CN115957742A - Catalyst for preparing acrylic acid by acrolein oxidation and preparation method and application thereof - Google Patents
Catalyst for preparing acrylic acid by acrolein oxidation and preparation method and application thereof Download PDFInfo
- Publication number
- CN115957742A CN115957742A CN202111183757.5A CN202111183757A CN115957742A CN 115957742 A CN115957742 A CN 115957742A CN 202111183757 A CN202111183757 A CN 202111183757A CN 115957742 A CN115957742 A CN 115957742A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- solution
- highest position
- desorption
- peak
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst for preparing acrylic acid by acrolein oxidation and a preparation method and application thereof. The catalyst comprises a carrier and an active component, wherein the active component comprises a composite metal oxide containing a V element, a Mo element, a Nb element, a Tl element, a transition metal element and an alkali metal element. The catalyst of the invention has the advantages of low abrasion and high yield of acrylic acid.
Description
Technical Field
The invention relates to the field of preparation of acrylic acid, and particularly relates to a catalyst for preparing acrylic acid by oxidizing acrolein and a preparation method and application thereof.
Background
Acrylic acid is an important organic chemical raw material, is mainly used for manufacturing multifunctional high polymer materials such as acrylates, and is widely applied to the fields of papermaking, leather, coating, textile, plastics, rubber, oil additives, petroleum exploitation and the like. In recent years, the market demand for acrylic acid has increased worldwide, and the production of acrylic acid has been a focus of research.
The catalyst used for synthesizing acrylic acid by acrolein oxidation method is generally Mo-V series oxide, and other elements for improving the catalyst performance, such as Nb, sn, cr, W, fe, co, ni, sb and the like, are generally added besides Mo and V elements. US7220698 discloses a catalyst for catalytic gas phase oxidation of acrolein and a method for producing acrylic acid by catalytic gas phase oxidation using the catalyst, which uses Mo-V as an essential component, controls hot spots of a catalyst reaction bed by introducing a trace amount of catalyst poison into a catalyst preparation process, inhibits thermal degradation of the catalyst, and thereby improves acrolein conversion rate. US7456129 discloses a carrier for a gas phase oxidation catalyst suitable for the selective oxidation of acrolein to produce acrylic acid and a method for producing the same, which improves the selectivity of acrylic acid by improving the catalyst performance by controlling the strength of the carrier acid, but the yield of acrylic acid is yet to be further improved. CN111659408A discloses a preparation method of acrylic acid catalyst by acrolein oxidation, which is characterized in that Mo element is taken as a reference, V, ni, cu and other elements are added, and salts or corresponding oxides thereof are subjected to coprecipitation reaction or physical compounding to obtain the catalyst, and the catalyst is spherical, cylindrical or special in geometric shape, and finally calcined to endow the catalyst with activity to form a catalyst product.
The acrylic acid catalyst can be prepared by the methods and the performance of the catalyst is improved, but the catalyst has poor mechanical strength and low catalytic activity ratio, and is limited in practical application, so that the acrylic acid catalyst with high acrylic acid yield and low abrasion needs to be further researched.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a catalyst for preparing acrylic acid by acrolein oxidation and a preparation method and application thereof. The catalyst of the invention has the advantages of low abrasion and high yield of acrylic acid.
The invention provides a catalyst for preparing acrylic acid by acrolein oxidation, which comprises a carrier and an active component, wherein the active component comprises a composite metal oxide containing a V element, a Mo element, a Nb element, a Tl element, a transition metal element and an alkali metal element.
The active ingredient may be represented by formula (1):
VMo a Nb b Tl c X d Z e O f formula (1)
In the formula (1), X represents a transition metal element, Z represents an alkali metal element, and a, b, c, d and e represent molar ratios of Mo, nb, tl, X, Z and V, respectively. a is 1.0 to 10.0; b is 0.1 to 1.0; c is 0.1 to 1.0; d is 0.05 to 1.0; e is 0.05 to 1.0; f is the mole number of oxygen atoms required to satisfy the valence of other elements in the active component. Preferably a is 2.0 to 6.0; b is 0.2 to 0.6; c is 0.1 to 0.5; d is 0.1 to 0.5; e is 0.1 to 0.6. More preferably, a is 3.0 to 5.0; b is 0.3 to 0.5; c is 0.1 to 0.3; d is 0.1 to 0.3; e is 0.1 to 0.3.
