temperature of 150-600 ℃ for 0.5-12h to obtain a catalyst for synthesizing acrolein by catalyzing propylene oxidation;
step one the method of preparing the first catalytic precursor specifically comprises:
step 101, mixing Mo-containing soluble salt, bi-containing soluble salt, fe-containing soluble salt and Co-containing soluble salt with water at the temperature of 60-70 ℃ to obtain solution A; in the solution A, the molar concentration of the Mo element is 1.0-10.0 mol/L;
102, stirring and precipitating the solution A in the step 101 for 0.5 to 6 hours under the conditions that the pH is 3.0 to 10.5 and the temperature is 25 to 80 ℃ to obtain slurry A; a reagent for adjusting the pH is a sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 0.2-3.0 mol/L;
103, adding silicon dioxide into the slurry A obtained in the step 102, and continuously stirring and precipitating for 0.5-6 h under the conditions that the pH is 3.0-10.5 and the temperature is 25-80 ℃ to obtain slurry B;
step 104, carrying out hydrothermal treatment on the slurry B in the step 103 at 60-110 ℃ for 3-10h, carrying out suction filtration, drying the retentate at 60-150 ℃ for 5-24h, and grinding to obtain a first catalytic precursor;
step two the preparation method of the second catalytic precursor specifically includes:
step 201, mixing soluble salt containing X, soluble salt containing Y, soluble salt containing Z, soluble salt containing Al and water at the temperature of 60-70 ℃ to obtain solution B; in the solution B, the molar concentration of the X element is 0.01-6.0 mol/L;
202, stirring and precipitating the solution B in the step 201 for 0.5 to 3h under the conditions that the pH value is 3.0 to 8.5 and the temperature is 25 to 80 ℃ to obtain slurry C; a reagent for adjusting the pH value is a sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 0.2-3.0 mol/L;
step 203, carrying out hydrothermal treatment on the slurry C obtained in the step 202 at the temperature of 60-110 ℃ for 3-10h, carrying out suction filtration, drying the retentate obtained by the suction filtration at the temperature of 60-150 ℃ for 5-24h, and grinding to obtain a second catalytic precursor;
step 103, soaking the powdery silicon dioxide in ammonia water for 1h to 12h, filtering and drying to obtain modified silicon dioxide; the mass of the ammonia water is based on the fact that the powdery silicon dioxide can be immersed, and the mass percentage of ammonia in the ammonia water is 20% -30%.
2. The catalyst for catalyzing the oxidation of propylene to acrolein and is used as claimed in claim 1, wherein X is one or more of Mg, ca, zn and Mn; z is one or more of Na, K and Cs; the mass percentage of the carrier in the catalyst is 15-50%, and the molar ratio of the Si element to the Al element in the carrier is (3-5): (2 to 9).
3. The catalyst for catalytic oxidation of propylene to acrolein according to claim 1, wherein the temperature rise rate of the calcination in the third step is 1 ℃/min to 10 ℃/min.
4. The catalyst for catalytic oxidation of propylene to acrolein according to claim 1, wherein the pH values in steps 102 and 103 are 3.0 to 8.5.
5. The catalyst for synthesizing acrolein by catalyzing propylene oxidation is characterized by comprising a carrier and active components, wherein the active components comprise Mo, bi, fe, co, X, Y and Z;
in the active component, the molar ratio of Bi to Mo is (0.1 to 10): 12; the molar ratio of Fe to Mo is (0.05-9): 12; the molar ratio of Co to Mo is (0.2 to 5): 12; the molar ratio of X to Mo is (0.08-10): 12; the molar ratio of Y to Mo is (0.01-9): 12; the molar ratio of Z to Mo is (0.1 to 3.2): 12;
x is one or more of Mg, ca, be, cu, zn and Mn; the Y is one or two of Ti and Zr; z is one or more of Li, na, K and Cs;
the catalyst comprises 5-50% of a carrier by mass, wherein the carrier comprises a Si element and an Al element, and the molar ratio of the Si element to the Al element in the carrier is (0.2-15): (0.05 to 15);
the catalyst for catalyzing the oxidation of propylene to synthesize the acrolein is prepared by the following method, and the method comprises the following steps:
step one, preparing a first catalytic precursor; the first catalytic precursor comprises a carrier containing Si element, mo, bi, fe and Co;
step two, preparing a second catalytic precursor; the second catalytic precursor comprises a carrier containing silicon element and aluminum element, mo, bi, fe, co, X, Y and Z;
step three, mixing and grinding the first catalytic precursor in the step one and the second catalytic precursor in the step two, carrying out extrusion forming, and roasting at the temperature of 150-600 ℃ for 0.5-12h to obtain a catalyst for synthesizing acrolein by catalyzing propylene oxidation;
step one preparation of the first catalytic precursor specifically comprises:
step 101, mixing Mo-containing soluble salt, bi-containing soluble salt, fe-containing soluble salt and Co-containing soluble salt with water at the temperature of 60-70 ℃ to obtain solution A; in the solution A, the molar concentration of Mo element is 1.0-10.0 mol/L;
