CN114797982A - Catalyst for preparing methacrylic acid by isobutane one-step method, and preparation method and application thereof - Google Patents
Catalyst for preparing methacrylic acid by isobutane one-step method, and preparation method and application thereof Download PDFInfo
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Abstract
本发明提供了一种用于异丁烷一步法制甲基丙烯酸的催化剂、其制备方法及应用。本发明提供的催化剂，具有式(1)所示结构：(Cs2.230Cu0.255V0.382)yPMo12O40式(1)；其中，0.88≤y≤1.29。本发明控制Cs、Cu和V的比例并控制整体(Cs2.230Cu0.255V0.382)与H3PMo12O40的比例来控制表面酸度，从而得到特定组成的keggin结构杂多酸催化剂；同时，在制备过程中按照Cs、Cu、V的特定添加顺序实施，使所得催化剂呈球形并使得催化剂中晶格氧的释放速率适度，进而使催化剂在保证氧化异丁烷能力的同时避免了过渡氧化，保证异丁烷转化率并提高甲基丙烯酸收率。The invention provides a catalyst for preparing methacrylic acid by one-step method of isobutane, its preparation method and application. The catalyst provided by the present invention has the structure shown in formula (1): (Cs 2.230 Cu 0.255 V 0.382 ) y PMo 12 O 40 formula (1); wherein, 0.88≤y≤1.29. The invention controls the ratio of Cs, Cu and V and controls the ratio of the whole (Cs 2.230 Cu 0.255 V 0.382 ) to H 3 PMo 12 O 40 to control the surface acidity, thereby obtaining a keggin structure heteropolyacid catalyst with a specific composition; In the preparation process, the specific addition order of Cs, Cu, and V is carried out, so that the obtained catalyst is spherical and the release rate of lattice oxygen in the catalyst is moderate, so that the catalyst can ensure the isobutane oxidation ability while avoiding transition oxidation, ensuring Isobutane conversion and improved methacrylic acid yield.
Description
Technical Field
The invention relates to the field of catalysis, and particularly relates to a catalyst for preparing methacrylic acid by an isobutane one-step method, and a preparation method and application thereof.
Background
Methacrylic acid can be used for the synthesis of organic substances or the preparation of polymers, for example for the esterification to form methyl methacrylate and the further processing to synthesize polymethyl methacrylate, and can also be used as a raw material of synthetic rubber.
However, the currently widely accepted large-scale synthesis of methacrylic acid includes: acetone cyanohydrin (using virulent hydrocyanic acid as a raw material), isobutylene oxidation (high raw material cost), and ethylene carbonylation (complex multi-step synthesis). Due to the above disadvantages, the low cost, safe one-step oxidation of isobutane to methacrylic acid is receiving increasing attention from researchers.
Taking into account the features of heteropoly acid compounds in selective catalytic oxidation, e.g. using H in the oxidation of isobutyraldehyde 3 PMo 12 O 40 Instead of an aldehyde group, a dehydrogenation reaction occurs at α. Producing methacrolein; h 3 PMo 12 O 40 When the catalyst is used as an oxidation catalyst of methacrolein, methacrylic acid is generated by the reaction on the aldehyde group, and C ═ C is not affected. Thus, modified keggin-structured heteropoly acid H 3 PMo 12 O 40 Are preferably considered as catalysts for the one-stage oxidation of isobutane to methacrylic acid.
At present, it is generally accepted that modified H is used for selective oxidation of isobutane to methacrylic acid 3 PMo 12 O 40 The catalyst follows the Mars-van Krevelen mechanism. Lattice oxygen around the Mo atoms plays a particularly important role in the oxidation of isobutane. However, in practice, how to modify H 3 PMo 12 O 40 Good catalytic effect can be obtained, and still great challenges are faced.
Disclosure of Invention
In view of the above, the present invention aims to provide a catalyst for preparing methacrylic acid by an isobutane one-step method, a preparation method and an application thereof. The catalyst provided by the invention can catalyze isobutane to be oxidized in one step to directly generate methacrylic acid, and has good catalytic activity.
The invention provides a catalyst for preparing methacrylic acid by an isobutane one-step method, which has a structure shown in a formula (1):
(Cs 2.230 Cu 0.255 V 0.382 ) y PMo 12 O 40 formula (1);
wherein y is more than or equal to 0.88 and less than or equal to 1.29.
Preferably, y is 0.88, 1.0, 1.12 or 1.29.
The invention also provides a preparation method of the catalyst for preparing methacrylic acid by the isobutane one-step method in the technical scheme, which comprises the following steps:
a) phosphomolybdic acid H 3 PMo 12 O 40 ·xH 2 Dissolving O in water to obtain a phosphomolybdic acid solution;
b) sequentially reacting CsCO 3 Solution, Cu (NO) 3 ) 2 Solution, VOSO 4 Adding the solution into the phosphomolybdic acid solution to obtain a mixed solution;
c) and heating the mixed solution, stirring until the mixed solution is evaporated to dryness, and then calcining to obtain the catalyst shown in the formula (1).
Preferably, in the step a), the dissolving temperature is 80-100 ℃.
Preferably, in the step c), the heating temperature is 90-110 ℃.
Preferably, in the step c), the calcining temperature is 300-370 ℃ and the time is 1-5 h.
The invention also provides the catalyst for preparing methacrylic acid by the isobutane one-step method in the technical scheme or the application of the catalyst prepared by the preparation method in the technical scheme in the preparation of methacrylic acid by the isobutane one-step method.