Further, the transition metal element is one or more of Sc element, tl element, Y element, zr element, hf element, ta element, cr element, W element, mn element, tc element, re element, fe element, ru element, os element, co element, rh element, ir element, ni element, pd element, pt element, cu element, ag element, au element, zn element and Cd element; preferably one or more of Ta element, zr element, Y element, hf element and W element. The alkali metal element is one or more of Li element, na element, K element, rb element and Cs element, and is preferably Na element and/or K element.
Further, the carrier is selected from one or more of lithium oxide, magnesium oxide, aluminum oxide, zirconium dioxide, silicon dioxide, titanium dioxide, vanadium dioxide, diatomite, kaolin and pumice.
Further, based on the weight of the catalyst, the content of the carrier is 20-60%, and the content of the active component is 40-80%.
Furthermore, two desorption peaks exist in the ammonia temperature programmed desorption curve of the catalyst, and the relative intensities of the two desorption peaks are different, wherein the temperature corresponding to the highest position of the stronger desorption peak is 175-250 ℃, and the temperature corresponding to the highest position of the weaker desorption peak is 300-350 ℃.
Further, the ratio of the relative intensity corresponding to the highest position of the stronger desorption peak to the relative intensity corresponding to the highest position of the weaker desorption peak is (1.5-2.5): 1.
Further, the temperature difference corresponding to the highest position of the stronger desorption peak and the highest position of the weaker desorption peak is 90-130 ℃; and/or the ratio of the peak area of the stronger desorption peak to the peak area of the weaker desorption peak is (10-50): 1.
The second aspect of the present invention provides a method for preparing an acrylic acid catalyst by oxidation of acrolein, comprising the steps of:
1) Mixing a precursor containing Nb element and Tl element with a dispersion medium to obtain a solution I;
2) Mixing a precursor containing a V element, a Mo element, a transition metal element and an alkali metal element with a dispersion medium to obtain a solution II;
3) Mixing the solution I obtained in the step 1) and the solution II obtained in the step 2) to obtain a solution III;
4) Impregnating the solution III obtained in the step 3) into a catalyst carrier, and then drying and roasting to obtain the catalyst.
Further, in the step 1), the precursor containing the Nb element is at least one of niobium oxalate, niobium oxide and ammonium niobate oxalate hydrate; the precursor containing the Tl element is at least one of thallium nitrate, thallium carbonate and thallium oxide.
Further, the molar ratio of the Mo element to the V element is (1.0-10.0): 1, preferably (2.0-8.0): 1; and/or the molar ratio of the Nb element to the V element is (0.1-1.0): 1, preferably (0.2-0.6): 1; and/or the molar ratio of the Tl element to the V element is (0.1-1.0): 1, preferably (0.1-0.5): 1; and/or the molar ratio of the Nb element to the Tl element is (1-5): 5-1, preferably (1-3): 3-1, and more preferably (1-3): 1.
Further, the molar ratio of the transition metal element to the V element is (0.05-1.0): 1, preferably (0.1-0.5): 1; the molar ratio of the alkali metal element to the V element is (0.05-1.0): 1, preferably (0.1-0.6): 1.
Further, in the step 2), the precursor containing the V element is ammonium metavanadate; the precursor containing Mo element is ammonium molybdate; the precursor of the transition metal element is nitrate and/or ammonium salt of the transition metal, and the precursor of the alkali metal element is nitrate and/or ammonium salt of the alkali metal.
Further, the dispersion medium in both solution I and solution II is or is mainly water. When preparing the solution I and the solution II, the dispersion medium can be heated to 60-90 ℃, and then precursors of corresponding elements are added.
Further, in step 3), the solution I is preferably added to the solution II.