102, stirring and precipitating the solution A in the step 101 for 0.5 to 6 hours at the pH of 3.0 to 10.5 and the temperature of 25 to 80 ℃ to obtain slurry A; a reagent for adjusting the pH value is a sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 0.2-3.0 mol/L;
103, adding silicon dioxide into the slurry A obtained in the step 102, and continuously stirring and precipitating for 0.5-6 h under the conditions that the pH is 3.0-10.5 and the temperature is 25-80 ℃ to obtain slurry B;
104, dividing the slurry B in the step 103 into two parts, wherein the mass of the first part accounts for 1/5 to 1/3 of the total mass of the slurry B, carrying out hydrothermal treatment on the first part at 60-110 ℃ for 3 h-10h, carrying out suction filtration, drying the intercepted material at 60-150 ℃ for 5 h-24h, and grinding to obtain a first catalytic precursor;
step two preparation of the second catalytic precursor specifically comprises:
step 201, mixing soluble salt containing X, soluble salt containing Y, soluble salt containing Z, soluble salt containing Al and water at the temperature of 60-70 ℃ to obtain solution B; in the solution B, the molar concentration of the X element is 0.01-6.0 mol/L;
step 202, mixing the second part of slurry B in the step 104 with the solution B in the step 201 to obtain a mixed system;
203, stirring and precipitating the mixed system obtained in the step 202 for 0.5h to 3h under the conditions that the pH value is 3.0 to 8.5 and the temperature is 25 ℃ to 80 ℃ to obtain slurry C; a reagent for adjusting the pH is a sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 0.2-3.0 mol/L;
204, carrying out hydrothermal treatment on the slurry C obtained in the step 203 at the temperature of 60-110 ℃ for 3-10h, carrying out suction filtration, drying the retentate obtained by the suction filtration at the temperature of 60-150 ℃ for 5-24h, and grinding to obtain a second catalytic precursor;
step 103, soaking the powdery silicon dioxide in ammonia water for 1h to 12h, filtering and drying to obtain modified silicon dioxide; the mass of the ammonia water is based on the fact that the powdery silicon dioxide can be immersed, and the mass percentage of the ammonia in the ammonia water is 20% -30%.
6. The catalyst for catalyzing the oxidation of propylene to acrolein according to claim 5, wherein X is one or more of Mg, ca, zn and Mn; z is one or more of Na, K and Cs; the mass percentage of the carrier in the catalyst is 15-50%, and the molar ratio of the Si element to the Al element in the carrier is (3-5): (2 to 9).
7. The catalyst for catalytic oxidation of propylene to acrolein according to claim 5, wherein the temperature rise rate of the calcination in the third step is 1 ℃/min to 10 ℃/min.
8. The catalyst of claim 5, wherein the pH ranges from 3.0 to 8.5 in steps 102 and 103.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101690900A (en) * | 2009-10-21 | 2010-04-07 | 中国海洋石油总公司 | Method for preparing catalyst for acrolein and acrylic acid |
| CN101850259A (en) * | 2010-06-01 | 2010-10-06 | 上海华谊丙烯酸有限公司 | Preparation method of catalyst of acrolein through propylene oxidation at high airspeed |
| CN103418401A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Catalyst for preparing acrolein by propylene oxidation method and preparation method thereof |
| CN103816917A (en) * | 2014-03-14 | 2014-05-28 | 厦门大学 | Propylene selective-oxidation prepared acrolein catalyst and preparation method thereof |
| CN111068696A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Supported acrolein catalyst and application thereof |
| CN111068698A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst for preparing acrolein by propylene oxidation and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2343124B1 (en) * | 2001-11-08 | 2021-01-06 | Mitsubishi Chemical Corporation | METHOD FOR PREPARATION of a COMPOSITE OXIDE CATALYST |
| CN1931434A (en) * | 2006-09-29 | 2007-03-21 | 浙江大学 | Prepn process of catalyst for catalytic oxidation of propane to prepare acryl aldehyde |
| EP3219386A1 (en) * | 2016-03-14 | 2017-09-20 | Evonik Degussa GmbH | Method for the hydrothermal preparation of molybdenum-bismuth-cobalt-iron-based mixed oxide catalysts |
-
2021
- 2021-02-09 CN CN202110176717.1A patent/CN112958103B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101690900A (en) * | 2009-10-21 | 2010-04-07 | 中国海洋石油总公司 | Method for preparing catalyst for acrolein and acrylic acid |
| CN101850259A (en) * | 2010-06-01 | 2010-10-06 | 上海华谊丙烯酸有限公司 | Preparation method of catalyst of acrolein through propylene oxidation at high airspeed |
| CN103418401A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Catalyst for preparing acrolein by propylene oxidation method and preparation method thereof |
| CN103816917A (en) * | 2014-03-14 | 2014-05-28 | 厦门大学 | Propylene selective-oxidation prepared acrolein catalyst and preparation method thereof |
| CN111068696A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Supported acrolein catalyst and application thereof |
| CN111068698A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst for preparing acrolein by propylene oxidation and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 丙烯氧化合成丙烯酸工艺及催化剂的研究进展;张立岩等;《石油化工》;20101231(第07期);第818-822页 * |
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