The invention also provides a method for preparing methacrylic acid by using the isobutane in one step, which comprises the following steps:
under the action of a catalyst, raw material gas is heated and reacts to form methacrylic acid;
wherein, the catalyst is the catalyst for preparing methacrylic acid by the isobutane one-step method in the technical scheme or the catalyst prepared by the preparation method in the technical scheme.
Preferably, the feed gas comprises: isobutane gas, oxygen and inert gases; the temperature of the heating reaction is 300-350 ℃.
Preferably, in the feed gas, the volume ratio of isobutane to oxygen is 1.0-1.8.
In the catalyst prepared by the invention, Cs, Cu and V are introduced to regulate H 3 PMo 12 O 40 In particular, the ratio of Cs, Cu and V and the overall (Cs) ratio are controlled 2.230 Cu 0.255 V 0.382 ) And H 3 PMo 12 O 40 The surface acidity is controlled by the proportion of the (C) to obtain the Keggin structure heteropoly acid (Cs) with specific composition 2.230 Cu 0.255 V 0.382 ) x PMo 12 O 40 A catalyst; meanwhile, in the preparation process, the specific addition sequence of Cs, Cu and V is implemented, so that the obtained catalyst is spherical, the release rate of lattice oxygen in the catalyst is moderate, the catalyst can ensure the capability of oxidizing isobutane, meanwhile, the condition of transitional oxidation is avoided, the conversion rate of isobutane is ensured, and the yield of methacrylic acid prepared by oxidizing isobutane in one step is effectively improved. And, controlling surface acidity: (
And the number of Lewis acid sites) can further significantly enhance the selectivity of methacrylic acid, thereby increasing the yield of methacrylic acid. Therefore, the catalyst for the invention can catalyze the isobutane raw material to be oxidized in one step to directly generate the methacrylic acid, and can improve the raw material conversion rate and the yield of the methacrylic acid.
The experimental result shows that the catalyst can oxidize isobutane to generate methacrylic acid by a one-step method, and under the condition that the alkane-oxygen ratio is 1.8, the conversion rate of an isobutane raw material reaches more than 13%, the selectivity of the methacrylic acid reaches more than 4.3%, and the yield of the methacrylic acid reaches more than 0.6%; under the condition of the alkoxy ratio of 1.0, the conversion rate of the isobutane raw material reaches more than 20%, the selectivity of methacrylic acid reaches more than 4.9%, and the yield of the methacrylic acid reaches more than 1.2%. Among them, catalyst (Cs) 2.230 Cu 0.255 V 0.382 )PMo 12 O 40 And (Cs) 2.230 Cu 0.255 V 0.382 ) 0.88 PMo 12 O 40 The catalytic effect is further remarkably improved, under the condition that the alkane-oxygen ratio is 1.8, the conversion rate of the isobutane raw material reaches more than 15%, the selectivity of methacrylic acid reaches more than 37%, and the yield of the methacrylic acid reaches more than 6.5%; under the condition of the alkoxy ratio of 1.0, the conversion rate of the isobutane raw material reaches more than 20%, the selectivity of methacrylic acid reaches more than 41%, and the yield of the methacrylic acid reaches more than 9.0%. Among them, catalyst (Cs) 2.230 Cu 0.255 V 0.382 )PMo 12 O 40 The catalytic effect of the catalyst is optimal, under the condition that the alkane-oxygen ratio is 1.8, the conversion rate of the isobutane raw material reaches more than 15%, the selectivity of methacrylic acid reaches more than 48%, and the yield of the methacrylic acid reaches 7.5%; under the condition of the alkoxy ratio of 1.0, the conversion rate of the isobutane raw material reaches more than 20%, the selectivity of methacrylic acid reaches more than 50%, and the yield of the methacrylic acid reaches more than 10%.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an XRD spectrum of the catalyst obtained in examples 1-4 before and after the catalytic experiment;
FIG. 2 is an ammonia in-situ diffuse reflectance spectrum of the catalyst A obtained in example 1;
FIG. 3 is an ammonia in-situ diffuse reflectance spectrum of the catalyst C obtained in example 3;
FIG. 4 is a graph showing the effects of the catalytic reactions of the catalysts obtained in examples 1 to 4 at 4 temperatures (300 ℃, 320 ℃, 335 ℃, 350 ℃).
Detailed Description
The invention provides a catalyst for preparing methacrylic acid by an isobutane one-step method, which has a structure shown in a formula (1):
(Cs 2.230 Cu 0.255 V 0.382 ) y PMo 12 O 40 formula (1);
wherein y is more than or equal to 0.88 and less than or equal to 1.29.
In the present invention, it is preferable that y is 0.88, 1.0, 1.12 or 1.29, that is, each of the formula (1) is (Cs) 2.230 Cu 0.255 V 0.382 ) 0.88 PMo 12 O 40 、(Cs 2.230 Cu 0.255 V 0.382 )PMo 12 O 40 、(Cs 2.230 Cu 0.255 V 0.382 ) 1.12 PMo 12 O 40 、(Cs 2.230 Cu 0.255 V 0.382 ) 1.29 PMo 12 O 40 . Most preferably, y is 1.0, i.e., formula (1) is (Cs) 2.230 Cu 0.255 V 0.382 )PMo 12 O 40 。
In the invention, the catalyst is spherical. In the invention, the granularity of the catalyst is preferably 20-40 meshes.