Further, in step 3), the pH of the resulting solution III is controlled to 1 to 6, preferably 2 to 4. Acidic solutions may be used to control the pH of solution III. The acidic solution is one or more solutions selected from nitric acid, citric acid and formic acid.
Further, in the step 3), the temperature of the solution I is 10 to 50 ℃, preferably 20 to 30 ℃, and the temperature of the solution II is 10 to 50 ℃, preferably 20 to 30 ℃ before mixing.
Further, in step 4), the catalyst support is treated with the surface treatment solution and then immersed in the solution III. The surface treatment liquid is a mixture of polyacrylamide and water, and the treatment time is 10min to 300min, preferably 30min to 100min.
Preferably, the polyacrylamide has a molecular weight of: 800 to 2000 ten thousand, preferably 800 to 1200 ten thousand; the mass concentration of the surface treatment liquid is as follows: 1 to 25%, preferably 5 to 15%; the pH of the surface treatment liquid is 6 to 10, preferably 7 to 9. The mass ratio of the polyacrylamide to the catalyst carrier is 0.1-5, preferably 0.2-1.
Further, in step 4), the drying conditions include: the temperature is 60-150 ℃; the time is 1-48 h. The roasting treatment conditions comprise: the temperature is 300-500 ℃; the time is 1-72 h. The roasting atmosphere is an inert atmosphere or an oxygen-containing atmosphere, preferably, the inert atmosphere is a nitrogen atmosphere, the oxygen content in the oxygen-containing atmosphere is 10-30%, and air is preferred.
The third aspect of the present invention provides a use of the above catalyst or the catalyst obtained by the above production method for producing acrylic acid by selective oxidation of acrolein.
The application is as follows: acrolein is contacted with an oxygen-containing gas in the presence of the catalyst and a dilute gas phase feed to obtain acrylic acid.
Further, the dilute gas phase material is water vapor. The oxygen-containing gas is air, pure oxygen or oxygen-enriched.
Further, the contacting conditions include: the temperature is 200-350 ℃; the volume ratio of the acrolein to the oxygen-containing gas is 1 (1-12); the volume ratio of the acrolein to the dilute gas phase material is 1 (0.5-5), and the total volume space velocity is 800h -1 ～3000h -1 。
Compared with the prior art, the invention has the following advantages:
when the catalyst is used for preparing acrylic acid by selectively oxidizing acrolein, the yield of the acrylic acid can reach more than 89 percent, even can reach 91 percent, and the abrasion can reach less than 1.5 percent, even can reach less than 0.9 percent.
The preparation method is simple, and the yield of the catalyst acrylic acid can be effectively improved through the mutual matching of the steps.
Drawings
FIG. 1 shows temperature programmed desorption (NH) of ammonia gas of the catalysts obtained in example 1 and comparative example 1 3 -TPD) profile.
Detailed Description
The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following examples.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are commercially available, and are not indicated by manufacturers.
In the present invention, the catalyst performance is evaluated as follows:
a reactor: a fixed bed microreactor with an internal diameter of 10 mm and a reactor length of 330 mm;
catalyst loading amount: 1 g;
reaction temperature: 270 ℃;
reaction time: 4 hours;
the volume ratio of raw materials is as follows: acrolein: air: steam =1:8:2;
total volume space velocity: 1300h -1 。
In the present invention, the method for evaluating the catalyst abrasion is as follows:
20g of catalyst was placed in a attrition exponent measuring device, vibrated rotationally, and after 30min, the broken catalyst particles were sieved out and weighed. The proportion of the damaged catalyst is the catalyst attrition.
In the present invention, NH 3 The TPD profile was obtained as follows:
(1) Weighing 0.2g of 20-40 mesh sample, and filling the sample into a U-shaped quartz tube; (2) purging with helium for 2h, and heating to 400 ℃; (3) cooling to room temperature, and adsorbing ammonia gas for 30min; (4) And heating to 400 ℃ at a heating rate of 10 ℃/min, and recording a curve.
In the following embodiments, "g" represents the number of moles of oxygen atoms required to satisfy the valences of other elements in the active component.