The invention also provides a preparation method of the catalyst for preparing methacrylic acid by the isobutane one-step method in the technical scheme, which comprises the following steps:
a) phosphomolybdic acid H 3 PMo 12 O 40 ·xH 2 Dissolving O in water to obtain a phosphomolybdic acid solution;
b) sequentially reacting CsCO 3 Solution, Cu (NO) 3 ) 2 Solution, VOSO 4 Adding the solution into the phosphomolybdic acid solution to obtain a mixed solution;
c) and heating the mixed solution, stirring until the mixed solution is evaporated to dryness, and then calcining to obtain the catalyst shown in the formula (1).
[ with respect to step a ]:
a) phosphomolybdic acid H 3 PMo 12 O 40 ·xH 2 Dissolving O in water to obtain phosphomolybdic acid solution.
In the present invention, the phosphomolybdic acid H 3 PMo 12 O 40 ·xH 2 In the O raw material, the value of x is not particularly limited and may be0 (i.e., anhydrous phosphomolybdic acid) or not (i.e., phosphomolybdic acid hydrate). The invention is directed to said phosphomolybdic acid H 3 PMo 12 O 40 ·xH 2 The source of the raw material O is not particularly limited, and may be a commercially available product.
In the present invention, the water is preferably deionized water.
In the present invention, the phosphomolybdic acid H 3 PMo 12 O 40 ·xH 2 The amount ratio of O to water is preferably such that the concentration of the target solution is 0.01 to 0.10g/mL, more specifically, 0.01g/mL, 0.02g/mL, 0.03g/mL, 0.04g/mL, 0.05g/mL, 0.06g/mL, 0.07g/mL, 0.08g/mL, 0.09g/mL, or 0.10 g/mL.
In the present invention, the dissolving temperature is preferably 80 to 100 ℃, and specifically 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃, 90 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃, 100 ℃. The dissolution is preferably accompanied by stirring, i.e. heating to the above target temperature and continuing stirring until sufficient dissolution has occurred to obtain a clear and transparent solution, i.e. a phosphomolybdic acid solution.
[ regarding step b ]:
b) sequentially reacting CsCO 3 Solution, Cu (NO) 3 ) 2 Solution, VOSO 4 Adding the solution into the phosphomolybdic acid solution to obtain a mixed solution.
In the present invention, the CsCO is 3 The solution is CsCO 3 An aqueous solution of (a). In the present invention, the CsCO is 3 The solution is preferably prepared in the following manner: mixing CsCO 3 Dissolving in water, and ultrasonic dispersing to obtain CsCO 3 And (3) solution. Wherein the water is preferably deionized water. The time for ultrasonic dispersion is preferably 5-10 min. In the present invention, the CsCO is 3 The concentration of the solution is preferably 0.08 to 0.3g/mL, and specifically may be 0.08g/mL, 0.1g/mL, 0.15g/mL, 0.2g/mL, 0.25g/mL, or 0.3 g/mL.
In the present invention, the Cu (NO) is 3 ) 2 The solution is Cu (NO) 3 ) 2 An aqueous solution of (a). In the present invention, the Cu (NO) is 3 ) 2 The solution is preferably prepared in the following manner:adding Cu (NO) 3 ) 2 Dissolving in water, and ultrasonic dispersing to obtain Cu (NO) 3 ) 2 And (3) solution. Wherein the water is preferably deionized water. The time for ultrasonic dispersion is preferably 5-10 min. In the present invention, the Cu (NO) is 3 ) 2 The concentration of the solution is preferably 0.01 to 0.04g/mL, and specifically may be 0.01g/mL, 0.02g/mL, 0.03g/mL, or 0.04 g/mL.
In the invention, the VOSO 4 The solution is VOSO 4 An aqueous solution of (a). In the invention, the VOSO 4 The solution is preferably prepared in the following manner: adding VOSO 4 Dissolving in water, and ultrasonic dispersing to obtain VOSO 4 And (3) solution. Wherein the water is preferably deionized water. The time for ultrasonic dispersion is preferably 5-10 min. In the invention, the VOSO 4 The concentration of the solution is preferably 0.01 to 0.06g/mL, and specifically may be 0.01g/mL, 0.02g/mL, 0.03g/mL, 0.04g/mL, 0.05g/mL, 0.06g/mL or less.
In the invention, the charging sequence is that CsCO is sequentially added into the phosphomolybdic acid solution obtained in the step a) 3 Solution, Cu (NO) 3 ) 2 Solution, VOSO 4 Adding the solution in sequence according to the sequence of the materials corresponding to the Cs, Cu and V elements; the invention controls the specific feeding sequence, is beneficial to obtaining the spherical catalyst and ensuring the activity of the catalyst, and if the feeding sequence is broken, the spherical shape can not be obtained and the activity of the catalyst is reduced. In the present invention, CsCO is added 3 Solution, Cu (NO) 3 ) 2 Solution, VOSO 4 The solution is preferably added dropwise to the phosphomolybdic acid solution.
In the invention, when mixing materials, the proportion of the materials is preferably controlled as follows: the CsCO 3 The volume ratio of the solution to the phosphomolybdic acid solution is preferably 1: 6 to (6-20), and specifically may be 1: 6, 1: 7, 1: 8, 1: 9, 1: 10, 1: 11, 1: 12, 1: 13, 1: 14, 1: 15, 1: 16, 1: 17, 1: 18, 1: 19, or 1: 20. The Cu (NO) 3 ) 2 The volume ratio of the solution to the phosphomolybdic acid solution is preferably 1: 6-20, and specifically may be 1: 6, 1: 7, 1: 8, 1: 9, 1: 10, 1: 11, 1: 12, 1: 13, 1: 14, 1: 15, 1: 16, 1: 17, 1: 118. 1: 19, 1: 20. The VOSO 4 The volume ratio of the solution to the phosphomolybdic acid solution is preferably 1: 6 to (6-20), and specifically may be 1: 6, 1: 7, 1: 8, 1: 9, 1: 10, 1: 11, 1: 12, 1: 13, 1: 14, 1: 15, 1: 16, 1: 17, 1: 18, 1: 19, or 1: 20. In the present invention, it is preferable to control CsCO at the time of addition 3 Solution, Cu (NO) 3 ) 2 Solution and VOSO 4 The molar ratio of Cs to Cu to V in the solution was 2.230: 0.255: 0.382. And control (Cs) 2.230 Cu 0.255 V 0.382 ) Integer H 3 PMo 12 O 40 The ratio of (a) to (b) is y. And adding the three solutions into a phosphomolybdic acid solution to obtain a mixed solution.
[ with respect to step c ]:
c) and heating the mixed solution, stirring until the mixed solution is evaporated to dryness, and then calcining to obtain the catalyst shown in the formula (1).
In the present invention, after the mixed solution is obtained in the step b), the mixed solution is heated with stirring. Wherein the heating temperature is preferably 90-110 deg.C, and specifically 90 deg.C, 91 deg.C, 92 deg.C, 93 deg.C, 94 deg.C, 95 deg.C, 96 deg.C, 97 deg.C, 98 deg.C, 99 deg.C, 100 deg.C, 101 deg.C, 102 deg.C, 103 deg.C, 104 deg.C, 105 deg.C, 106 deg.C, 107 deg.C, 108 deg.C, 109 deg.C, 110 deg.C. Stirring is continued under the above-mentioned heating conditions until the mixed solution is evaporated to dryness. After evaporation to dryness, spherical particles with the particle size of about 500nm can be obtained.
In the present invention, the above-mentioned vapor is evaporated and then calcined. In the present invention, the calcination may be carried out in a muffle furnace. In the present invention, the calcination is preferably performed under air atmosphere conditions. In the invention, the target temperature of the calcination is preferably 300-370 ℃, and specifically can be 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃ and 370 ℃, and more preferably is 350 ℃. The heating rate of the calcination is preferably 1-10 ℃/min, specifically 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, 10 ℃/min, more preferably 5 ℃/min. The heat preservation time of the calcination is preferably 1-5 h, and specifically can be 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h and 5 h. In the invention, after the calcination, the catalyst is naturally cooled to room temperature, and the product, namely the catalyst shown in the formula (1), is taken out, wherein the obtained catalyst is spherical.
In the present invention, the molar ratio of Cs, Cu and V in the catalyst is fixed (the molar ratio of Cs: Cu: V is 2.230: 0.255: 0.382), they are considered as a whole, and it is varied with H 3 PMo 12 O 40 To obtain different catalysts (Cs) 2.230 Cu 0.255 V 0.382 ) y PMo 12 O 40 (0.88≤y≤1.29)。
In the invention, when the catalyst is actually used, the catalyst is preferably firstly tableted and sieved to obtain the catalyst particles with the particle size of 20-40 meshes.
The invention also provides the application of the catalyst in the technical scheme or the catalyst prepared by the preparation method in the technical scheme in the one-step preparation of methacrylic acid from isobutane.
The invention also provides a method for preparing methacrylic acid by using the isobutane in one step, which comprises the following steps:
under the action of a catalyst, raw material gas is heated and reacts to form methacrylic acid;
wherein the catalyst is the catalyst described in the above technical scheme or the catalyst prepared by the preparation method described in the above technical scheme, and details are not repeated herein.
In the present invention, the raw material gas preferably includes: isobutane gas, oxygen and inert gas. The inert gas is not particularly limited, and may be any conventional inert gas known to those skilled in the art, such as nitrogen, helium, argon, or the like. In the invention, the volume ratio of the inert gas in the feed gas is preferably 50-62%, and the balance is isobutane gas and oxygen; the volume ratio may specifically be 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%. In the present invention, the volume ratio (i.e., the alkoxy ratio) of the isobutane gas to the oxygen gas is preferably 1.0 to 1.8, and specifically may be 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and more preferably is 1.0.
In the present invention, the heating temperature is preferably 300 to 350 ℃, and specifically 300 ℃, 305 ℃, 310 ℃, 315 ℃, 320 ℃, 325 ℃, 330 ℃, 335 ℃, 340 ℃, 345 ℃ and 350 ℃.
In the invention, under the action of the catalyst, isobutane gas is oxidized by a one-step method to directly generate methacrylic acid.
In the catalyst prepared by the invention, Cs, Cu and V are introduced to regulate H 3 PMo 12 O 40 In particular, the ratio of Cs, Cu and V and the overall (Cs) ratio are controlled 2.230 Cu 0.255 V 0.382 ) And H 3 PMo 12 O 40 The surface acidity is controlled by the proportion of the (C) to obtain the Keggin structure heteropoly acid (Cs) with specific composition 2.230 Cu 0.255 V 0.382 ) x PMo 12 O 40 A catalyst; meanwhile, in the preparation process, the specific addition sequence of Cs, Cu and V is implemented, so that the obtained catalyst is spherical, the release rate of lattice oxygen in the catalyst is moderate, the catalyst can ensure the capability of oxidizing isobutane, meanwhile, the condition of transitional oxidation is avoided, the conversion rate of isobutane is ensured, and the yield of methacrylic acid prepared by oxidizing isobutane in one step is effectively improved. And, controlling surface acidity: (
And the number of Lewis acid sites) can further significantly enhance the selectivity of methacrylic acid, thereby increasing the yield of methacrylic acid. Therefore, the catalyst for the invention can catalyze the isobutane raw material to be oxidized in one step to directly generate the methacrylic acid, and can improve the raw material conversion rate and the yield of the methacrylic acid.