Example 1
1) Niobium oxalate containing 0.04 mol of Nb (molecular formula: c 10 H 5 NbO 20 ) With thallium nitrate containing 0.02 mol Tl (molecular formula: tlNO 3 ) Mixing and dissolving in hot water at 80 ℃, and cooling to room temperature to obtain solution I.
2) Ammonium metavanadate (molecular formula: NH 4 VO 3 ) Ammonium molybdate containing 0.4 mol of Mo (molecular formula: (NH) 4 ) 2 MoO 4 ) And 0.02 mol of W of ammonium tungstate (molecular formula: (NH) 4 ) 10 W 12 O 41 ) Sodium nitrate containing 0.02 mol of Na (molecular formula: naNO 3 ) Respectively dissolving the two components in hot water of 80 ℃ and cooling to room temperature to obtain a solution II.
3) Adding the solution I into the solution II at room temperature at the rate of 20mL/min, uniformly mixing, and adjusting the pH value of the solution to 3.0 by using 0.1 mol/L nitric acid. Then stirring and evaporating at 80 ℃ until the mixed material solution is equivalent to VMo containing active component 4 Nb 0.4 Tl 0.2 W 0.2 Na 0.2 O g Was 0.5g/g, to obtain a solution III.
4) 1g of polyacrylamide having a molecular weight of 800 ten thousand was mixed with 10g of water, and the pH of the mixture was adjusted to 8.0 using 0.1 mol/liter of aqueous ammonia to obtain a surface treatment liquid. The surface treatment liquid was mixed with 100g of spherical silica carrier particles having a diameter of 5mm, and then mixed with 300g of solution III to obtain a catalyst precursor.
The catalyst precursor was dried in an oven at 100 ℃ for 4 hours and then calcined in a muffle oven at 400 ℃ for 5 hours to give a catalyst having the following composition:
60w％VMo 4 Nb 0.4 Tl 0.2 W 0.2 Na 0.2 O g +40w％SiO 2 。
the obtained catalyst was evaluated, and the results are shown in table 1. Wherein, according to the ammonia temperature programmed desorption curve of the catalyst, the catalyst has two desorption peaks, the temperature corresponding to the highest position of the stronger desorption peak is 208 ℃, and the temperature corresponding to the highest position of the weaker desorption peak is 325 ℃; the ratio of the relative intensity corresponding to the highest position of the stronger desorption peak to the relative intensity corresponding to the highest position of the weaker desorption peak is 1.8; the temperature difference corresponding to the highest position of the stronger desorption peak and the highest position of the weaker desorption peak is 117 ℃; the ratio of the peak area of the stronger desorption peak to the peak area of the weaker desorption peak is 30.
Example 2
Example 2 is essentially the same as example 1, except that 1g of polyacrylamide having a molecular weight of 1200 ten thousand is mixed with 10g of water in step 4). The obtained catalyst was evaluated, and the results are shown in table 1. According to the ammonia gas temperature programmed desorption curve of the catalyst, the temperature corresponding to the highest position of the stronger desorption peak is 210 ℃, and the temperature corresponding to the highest position of the weaker desorption peak is 327 ℃. The ratio of the relative intensity corresponding to the highest position of the stronger desorption peak to the relative intensity corresponding to the highest position of the weaker desorption peak is 1.6; the temperature difference corresponding to the highest position of the stronger desorption peak and the highest position of the weaker desorption peak is 117 ℃; the ratio of the peak area of the stronger desorption peak to the peak area of the weaker desorption peak was 28.
Example 3
Example 3 is essentially the same as example 1, except that in step 4) 1g of polyacrylamide having a molecular weight of 2000 ten thousand is mixed with 10g of water. The obtained catalyst was evaluated, and the results are shown in table 1. Wherein, according to the ammonia temperature programmed desorption curve of the catalyst, the temperature corresponding to the highest position of the stronger desorption peak is 210 ℃, and the temperature corresponding to the highest position of the weaker desorption peak is 328 ℃; the ratio of the relative intensity corresponding to the highest position of the stronger desorption peak to the relative intensity corresponding to the highest position of the weaker desorption peak is 1.6; the temperature difference corresponding to the highest position of the stronger desorption peak and the highest position of the weaker desorption peak is 118 ℃; the ratio of the peak area of the stronger desorption peak to the peak area of the weaker desorption peak was 27.