The invention has the following beneficial effects:
1. the invention obtains the spherical catalyst by controlling the adding sequence of Cs, Cu and V elements in the synthesis process, changes the content of the Cs, Cu and V elements in the catalyst to control the release rate of lattice oxygen and the distribution of acid sites in the catalyst, and finally obtains the catalyst (Cs) by a precipitation method 2.230 Cu 0.255 V 0.382 ) y PMo 12 O 40 A heteropolyacid catalyst. The catalyst has excellent catalytic activity which can reach 0.68mmol Methacrylic acid ·h -1 ·g -1 Catalyst and process for preparing same 。
2. The catalyst has the advantages of simple preparation process, simple and convenient operation, good repeatability, low price of raw material and reagent, and convenient industrial scale production and application.
The experimental result shows that the catalyst can oxidize isobutane to generate methacrylic acid by a one-step method, and under the condition that the alkane-oxygen ratio is 1.8, the conversion rate of an isobutane raw material reaches more than 13%, the selectivity of the methacrylic acid reaches more than 4.3%, and the yield of the methacrylic acid reaches more than 0.6%; under the condition of the alkoxy ratio of 1.0, the conversion rate of the isobutane raw material reaches more than 20%, the selectivity of methacrylic acid reaches more than 4.9%, and the yield of the methacrylic acid reaches more than 1.2%. Among them, catalyst (Cs) 2.230 Cu 0.255 V 0.382 )PMo 12 O 40 And (Cs) 2.230 Cu 0.255 V 0.382 ) 0.88 PMo 12 O 40 The catalytic effect is further remarkably improved, under the condition that the alkane-oxygen ratio is 1.8, the conversion rate of the isobutane raw material reaches more than 15%, the selectivity of methacrylic acid reaches more than 37%, and the yield of the methacrylic acid reaches more than 6.5%; under the condition of the alkoxy ratio of 1.0, the conversion rate of the isobutane raw material reaches more than 20%, the selectivity of methacrylic acid reaches more than 41%, and the yield of the methacrylic acid reaches more than 9.0%. Among them, catalyst (Cs) 2.230 Cu 0.255 V 0.382 )PMo 12 O 40 The catalytic effect of the catalyst is optimal, under the condition that the alkane-oxygen ratio is 1.8, the conversion rate of the isobutane raw material reaches more than 15%, the selectivity of methacrylic acid reaches more than 48%, and the yield of the methacrylic acid reaches 7.5%; under the condition of the alkoxy ratio of 1.0, the conversion rate of the isobutane raw material reaches more than 20%, the selectivity of methacrylic acid reaches more than 50%, and the yield of the methacrylic acid reaches more than 10%.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In the following examples, phosphomolybdic acid (H) was used 3 PMo 12 O 40 ·xH 2 O)、CsCO 3 、Cu(NO 3 ) 2 、VOSO 4 The reagents and gases used (isobutane, oxygen, nitrogen, etc.) are commercially available.
Example 1: preparation of catalyst (Cs) 2.230 Cu 0.255 V 0.382 ) 1.29 PMo 12 O 40
The molar ratio of Cs to Cu to V is fixed, and the whole of the Cs to Cu to V and H are regulated and controlled 3 PMo 12 O 40 Is 1.29.
S1, mixing phosphomolybdic acid (H) 3 PMo 12 O 40 ·xH 2 O) is dissolved in deionized water, heated to 90 ℃, and stirred until the solution is clear and transparent, thus obtaining the phosphomolybdic acid solution with the concentration of 0.04 g/mL.
S2, respectively mixing CsCO 3 、Cu(NO 3 ) 2 、VOSO 4 Dissolving in deionized water, and performing ultrasonic treatment for 10 minutes to respectively obtain CsCO 3 Solution, Cu (NO) 3 ) 2 Solution, VOSO 4 Solutions (concentrations of 0.119g/mL, 0.017g/mL, and 0.028g/mL, respectively). CsCO is added according to the sequence of Cs, Cu and V elements 3 Solution, Cu (NO) 3 ) 2 Solution, VOSO 4 The solutions are sequentially dripped into the phosphomolybdic acid solution obtained in the step S1, the molar ratio of Cs to Cu to V is controlled to be 2.230: 0.255: 0.382 in the charging process, and the volume ratio of the three solutions to the phosphomolybdic acid solution is regulated and controlled to be 1: 6-20, so that the (Cs) 2.230 Cu 0.255 V 0.382 ) Integral with H 3 PMo 12 O 40 Is 1.29. After the addition was completed, a mixed solution was obtained.
S3, placing the mixed solution in an open beaker, raising the temperature of the oil bath to 100 ℃, and continuously stirring until the mixed solution is evaporated to dryness. Then transferring the mixture to a muffle furnace, raising the temperature to 350 ℃ at the speed of 5 ℃/min under the air condition, preserving the heat and calcining the mixture for 3 hours, and then naturally lowering the temperatureAnd cooling to room temperature to obtain the catalyst. Putting the catalyst into a die, tabletting and sieving to obtain catalyst particles with the particle size of 20-40 meshes and the specific surface area of 67.4m 2 (ii) in terms of/g. The obtained catalyst is (Cs) 2.230 Cu 0.255 V 0.382 ) 1.29 PMo 12 O 40 And is marked as catalyst A.
Example 2: preparation of catalyst (Cs) 2.230 Cu 0.255 V 0.382 ) 1.12 PMo 12 O 40
The molar ratio of Cs to Cu to V is fixed, and the whole of the Cs to Cu to V and H are regulated and controlled 3 PMo 12 O 40 Is 1.12.
S1, mixing phosphomolybdic acid (H) 3 PMo 12 O 40 ·xH 2 O) is dissolved in deionized water, heated to 90 ℃, and stirred until the solution is clear and transparent, thus obtaining the phosphomolybdic acid solution with the concentration of 0.04 g/mL.
S2, respectively mixing CsCO 3 、Cu(NO 3 ) 2 、VOSO 4 Dissolving in deionized water, and performing ultrasonic treatment for 10 minutes to respectively obtain CsCO 3 Solution, Cu (NO) 3 ) 2 Solution, VOSO 4 Solutions (concentrations of 0.103g/mL, 0.015g/mL, 0.024g/mL in this order). CsCO is added according to the sequence of Cs, Cu and V elements 3 Solution, Cu (NO) 3 ) 2 Solution, VOSO 4 The solutions are sequentially dripped into the phosphomolybdic acid solution obtained in the step S1, the molar ratio of Cs to Cu to V is controlled to be 2.230: 0.255: 0.382 in the charging process, and the volume ratio of the three solutions to the phosphomolybdic acid solution is regulated and controlled to be 1: 6-20, so that the (Cs) 2.230 Cu 0.255 V 0.382 ) Integral with H 3 PMo 12 O 40 Is 1.12. After the addition was completed, a mixed solution was obtained.
S3, placing the mixed solution in an open beaker, raising the temperature of the oil bath to 100 ℃, and continuously stirring until the mixed solution is evaporated to dryness. And then transferring the mixture to a muffle furnace, heating the mixture to 350 ℃ at the speed of 5 ℃/min under the air condition, carrying out heat preservation and calcination for 3h, and then naturally cooling the mixture to room temperature to obtain the catalyst. Putting the catalyst into a die, tabletting and sieving to obtain catalyst particles with the particle size of 20-40 meshes, wherein the ratio of the catalyst particles to the catalyst particlesSurface area of 4m 2 (ii) in terms of/g. The obtained catalyst is (Cs) 2.230 Cu 0.255 V 0.382 ) 1.12 PMo 12 O 40 And is marked as catalyst B.
Example 3: preparation of catalyst (Cs) 2.230 Cu 0.255 V 0.382 )PMo 12 O 40
The molar ratio of Cs to Cu to V is fixed, and the whole of the Cs to Cu to V and H are regulated and controlled 3 PMo 12 O 40 Is 1.0.
S1, mixing phosphomolybdic acid (H) 3 PMo 12 O 40 ·xH 2 O) is dissolved in deionized water, heated to 90 ℃, and stirred until the solution is clear and transparent, thus obtaining the phosphomolybdic acid solution with the concentration of 0.04 g/mL.
S2, respectively mixing CsCO 3 、Cu(NO 3 ) 2 、VOSO 4 Dissolving in deionized water, and performing ultrasonic treatment for 10 minutes to respectively obtain CsCO 3 Solution, Cu (NO) 3 ) 2 Solution, VOSO 4 The solution (concentration: 0.092g/mL, 0.014g/mL, 0.022g/mL in this order). CsCO is added according to the sequence of Cs, Cu and V elements 3 Solution, Cu (NO) 3 ) 2 Solution, VOSO 4 The solutions are sequentially dripped into the phosphomolybdic acid solution obtained in the step S1, the molar ratio of Cs to Cu to V is controlled to be 2.230: 0.255: 0.382 in the charging process, and the volume ratio of the three solutions to the phosphomolybdic acid solution is regulated and controlled to be 1: 6-20, so that the (Cs) 2.230 Cu 0.255 V 0.382 ) Integral with H 3 PMo 12 O 40 Is 1.0. After the addition was completed, a mixed solution was obtained.
S3, placing the mixed solution in an open beaker, raising the temperature of the oil bath to 100 ℃, and continuously stirring until the mixed solution is evaporated to dryness. And then transferring the mixture to a muffle furnace, heating the mixture to 350 ℃ at the speed of 5 ℃/min under the air condition, carrying out heat preservation and calcination for 3h, and then naturally cooling the mixture to room temperature to obtain the catalyst. Putting the catalyst into a die, tabletting and sieving to obtain catalyst particles with the granularity of 20-40 meshes and the specific surface area of 8m 2 (ii) in terms of/g. The obtained catalyst is (Cs) 2.230 Cu 0.255 V 0.382 )PMo 12 O 40 Is denoted as catalyst C。
Example 4: preparation of catalyst (Cs) 2.230 Cu 0.255 V 0.382 ) 0.88 PMo 12 O 40
The molar ratio of Cs to Cu to V is fixed, and the whole of the Cs to Cu to V and H are regulated and controlled 3 PMo 12 O 40 Is 0.88.
S1, mixing phosphomolybdic acid (H) 3 PMo 12 O 40 ·xH 2 O) is dissolved in deionized water, heated to 90 ℃, and stirred until the solution is clear and transparent, thus obtaining the phosphomolybdic acid solution with the concentration of 0.04 g/mL.
S2, respectively mixing CsCO 3 、Cu(NO 3 ) 2 、VOSO 4 Dissolving in deionized water, and performing ultrasonic treatment for 10 minutes to respectively obtain CsCO 3 Solution, Cu (NO) 3 ) 2 Solution, VOSO 4 Solutions (concentrations of 0.081g/mL, 0.012g/mL, 0.019g/mL in this order). CsCO is added according to the sequence of Cs, Cu and V elements 3 Solution, Cu (NO) 3 ) 2 Solution, VOSO 4 The solutions are sequentially dripped into the phosphomolybdic acid solution obtained in the step S1, the molar ratio of Cs to Cu to V is controlled to be 2.230: 0.255: 0.382 in the charging process, and the volume ratio of the three solutions to the phosphomolybdic acid solution is regulated and controlled to be 1: 6-20, so that the (Cs) 2.230 Cu 0.255 V 0.382 ) Integral with H 3 PMo 12 O 40 Is 0.88. After the addition was completed, a mixed solution was obtained.
S3, placing the mixed solution in an open beaker, raising the temperature of the oil bath to 100 ℃, and continuously stirring until the mixed solution is evaporated to dryness. And then transferring the mixture to a muffle furnace, heating the mixture to 350 ℃ at the speed of 5 ℃/min under the air condition, carrying out heat preservation and calcination for 3h, and then naturally cooling the mixture to room temperature to obtain the catalyst. Putting the catalyst into a die, tabletting and sieving to obtain catalyst particles with the particle size of 20-40 meshes and the specific surface area of 3.6m 2 (ii) in terms of/g. The obtained catalyst is (Cs) 2.230 Cu 0.255 V 0.382 ) 0.88 PMo 12 O 40 And is marked as catalyst D.
Example 5: characterization and testing
1. Catalytic experiment
2g of catalyst particles are loaded into a quartz tube with the inner diameter of 8mm, then the quartz tube is transferred into a reactor, feed gas (isobutane gas, oxygen and inert gas) is filled, the temperature is heated to 335 ℃, and catalytic reaction is carried out for 2 hours. Wherein the total flow rate of the raw material gas is 20 mL/min. In the experimental process, a chromatograph is adopted for on-line monitoring, and a pipeline between a product outlet of the reaction system and a sample inlet of the chromatograph is heated to 150 ℃, so that the generated methacrylic acid product enters a chromatographic quantitative ring in a gas form, and the purpose of on-line monitoring is realized. The Shimadzu GC-2014 gas chromatograph is equipped with five types of chromatography columns: PQ 80/100mesh 3.2X 2.1mm X1.0M, MS-13X 80/100mesh 3.2X 2.1mm X3.0M, Rtx-10.32 mm X5 um X5M, HP-Al 2 O 3 /s 0.32mm×25m×8um，Rtx-1 0.32mm×60m×5um。
According to the experimental process, catalytic experiments are carried out under the conditions of two different raw material gas composition ratios:
(ii) an alkoxy ratio of 1.8: i-C 4 H 10 /O 2 /N 2 The volume ratio is 25%/13.9%/61.1%;
(ii) an alkoxy ratio of 1.0: i-C 4 H 10 /O 2 /N 2 The volume ratio is 25%/25%/50%.
The catalysts obtained in examples 1 to 4 were subjected to the above-mentioned catalytic experiments, and the results are shown in Table 1.
Table 1: catalytic reaction Effect of the catalysts obtained in examples 1 to 4
The test results in table 1 show that the catalyst obtained in the invention can oxidize isobutane to generate methacrylic acid by one-step method, and under the condition that the alkane-oxygen ratio is 1.8, the conversion rate of isobutane raw material reaches more than 13%, the selectivity of methacrylic acid reaches more than 4.3%, and the yield of methacrylic acid reaches more than 0.6%; under the condition of the alkoxy ratio of 1.0, the conversion rate of the isobutane raw material reaches more than 20%, the selectivity of methacrylic acid reaches more than 4.9%, and the yield of the methacrylic acid reaches more than 1.2%. The catalytic effects of the catalyst C and the catalyst D obtained in the embodiments 3 to 4 are further remarkably improved, the conversion rate of an isobutane raw material reaches more than 15%, the selectivity of methacrylic acid reaches more than 37%, and the yield of the methacrylic acid reaches more than 6.5% under the condition that the alkane-oxygen ratio is 1.8; under the condition of the alkoxy ratio of 1.0, the conversion rate of the isobutane raw material reaches more than 20%, the selectivity of methacrylic acid reaches more than 41%, and the yield of the methacrylic acid reaches more than 9.0%. The catalytic effect of the catalyst C is optimal, under the condition that the alkane-oxygen ratio is 1.8, the conversion rate of the isobutane raw material reaches more than 15%, the selectivity of methacrylic acid reaches more than 48%, and the yield of the methacrylic acid reaches 7.5%; under the condition of the alkoxy ratio of 1.0, the conversion rate of the isobutane raw material reaches more than 20%, the selectivity of methacrylic acid reaches more than 50%, and the yield of the methacrylic acid reaches more than 10%. For the four catalysts, the catalytic effect under the condition of the alkane-oxygen ratio of 1.0 is better than that under the condition of the alkane-oxygen ratio of 1.8.
2. Characterization of
After the above catalytic experiment was completed, the catalyst was taken out. The catalysts subjected to the catalytic experiment I are respectively marked as catalyst A1, catalyst B1, catalyst C1 and catalyst D1. The catalysts subjected to the catalytic experiment II are respectively marked as catalyst A2, catalyst B2, catalyst C2 and catalyst D2.
(1) Characterization of XRD
The four original catalysts before the catalytic experiment (i.e. catalst a, catalst B, catalst C, catalst D obtained after the calcination in step S3 in examples 1 to 4), the four catalysts after the first catalytic experiment (i.e. catalst a1, catalst B1, catalst C1, catalst D1), and the four catalysts after the second catalytic experiment (i.e. catalst a2, catalst B2, catalst C2, catalst D2) were subjected to X-ray diffraction characterization tests, respectively. The results are shown in fig. 1, and fig. 1 is an XRD spectrogram of the catalyst obtained in examples 1-4 before and after a catalytic experiment; wherein, (1), (4), (7) and (10) respectively correspond to four original catalysts, namely, the catalyst A, the catalyst B, the catalyst C and the catalyst D obtained after the calcination of the step S3 in the embodiments 1 to 4; (2) (5) (8) and (11) respectively correspond to four catalysts, namely, catalyst A1, catalyst B1, catalyst C1 and catalyst D1 which are subjected to catalytic experiment (i.e. under the condition that the alkoxy ratio is 1.8); (3) (6), (9) and (12) respectively correspond to four catalysts, namely, catalyst A2, catalyst B2, catalyst C2 and catalyst D2 which are subjected to catalytic experiment (namely, the condition that the alkoxy ratio is 1.0).
It can be seen that: the characteristic peaks of keggin structure in the lines (1), (2) and (3) (i.e. catalyst A, catalyst A1 and catalyst A2) have not changed, which proves that the structure of catalyst A obtained in example 1 is stable whether calcined during the preparation of the catalyst or the catalyst is in the catalytic reaction (whether under the condition of the alkane-oxygen ratio of 1.8 or 1.0). Similarly, the characteristic peaks of the keggin structure in (4) (5) (6) (i.e. catalyst B, catalyst B1, and catalyst B2) have not changed, the characteristic peaks of the keggin structure in (7) (8) (9) (i.e. catalyst C, catalyst C1, and catalyst C2) have not changed, and the characteristic peaks of the keggin structure in (10) (11) (12) (i.e. catalyst D, catalyst D1, and catalyst D2) have not changed, which also proves that the structure of the catalyst B, catalyst C, and catalyst D obtained in examples 2-4 is stable during calcination or catalytic reaction (no matter whether the condition of the ratio of alkane to oxygen is 1.8 or 1.0).
(2) Characterization of diffuse reflectance
The in-situ ammonia diffuse reflectance characterization of the catalyst A obtained in example 1 and the catalyst C obtained in example 3 is shown in FIGS. 2-3, wherein FIG. 2 is an in-situ ammonia diffuse reflectance spectrum of the catalyst A obtained in example 1, and FIG. 3 is an in-situ ammonia diffuse reflectance spectrum of the catalyst C obtained in example 3. It can be seen that all show that the desorption of methacrylic acid is facilitated
The strength of the acid sites of the catalyst C obtained in example 3, which is superior to the catalyst A with the lowest methacrylic acid yield, is verified
The strength of the acid site is correlated with the yield of methacrylic acid in the reaction.
Example 6: testing
Catalytic experiment:
the catalytic experiment (i.e., the catalytic reaction was carried out at an alkoxy ratio of 1.0) in example 5 was carried out, except that the temperatures of the catalytic reaction were adjusted to 300 deg.C, 320 deg.C, and 350 deg.C, respectively. The catalysts obtained in examples 1 to 4 (catalyst A, catalyst B, catalyst C, and catalyst D) were subjected to the above-described catalytic experiments. Isobutane conversion and methacrylic acid yield were tested.
By combining the catalyst experiments (reaction temperature of 300 ℃, 320 ℃ and 350 ℃) and the catalytic experiments (reaction temperature of 335 ℃) in example 5, the test results of the isobutane conversion rate and the methacrylic acid selectivity of each catalyst at 4 temperatures are shown in fig. 4, and fig. 4 is a graph of the catalytic reaction effect of the catalysts obtained in examples 1-4 at 4 temperatures (300 ℃, 320 ℃, 335 ℃ and 350 ℃), wherein the round sphere represents the isobutane conversion rate, and the column represents the methacrylic acid selectivity.
It can be seen that: (1) under 4 different temperatures, the catalysts obtained in the embodiments 1 to 4 can obtain good isobutane conversion rate and methacrylic acid yield, and especially the effect of the catalysts obtained in the embodiments 2 to 4 is further obviously improved. (2) For the catalysts obtained in examples 1-4, with the increase of the catalytic reaction temperature, the isobutane conversion rate of most of the catalysts is increased, and meanwhile, the selectivity of methacrylic acid is reduced. (3) The conversion of the catalyst A obtained in example 1 almost reaches the maximum value at the beginning, which shows that the catalyst has strong activation capability to isobutane, but the selectivity of methacrylic acid is always low, which shows that the catalyst has weak selective activation capability to isobutane. (4) Of the four catalysts, the catalyst C obtained in example 3 has the maximum selectivity to methacrylic acid at four reaction temperature points, which shows the outstanding selectivity in the reaction of preparing methacrylic acid from isobutane.
As can be seen from all the examples, the catalyst obtained by the invention can oxidize isobutane into methacrylic acid by a one-step method, so that good isobutane conversion rate and methacrylic acid selection are achievedSex and yield; of these, the catalyst C (i.e., (Cs) obtained in example 3 2.230 Cu 0.255 V 0.382 )PMo 12 O 40 ) The catalytic effect of (3) is optimal.
The foregoing examples are provided to facilitate an understanding of the principles of the invention and their core concepts, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that approximate the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
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