Example 4
Example 4 is basically the same as example 1 except that the pH of the surface treatment liquid in step 4) is adjusted to 6. The obtained catalyst was evaluated, and the results are shown in table 1. Wherein, according to the ammonia temperature programmed desorption curve of the catalyst, the temperature corresponding to the highest position of the stronger desorption peak is 222 ℃, and the temperature corresponding to the highest position of the weaker desorption peak is 338 ℃; the ratio of the relative intensity corresponding to the highest position of the stronger desorption peak to the relative intensity corresponding to the highest position of the weaker desorption peak is 1.8; the temperature difference corresponding to the highest position of the stronger desorption peak and the highest position of the weaker desorption peak is 116 ℃; the ratio of the peak area of the stronger desorption peak to the peak area of the weaker desorption peak was 29.
Example 5
Example 5 is basically the same as example 1 except that the pH of the surface treatment liquid in step 4) is adjusted to 10. The obtained catalyst was evaluated, and the results are shown in table 1. Wherein, according to the ammonia temperature programmed desorption curve of the catalyst, the temperature corresponding to the highest position of the stronger desorption peak is 220 ℃, and the temperature corresponding to the highest position of the weaker desorption peak is 336 ℃; the ratio of the relative intensity corresponding to the highest position of the stronger desorption peak to the relative intensity corresponding to the highest position of the weaker desorption peak is 1.7; the temperature difference corresponding to the highest position of the stronger desorption peak and the highest position of the weaker desorption peak is 16 ℃; the ratio of the peak area of the stronger desorption peak to the peak area of the weaker desorption peak was 28.
Example 6
Example 6 is essentially the same as example 1, except that the amounts of niobium oxalate and thallium nitrate used in step 1) are adjusted so that the resulting catalyst has a composition:
60w％VMo 4 Nb 0.2 Tl 0.4 W 0.2 Na 0.2 O g +40w％SiO 2 。
the obtained catalyst was evaluated, and the results are shown in table 1. Wherein, according to the ammonia temperature programmed desorption curve of the catalyst, the temperature corresponding to the highest position of the stronger desorption peak is 218 ℃, and the temperature corresponding to the highest position of the weaker desorption peak is 335 ℃; the ratio of the relative intensity corresponding to the highest position of the stronger desorption peak to the relative intensity corresponding to the highest position of the weaker desorption peak is 1.8; the temperature difference corresponding to the highest position of the stronger desorption peak and the highest position of the weaker desorption peak is 117 ℃; the ratio of the peak area of the stronger desorption peak to the peak area of the weaker desorption peak was 28.
Example 7
Example 7 is essentially the same as example 1, except that the amounts of niobium oxalate and thallium nitrate are adjusted so that the resulting catalyst has a composition:
60w％VMo 4 Nb 0.1 Tl 0.5 W 0.2 Na 0.2 O g +40w％SiO 2 。
the obtained catalyst was evaluated, and the results are shown in table 1. Wherein, according to the ammonia temperature programmed desorption curve of the catalyst, the temperature corresponding to the highest position of a stronger desorption peak is 223 ℃, and the temperature corresponding to the highest position of a weaker desorption peak is 339 ℃; the ratio of the relative intensity corresponding to the highest position of the stronger desorption peak to the relative intensity corresponding to the highest position of the weaker desorption peak is 2.0; the temperature difference corresponding to the highest position of the stronger desorption peak and the highest position of the weaker desorption peak is 16 ℃; the ratio of the peak area of the stronger desorption peak to the peak area of the weaker desorption peak is 31.
Example 8
Example 8 is essentially the same as example 1, except that the amounts of niobium oxalate and thallium nitrate are adjusted so that the resulting catalyst has a composition:
60w％VMo 4 Nb 0.5 Tl 0.1 W 0.2 Na 0.2 O g +40w％SiO 2 。
the obtained catalyst was evaluated, and the results are shown in table 1. Wherein, according to the ammonia temperature programmed desorption curve of the catalyst, the temperature corresponding to the highest position of the stronger desorption peak is 212 ℃, and the temperature corresponding to the highest position of the weaker desorption peak is 329 ℃; the ratio of the relative intensity corresponding to the highest position of the stronger desorption peak to the relative intensity corresponding to the highest position of the weaker desorption peak is 1.7; the temperature difference corresponding to the highest position of the stronger desorption peak and the highest position of the weaker desorption peak is 117 ℃; the ratio of the peak area of the stronger desorption peak to the peak area of the weaker desorption peak is 26.
Example 9
Example 9 was substantially the same as example 1 except that in step 4), the surface treatment liquid was mixed with 150g of spherical silica carrier particles having a diameter of 5mm and then mixed with 200g of the first solution to obtain a catalyst precursor. So that the composition of the resulting catalyst is:
40w％VMo 4 Nb 0.4 Tl 0.2 W 0.2 Na 0.2 O g +60w％SiO 2 。
the obtained catalyst was evaluated, and the results are shown in table 1. Wherein, according to the ammonia temperature programmed desorption curve of the catalyst, the temperature corresponding to the highest position of the stronger desorption peak is 215 ℃, and the temperature corresponding to the highest position of the weaker desorption peak is 333 ℃; the ratio of the relative intensity corresponding to the highest position of the stronger desorption peak to the relative intensity corresponding to the highest position of the weaker desorption peak is 1.8; the temperature difference corresponding to the highest position of the stronger desorption peak and the highest position of the weaker desorption peak is 18 ℃; the ratio of the peak area of the stronger desorption peak to the peak area of the weaker desorption peak was 27.
Example 10
Example 10 was substantially the same as example 1 except that in step 4), the surface treatment liquid was mixed with 100g of spherical silica carrier particles having a diameter of 5mm and then with 800g of the first solution to obtain a catalyst precursor. So that the composition of the resulting catalyst is:
80w％VMo 4 Nb 0.4 Tl 0.2 W 0.2 Na 0.2 O g +20w％SiO 2 。
the obtained catalyst was evaluated, and the results are shown in table 1. Wherein, according to the ammonia temperature programmed desorption curve of the catalyst, the temperature corresponding to the highest position of the stronger desorption peak is 216 ℃, and the temperature corresponding to the highest position of the weaker desorption peak is 335 ℃; the ratio of the relative intensity corresponding to the highest position of the stronger desorption peak to the relative intensity corresponding to the highest position of the weaker desorption peak is 1.8; the temperature difference corresponding to the highest position of the stronger desorption peak and the highest position of the weaker desorption peak is 19 ℃; the ratio of the peak area of the stronger desorption peak to the peak area of the weaker desorption peak was 28.
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that no surface treatment liquid was added in step 2), so that the composition of the resulting catalyst was:
60w％VMo 4 Nb 0.4 Tl 0.2 W 0.2 Na 0.2 O g +40w％SiO 2 。
the obtained catalyst was evaluated, and the results are shown in table 1. Wherein, according to the ammonia temperature programmed desorption curve of the catalyst, the catalyst only has one desorption peak, and the temperature corresponding to the highest position of the desorption peak is 190 ℃.
Comparative example 2
Comparative example 2 is substantially the same as example 1 except that in steps 1) to 3), precursor solutions containing Nb element, tl element, V element, mo element, W element, and Na element were directly mixed to obtain a mixed solution. 1g of polyacrylamide having a molecular weight of 800 ten thousand was mixed with 10g of water, and the pH of the mixture was adjusted to 8.0 using 0.1 mol/liter of aqueous ammonia to obtain a surface treatment liquid. The surface treatment liquid was mixed with 100g of spherical silica carrier particles having a diameter of 5mm, and then mixed with 300g of solution III to obtain a catalyst precursor:
60w％VMo 4 Nb 0.2 Tl 0.4 W 0.2 Na 0.2 O g +40w％SiO 2 。
the obtained catalyst was evaluated, and the results are shown in table 1. Wherein, according to the ammonia temperature programmed desorption curve of the catalyst, the catalyst only has one desorption peak, and the temperature corresponding to the highest position of the desorption peak is 195 ℃.
TABLE 1
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (13)
1. The catalyst for preparing acrylic acid by oxidizing acrolein comprises a carrier and an active component, wherein the active component comprises a composite metal oxide containing a V element, a Mo element, a Nb element, a Tl element, a transition metal element and an alkali metal element.
2. The catalyst of claim 1, wherein: the active component is represented by formula (1):
VMo a Nb b Tl c X d Z e O f the compound of the formula (1),
wherein X represents a transition metal element, Z represents an alkali metal element, and a, b, c, d and e represent molar ratios of Mo, nb, tl, X, Z and V, respectively; a is 1.0 to 10.0; b is 0.1 to 1.0; c is 0.1 to 1.0; d is 0.05 to 1.0; e is 0.05 to 1.0; f is the mole number of oxygen atoms required to satisfy the valence of other elements in the active component.
3. The catalyst of claim 1, wherein: the transition metal element is one or more of Sc element, tl element, Y element, zr element, hf element, ta element, cr element, W element, mn element, tc element, re element, fe element, ru element, os element, co element, rh element, ir element, ni element, pd element, pt element, cu element, ag element, au element, zn element and Cd element; the alkali metal element is one or more of Li element, na element, K element, rb element and Cs element.
4. The catalyst of claim 1, wherein: two desorption peaks exist in an ammonia temperature programming desorption curve of the catalyst, and the relative intensities of the two desorption peaks are different, wherein the temperature corresponding to the highest position of the stronger desorption peak is 175-250 ℃, and the temperature corresponding to the highest position of the weaker desorption peak is 300-350 ℃.
5. The catalyst of claim 4, wherein: the ratio of the relative intensity corresponding to the highest position of the stronger desorption peak to the relative intensity corresponding to the highest position of the weaker desorption peak is (1.5-2.5): 1.
6. The catalyst according to claim 4 or 5, characterized in that: the temperature difference corresponding to the highest position of the stronger desorption peak and the highest position of the weaker desorption peak is between 90 and 130 ℃; and/or the presence of a gas in the gas,
the ratio of the peak area of the stronger desorption peak to the peak area of the weaker desorption peak is (10-50): 1.
7. A process for preparing a catalyst as claimed in any one of claims 1 to 6, comprising the steps of:
1) Mixing a precursor containing Nb element and Tl element with a dispersion medium to obtain a solution I;
2) Mixing a precursor containing a V element, a Mo element, a transition metal element and an alkali metal element with a dispersion medium to obtain a solution II;
3) Mixing the solution I obtained in the step 1) and the solution II obtained in the step 2) to obtain a solution III;
4) Impregnating the solution III obtained in the step 3) into a catalyst carrier, and then drying and roasting to obtain the catalyst.
8. The method of claim 7, wherein: the dispersion media in the solution I and the solution II are both water; when preparing the solution I and the solution II, the dispersion medium is heated to 60-90 ℃ first, and then precursors of corresponding elements are added.
9. The method of claim 7, wherein: in step 3), the pH value of the obtained solution III is controlled to be 1-6, preferably 2-4.
10. The method of claim 7, wherein: in step 3), before mixing, the temperature of the solution I is 10-50 ℃, preferably 20-30 ℃, and the temperature of the solution II is 10-50 ℃, preferably 20-30 ℃.
11. The method of claim 7, wherein: in the step 4), the catalyst carrier is firstly treated by adopting the surface treatment solution and then is soaked in the solution III; the surface treatment liquid is a mixture of polyacrylamide and water, and the treatment time is 10-300 min.
12. The method of claim 11, wherein: the molecular weight of polyacrylamide is: 800 to 2000 ten thousand, preferably 800 to 1200 ten thousand; the concentration of the surface treatment liquid is as follows: 1 to 25%, preferably 5 to 15%; the pH value of the surface treatment liquid is 6 to 10, preferably 7 to 9; the mass ratio of the polyacrylamide to the catalyst carrier is 0.1 to 5, preferably 0.2 to 1.
13. Use of a catalyst as claimed in any one of claims 1 to 6 or prepared by a process as claimed in any one of claims 7 to 12 in the selective oxidation of acrolein to acrylic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111183757.5A CN115957742A (en) | 2021-10-11 | 2021-10-11 | Catalyst for preparing acrylic acid by acrolein oxidation and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111183757.5A CN115957742A (en) | 2021-10-11 | 2021-10-11 | Catalyst for preparing acrylic acid by acrolein oxidation and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115957742A true CN115957742A (en) | 2023-04-14 |
Family
ID=87363621
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111183757.5A Pending CN115957742A (en) | 2021-10-11 | 2021-10-11 | Catalyst for preparing acrylic acid by acrolein oxidation and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115957742A (en) |
-
2021
- 2021-10-11 CN CN202111183757.5A patent/CN115957742A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6143690A (en) | Ammoxidation catalyst for use in producing acrylonitrile or methacrylonitrile from propane or isobutane | |
| JP5152867B2 (en) | Process for producing mixed metal oxide catalysts for producing unsaturated aldehydes from olefins | |
| CN102441435B (en) | Method for preparing alumina carrier for silver catalyst, carrier prepared by using method and application thereof | |
| JP5011176B2 (en) | Catalyst for synthesizing acrylonitrile and method for producing acrylonitrile | |
| TWI341748B (en) | Method for regenerating catalyst for the production of methacrylic acid and process for preparing methacrylic acid | |
| CN108579781B (en) | Phenol hydrogenation catalyst and preparation method thereof | |
| US7429678B2 (en) | Composite-oxide catalyst and process for production of acrylic acid using said catalyst | |
| CN106693981A (en) | Iron-molybdenum catalyst for formaldehyde synthesis through methanol oxidation as well as preparation method and application | |
| CN103717306A (en) | Catalyst for manufacture of acrolein and acrylic acid by means of dehydration of glycerin, and manufacturing method for same | |
| CN110732321A (en) | Preparation method of silicotungstic acid modified cerium dioxide catalyst | |
| US5116801A (en) | Catalysts for the selective reduction of nitrogen oxides and process for preparing the catalyst | |
| TWI429483B (en) | Process for producing catalyst for use in producing unsaturated aldehyde and unsaturated carboxylic acid, and process for producing unsaturated aldehyde and unsaturated carboxylic acid | |
| CN109772416B (en) | Oxygen vacancy-containing phenol hydrogenation catalyst and preparation method thereof | |
| US7341974B2 (en) | Method for preparing a catalyst for partial oxidation of propylene | |
| CN115957742A (en) | Catalyst for preparing acrylic acid by acrolein oxidation and preparation method and application thereof | |
| JP2009522086A (en) | A method for synthesizing heteropolyacid catalysts for the oxidation of unsaturated aldehydes to unsaturated carboxylic acids. | |
| JP3797148B2 (en) | Method for producing catalyst for producing methacrylic acid and method for producing methacrylic acid | |
| JPS588894B2 (en) | Oxidation catalyst produced by NH↓3 and oxidation method | |
| CN114425323B (en) | Catalyst for preparing acrolein by propylene selective oxidation and preparation method thereof | |
| JP2013202564A (en) | Composite oxide catalyst | |
| CN113926463B (en) | Acrolein catalyst and preparation method and application thereof | |
| CN112547062B (en) | Catalyst for preparing acrylic acid from acrolein and preparation method and application thereof | |
| CN115487832B (en) | Catalyst for low-temperature propane oxidation and preparation method thereof | |
| JP3797146B2 (en) | Method for producing catalyst for producing methacrylic acid and method for producing methacrylic acid | |
| CN115957757A (en) | Catalyst for preparing acrylic acid, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |