CN111420688A - Preparation method and application of vanadyl phosphate catalyst - Google Patents
Preparation method and application of vanadyl phosphate catalyst Download PDFInfo
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- CN111420688A CN111420688A CN202010304102.8A CN202010304102A CN111420688A CN 111420688 A CN111420688 A CN 111420688A CN 202010304102 A CN202010304102 A CN 202010304102A CN 111420688 A CN111420688 A CN 111420688A
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- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 142
- 239000003054 catalyst Substances 0.000 title claims abstract description 133
- -1 vanadyl phosphate Chemical compound 0.000 title claims abstract description 125
- 239000010452 phosphate Substances 0.000 title claims abstract description 124
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 56
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000010992 reflux Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 58
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 42
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000012298 atmosphere Substances 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 230000007547 defect Effects 0.000 abstract description 12
- 239000012752 auxiliary agent Substances 0.000 abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 20
- 239000002245 particle Substances 0.000 description 18
- 238000005303 weighing Methods 0.000 description 18
- 239000012071 phase Substances 0.000 description 17
- 239000013078 crystal Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- 238000001514 detection method Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 9
- 229940035429 isobutyl alcohol Drugs 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000012495 reaction gas Substances 0.000 description 9
- 238000012216 screening Methods 0.000 description 9
- 238000001994 activation Methods 0.000 description 8
- 238000001069 Raman spectroscopy Methods 0.000 description 7
- 229910000540 VOPO4 Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000001000 micrograph Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000012018 catalyst precursor Substances 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 241000446313 Lamella Species 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- LEABNKXSQUTCOW-UHFFFAOYSA-N [O].[P].[V] Chemical compound [O].[P].[V] LEABNKXSQUTCOW-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/612—Surface area less than 10 m2/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Furan Compounds (AREA)
Abstract
The invention relates to a preparation method of a vanadyl phosphate catalyst, which comprises the following steps: will V2O5Adding the mixture into a mixed solution of isobutanol and benzyl alcohol, stirring and mixing, refluxing for 2-5H at 130-140 ℃, cooling to 100-120 ℃, keeping the temperature at 100-120 ℃, and adding H with the mass concentration of 85-90% at the speed of 0.6-1.5 m L/min3PO4Then heating to 130-140 ℃, continuously refluxing for 10-14 h, filtering and washing the product to obtain a vanadyl phosphate precursor; and roasting the vanadyl phosphate precursor to obtain the vanadyl phosphate catalyst. The method of the invention can overcome the defect that the traditional method of improving the performance of the phosphorus source by adding the auxiliary agent by controlling the adding process of the phosphorus sourceCan not only avoid secondary pollution and reduce cost, but also simplify the preparation process.
Description
Technical Field
The invention belongs to the field of chemical catalysis, and relates to a preparation method and application of a vanadyl phosphate catalyst.
Background
The vanadyl phosphate catalyst (also called vanadium phosphorus oxygen catalyst, abbreviated as VPO) is used as the most efficient and economic industrial catalyst for preparing Maleic Anhydride (MA) by selective oxidation of n-butane, and the precursor vanadyl phosphate is topologically converted into active phase vanadyl pyrophosphate in the activation process.
The organic phase method is the most extensive method for synthesizing VPO catalyst for industrial application at home and abroad. Aiming at the problem that the VPO catalyst is mainly concentrated on the basis of an organic phase method, the catalytic performance of the VPO catalyst is improved by adding a metal auxiliary agent, an organic auxiliary agent, a novel auxiliary agent and the like, but the batch performance of the VPO catalyst is not stable, and key factors in the VPO synthesis process are not clear.
Disclosure of Invention
In view of the above problems in the prior art, the present invention aims to provide a preparation method and application of vanadyl phosphate catalyst. The method can improve the batch stability of the vanadyl phosphate catalyst by controlling the regulation and control of phosphoric acid to prepare the vanadyl phosphate catalyst, and obviously improves the conversion rate of normal butane, the selectivity of maleic anhydride and the yield of maleic anhydride when the vanadyl phosphate catalyst is used for catalyzing the reaction of preparing maleic anhydride by the selective oxidation of the normal butane.
The invention provides a preparation method of a vanadyl phosphate catalyst, which comprises the following steps:
will V2O5Adding the mixture into a mixed solution of isobutanol and benzyl alcohol, stirring and mixing, refluxing for 2-5 h at the temperature of 130-140 ℃, and cooling to 100-120 ℃.
Keeping the temperature at 100-120 ℃, and adding H with the mass concentration of 85-90% at the speed of 0.6-1.5 m L/min3PO4Then heating to 130-140 ℃ and continuously refluxing for 10-14 h, filtering and washing the product,obtaining a vanadyl phosphate precursor;
and roasting the vanadyl phosphate precursor to obtain the vanadyl phosphate catalyst.
The invention also provides the application of the vanadyl phosphate catalyst obtained by the method in preparing maleic anhydride by selective oxidation of n-butane.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention regulates and controls the crystal structure of the VPO precursor by controlling the addition operation of the phosphorus source, avoids forming lattice defects and reduces the impure phase formed by the conversion of the precursor in the activation process. The VPO catalyst optimized by the operation conditions has good stability while maintaining excellent selectivity and conversion rate, and achieves or is superior to the same effect of the doping auxiliary agent in the prior art.
(2) The method does not use any auxiliary agent, is simple and cheap to synthesize, and cannot cause auxiliary agent loss.
(3) Compared with the traditional preparation method, the preparation method simplifies the process, and the obtained vanadyl phosphate catalyst has stable performance, low cost and simple operation, and is suitable for industrial production.
Drawings
FIG. 1 is a scanning electron microscope image of a vanadyl phosphate precursor obtained in step (2) of example 1 of the present invention.
FIG. 2 is a scanning electron microscope image of the calcined vanadyl phosphate catalyst obtained in step (4) of example 1 of the present invention.
Fig. 3 is a scanning electron microscope image of the vanadyl phosphate catalyst precursor obtained in step (2) of example 2 of the present invention.
FIG. 4 is a scanning electron microscope image of the calcined vanadyl phosphate catalyst obtained in step (4) of example 2 of the present invention.
FIG. 5 is a scanning electron microscope image of the vanadyl phosphate catalyst precursor obtained in step (2) of comparative example 1 according to the present invention.
FIG. 6 is a scanning electron microscope image of the calcined vanadyl phosphate catalyst obtained in step (4) of comparative example 1 according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a preparation method of a vanadyl phosphate catalyst, which comprises the following steps:
s01: will V2O5Adding the mixture into a mixed solution of isobutanol and benzyl alcohol, stirring and mixing, refluxing for 2-5 h at the temperature of 130-140 ℃, and cooling to 100-120 ℃.
S02, keeping the temperature at 100-120 ℃, adding H with the mass concentration of 85-90% at the speed of 0.6-1.6 m L/min3PO4Then heating to 130-140 ℃, continuously refluxing for 10-14 h, filtering and washing the product to obtain a vanadyl phosphate precursor;
s03: and roasting the vanadyl phosphate precursor to obtain the vanadyl phosphate catalyst.
Preferably, the volume ratio of the isobutanol to the benzyl alcohol is (3-5): 1, such as 3:1, 3.2:1, 3.5:1, 4:1, 4.5:1, 4.7:1, 4.9:1, or 5: 1.
Preferably, said V2O5Has a concentration of 0.02g/m L-0.12 g/m L, e.g., 0.02g/m L, 0.04g/m L, 0.06g/m L, 0.07g/m L, 0.08g/m L, 0.09g/m L, 0.1g/m L, or 0.12g/m L3PO4Phosphorus and V in (1)2O5The molar ratio of vanadium in (1) to (0.9-1.2) is 1, for example, 0.9:1, 1:1, 1.1:1, 1.2:1, etc.
Preferably, in step S02, V is set2O5Adding the mixture into a mixed solution of isobutanol and benzyl alcohol, stirring and mixing, refluxing for 2-5 h at 135 ℃, and cooling to 110 ℃. The reflux is a vanadium reduction process, the reduction time is short, so that the vanadium is insufficiently reduced, or a reduction product does not reach a stable state, so that the crystallinity of an obtained precursor is poor, and the conversion rate of the activated catalyst to n-butane is reduced. The reduction time is prolonged, the obtained reduction product tends to be stable, the performance of the activated catalyst is still good, but energy is wasted, and the industrial production is not economical.
Preferably, after the continuous reaction in the step (2) is completed, the product is filtered, washed by ethanol and water in sequence and dried at 100-140 ℃.
In step S02, H with the mass concentration of 85-90 percent is added3PO4Heating to 130-140 ℃, continuously refluxing for 10-14 h, wherein the water content of 100% concentrated phosphoric acid is too low, and two adjacent vanadium atoms in the precursor are connected by water, so that the precursor lamella cannot be thickened by 100% phosphoric acid, the obtained crystal grain is too small, the size of the activated catalyst crystal grain is also small, the peak is wider in an XRD result, a non-selective crystal face is exposed while an active face is exposed, the conversion rate of normal butane is higher, the selectivity of maleic anhydride is slightly reduced, and α -VOPO beneficial to preparing maleic anhydride by butane oxidation is not detected in the catalyst obtained by using 100% phosphoric acid4Therefore, the key point for obtaining the high-performance vanadyl phosphate catalyst is to select 85-90% of concentrated phosphoric acid.
The addition of phosphoric acid at low temperature has high supersaturation degree of the solution and high crystal nucleus generation rate, which is not beneficial to crystal growth, namely V and P are not stably combined, so that the addition of phosphoric acid at low temperature can cause the precursor to form lattice defects which are reflected by the shift of peaks in IR and Raman, and the specific surface area of the precursor is large (Table 1), so that the lattice defects are easier to expose, and the precursor is easy to be converted into gamma-VOPO which is not beneficial to the conversion of n-butane after activation4And (4) phase(s). And phosphoric acid is added at high temperature, so that the supersaturation degree of the solution is reduced, the crystal nucleus generation rate is reduced, and the crystal lattice defects formed in the precursor are less, so that the solution can be kept stable in the activation process and is not easy to be converted into gamma-VOPO4Phase is the main reason for its better performance. When the phosphoric acid addition temperature is too high, the nucleation rate is too low by crystal growth, and the performance is also deteriorated.
Further, too short dropping time and too fast dropping speed of phosphoric acid can cause lattice defects to be formed in the precursor, the specific surface area of the precursor is large, and the lattice defects are easily exposed in the activation process, so that gamma-VOPO is caused4The phase generation (table 2) further results in lower n-butane conversion rate, and the precursor crystallinity is good and the specific surface area is reduced and the crystal is crystallized as the adding speed of phosphoric acid is reduced to 0.8-1.2 m L/minLattice defects are not easily present and not easily exposed, and thus gamma-VOPO is not easily produced during the activation process4The crystalline phase also produces α -VOPO which is advantageous for the selective oxidation of n-butane4When the dropping speed of phosphoric acid is too slow, the crystallinity of the precursor is excellent, and the lamella is thickened and more tightly stacked, so that a gamma phase and an α phase are not easily generated in the activation process, and the obtained final vanadyl phosphate catalyst has poor selective oxidation effect on n-butane, more preferably, H with the mass concentration of 85-90 percent is added at the speed of 0.8-1.2 m L/min under the condition of keeping the temperature of 100-120 ℃3PO4。
Preferably, the roasting atmosphere in step (3) is nitrogen atmosphere, or a mixed atmosphere of n-butane and air, or a mixed atmosphere of n-butane, oxygen and nitrogen.
Preferably, in the mixed atmosphere of n-butane and air, the volume ratio of n-butane and air is (0.8-1.8): 100, such as 0.8:100, 1:100, 1.2:100, 1.5:100 or 1.8: 100.
Preferably, the volume ratio of the n-butane to the oxygen and nitrogen is (0.8-1.8): 10-25): 75-85, such as 0.8:10:75, 1:10:85, >, 1.5:10:80, 1.8:10:75, 0.8:20:75, 1:20:80, 1.8:25:85 or 1:20: 85;
preferably, the temperature of the calcination in step (3) is 350 to 550 ℃, such as 350 ℃, 360 ℃, 370 ℃, 380 ℃, 400 ℃, 420 ℃, 430 ℃, 450 ℃, 475 ℃, 500 ℃, 515 ℃, 530 ℃, or 550 ℃.
Preferably, the roasting time in the step (3) is 10h to 24h, such as 10h, 12h, 13.5h, 15h, 16h, 18h, 20h, 22h or 24h, etc.
In order to facilitate the effect evaluation of the catalyst, the roasting step can be carried out after the vanadyl phosphate precursor is formed, and the roasted vanadyl phosphate precursor is directly used for the effect evaluation of the catalyst; or the catalyst can be calcined and then formed and then used for evaluating the effect of the catalyst.
The roasting step can be carried out after the vanadyl phosphate precursor is formed, and the roasted vanadyl phosphate precursor is directly used for evaluating the effect of the catalyst; or the catalyst can be calcined and then formed and then used for evaluating the effect of the catalyst.
The embodiment of the invention also provides application of the vanadyl phosphate catalyst obtained by the preparation method of the vanadyl phosphate catalyst in preparation of maleic anhydride through selective oxidation of n-butane.
Preferably, the reaction conditions for preparing maleic anhydride by selective oxidation of n-butane are as follows: the reaction temperature is 400-550 ℃, the pressure is 0.1-0.3 MPa, and the space velocity of the n-butane mixed gas is 1000h-1～2500h-1And the concentration of the n-butane is 1.3 to 1.8 weight percent.
The structure of the catalyst is closely related to the synthesis conditions, and for the VPO catalyst, the synthesis conditions determine the structure of the obtained precursor, so that the structure of the active phase and the catalytic performance of the active phase are influenced.
The preparation of the vanadyl phosphate catalyst is illustrated by the following specific examples. The compounds in the following examples can be prepared directly according to the existing methods, but of course, in other examples, they can be directly commercially available, and are not limited thereto.
Example 1
Preparing a vanadyl phosphate catalyst:
(1) weighing 10g V2O5Placing the mixture into a three-neck flask with the diameter of 250m L, adding a mixed solution of 80m L isobutyl alcohol and 20m L benzyl alcohol, mechanically stirring and uniformly mixing, refluxing for 3 hours at the temperature of 135 ℃, and cooling to 110 ℃.
(2) Maintaining 110 deg.C, 7.53m L85% H was added dropwise over 7min3PO4And the temperature is increased to 135 ℃ and the reflux is continued for 12 h. Filtering the product, washing with absolute ethyl alcohol to obtain a blue precipitate, and drying in air at 120 ℃ for 24h to obtain the vanadyl phosphate precursor.
(3) Tabletting the obtained vanadyl phosphate precursor powder under the pressure of 15MPa, crushing, screening to obtain 20-40 mesh catalyst particles, and roasting the catalyst particles at the temperature of 430 ℃ from room temperature at the heating rate of 2 ℃/min for 12h under the atmosphere of n-butane/oxygen/nitrogen reaction gas with the volume ratio of 1.5:17:81.5 to obtain the vanadyl phosphate catalyst.
And (3) detection:
weighing 2.6g of vanadyl phosphate catalyst, and placing the vanadyl phosphate catalyst in a fixed bed reactor with the inner diameter of 14mmThe catalyst performance is evaluated, and the composition of the catalyst and the raw material gas is C4H10/O2/N21.4/19.5/79(v/v/v), the reaction temperature is 420 ℃, the reaction pressure is 0.12MPa, and the gas space velocity is 2000h-1The reaction under the conditions, the reaction tail gas is analyzed on line by gas chromatography, the conversion rate of the n-butane is 94.8 percent, the selectivity of the maleic anhydride is 65.1 percent, and the yield of the maleic anhydride is 61.6 percent.
Example 1 FT-IR and BET data for the vanadyl phosphate precursor obtained in step (2) are shown in table 1. The composition of the crystal phase obtained by the raman spectroscopy analysis of the vanadyl phosphate catalyst obtained in step (3) is shown in table 2.
Example 2
Preparing a vanadyl phosphate catalyst:
(1) weighing 10g V2O5Placing the mixture into a three-neck flask with the diameter of 250m L, adding a mixed solution of 80m L isobutyl alcohol and 20m L benzyl alcohol, mechanically stirring and uniformly mixing, refluxing for 3 hours at the temperature of 135 ℃, and cooling to 110 ℃.
(2) Maintaining 110 deg.C, 7.21m L87% H was added dropwise over 6.7min3PO4And the temperature is increased to 135 ℃ and the reflux is continued for 12 h. And filtering the product, washing the product with absolute ethyl alcohol to obtain a blue-black precipitate, and drying the precipitate in air at 120 ℃ for 24 hours to obtain the vanadyl phosphate precursor.
(3) Tabletting the obtained vanadyl phosphate precursor powder under the pressure of 15MPa, crushing, screening 20-40 mesh catalyst particles, and then heating the catalyst particles from room temperature to 430 ℃ at the heating rate of 2 ℃/min under the atmosphere of reaction gas to activate in situ for 12h to obtain the vanadyl phosphate catalyst.
And (3) detection:
weighing 2.6g of vanadyl phosphate catalyst, placing the vanadyl phosphate catalyst in a fixed bed reactor with the inner diameter of 14mm for catalyst performance evaluation, and forming a component C with the feed gas4H10/O2/N21.4/19.5/79(v/v/v), the reaction temperature is 420 ℃, the reaction pressure is 0.12MPa, and the gas space velocity is 2000h-1The reaction under the conditions, the reaction tail gas is analyzed on line by gas chromatography, the conversion rate of the n-butane is 91.2 percent, the selectivity of the maleic anhydride is 65.5 percent, and the yield of the maleic anhydride is 59.7 percent.
Example 2 FT-IR and BET data for the vanadyl phosphate precursor obtained in step (2) are shown in table 1. The composition of the crystal phase obtained by the raman spectroscopy analysis of the vanadyl phosphate catalyst obtained in step (3) is shown in table 2.
Example 3
Preparing a vanadyl phosphate catalyst:
(1) weighing 10g V2O5Placing the mixture into a three-neck flask with the diameter of 250m L, adding a mixed solution of 80m L isobutyl alcohol and 20m L benzyl alcohol, mechanically stirring and uniformly mixing, refluxing for 3 hours at the temperature of 135 ℃, and cooling to 120 ℃.
(2) Maintaining 120 deg.C, 77.2m L90% H was added dropwise over 9min3PO4And the temperature is increased to 135 ℃ and the reflux is continued for 12 h. Filtering the product, washing with absolute ethyl alcohol to obtain a blue precipitate, and drying in air at 120 ℃ for 24h to obtain the vanadyl phosphate precursor.
(3) Tabletting the obtained vanadyl phosphate precursor powder under the pressure of 15MPa, crushing, screening 20-40 mesh catalyst particles, and then heating the catalyst particles from room temperature to 430 ℃ at the heating rate of 2 ℃/min under the atmosphere of reaction gas to activate in situ for 12h to obtain the vanadyl phosphate catalyst.
And (3) detection:
weighing 2.6g of vanadyl phosphate catalyst, placing the vanadyl phosphate catalyst in a fixed bed reactor with the inner diameter of 14mm for catalyst performance evaluation, and forming a component C with the feed gas4H10/O2/N21.4/19.5/79(v/v/v), the reaction temperature is 420 ℃, the reaction pressure is 0.12MPa, and the gas space velocity is 2000h-1The reaction under the conditions, the reaction tail gas is analyzed on line by gas chromatography, the conversion rate of the n-butane is 96.8 percent, the selectivity of the maleic anhydride is 51.6 percent, and the yield of the maleic anhydride is 59.6 percent.
Comparative example 1
Preparing a vanadyl phosphate catalyst:
(1) weighing 10g V2O5Placing the mixture into a three-neck flask with the diameter of 250m L, adding a mixed solution of 80m L isobutyl alcohol and 20m L benzyl alcohol, mechanically stirring and uniformly mixing, refluxing for 3 hours at the temperature of 135 ℃, and cooling to 60 ℃.
(2) Maintaining 60 deg.C, 7.53m L85% H was added dropwise over 7min3PO4And the temperature is increased to 135 ℃ and the reflux is continued for 12 h. Filtering the product, washing with absolute ethyl alcohol to obtain a blue precipitate, and drying in air at 120 ℃ for 24h to obtain the vanadyl phosphate precursor.
(3) Tabletting the obtained vanadyl phosphate precursor powder under the pressure of 15MPa, crushing, screening to obtain 20-40 mesh catalyst particles, and roasting the catalyst particles at the temperature of 430 ℃ from room temperature at the heating rate of 2 ℃/min for 12h under the atmosphere of n-butane/oxygen/nitrogen reaction gas with the volume ratio of 1.5:17:81.5 to obtain the vanadyl phosphate catalyst.
And (3) detection:
weighing 2.6g of vanadyl phosphate catalyst, placing the vanadyl phosphate catalyst in a fixed bed reactor with the inner diameter of 14mm for catalyst performance evaluation, and forming a component C with the feed gas4H10/O2/N21.4/19.5/79(v/v/v), the reaction temperature is 420 ℃, the reaction pressure is 0.12MPa, and the gas space velocity is 2000h-1The reaction under the conditions, the reaction tail gas is analyzed on line by gas chromatography, the conversion rate of the n-butane is 77.1 percent, the selectivity of the maleic anhydride is 66.3 percent, and the yield of the maleic anhydride is 51.5 percent.
Comparative example 1 FT-IR and BET data for the vanadyl phosphate precursor obtained in step (2) are shown in table 1. The composition of the crystal phase obtained by the raman spectroscopy analysis of the vanadyl phosphate catalyst obtained in step (3) is shown in table 2.
Comparative example 2
Preparing a vanadyl phosphate catalyst:
(1) weighing 10g V2O5Placing the mixture into a three-neck flask with the diameter of 250m L, adding a mixed solution of 80m L isobutyl alcohol and 20m L benzyl alcohol, mechanically stirring and uniformly mixing, refluxing for 3 hours at the temperature of 135 ℃, and cooling to 110 ℃.
(2) Maintaining 110 deg.C, 7.53m L85% H was added over 1s3PO4And the temperature is increased to 135 ℃ and the reflux is continued for 12 h. Filtering the product, washing with absolute ethyl alcohol to obtain a blue precipitate, and drying in air at 120 ℃ for 24h to obtain the vanadyl phosphate precursor.
(3) Tabletting the obtained vanadyl phosphate precursor powder under the pressure of 15MPa, crushing, screening to obtain 20-40 mesh catalyst particles, and roasting the catalyst particles at the temperature of 430 ℃ from room temperature at the heating rate of 2 ℃/min for 12h under the atmosphere of n-butane/oxygen/nitrogen reaction gas with the volume ratio of 1.5:17:81.5 to obtain the vanadyl phosphate catalyst.
And (3) detection:
weighing 2.6g of vanadyl phosphate catalyst, placing the vanadyl phosphate catalyst in a fixed bed reactor with the inner diameter of 14mm for catalyst performance evaluation, and forming a component C with the feed gas4H10/O2/N21.4/19.5/79(v/v/v), the reaction temperature is 420 ℃, the reaction pressure is 0.12MPa, and the gas space velocity is 2000h-1The reaction under the conditions, the reaction tail gas is analyzed on line by gas chromatography, the conversion rate of the n-butane is 83.8 percent, the selectivity of the maleic anhydride is 61.0 percent, and the yield of the maleic anhydride is 51.1 percent.
Comparative example 2 FT-IR and BET data for the vanadyl phosphate precursor obtained in step (2) are shown in table 1. The composition of the crystal phase obtained by the raman spectroscopy analysis of the vanadyl phosphate catalyst obtained in step (3) is shown in table 2.
Comparative example 3
Preparing a vanadyl phosphate catalyst:
(1) weighing 10g V2O5Placing the mixture into a three-neck flask with the diameter of 250m L, adding a mixed solution of 80m L isobutyl alcohol and 20m L benzyl alcohol, mechanically stirring and uniformly mixing, refluxing for 3 hours at the temperature of 135 ℃, and cooling to 110 ℃.
(2) Maintaining at 110 deg.C, 7.53m L85% H was added dropwise over 35min3PO4And the temperature is increased to 135 ℃ and the reflux is continued for 12 h. Filtering the product, washing with absolute ethyl alcohol to obtain a blue precipitate, and drying in air at 120 ℃ for 24h to obtain the vanadyl phosphate precursor.
(3) Tabletting the obtained vanadyl phosphate precursor powder under the pressure of 15MPa, crushing, screening to obtain 20-40 mesh catalyst particles, and roasting the catalyst particles at the temperature of 430 ℃ from room temperature at the heating rate of 2 ℃/min for 12h under the atmosphere of n-butane/oxygen/nitrogen reaction gas with the volume ratio of 1.5:17:81.5 to obtain the vanadyl phosphate catalyst.
And (3) detection:
weighing 2.6g of vanadyl phosphate catalyst, placing the vanadyl phosphate catalyst in a fixed bed reactor with the inner diameter of 14mm for catalyst performance evaluation, and forming a component C with the feed gas4H10/O2/N21.4/19.5/79(v/v/v), the reaction temperature is 420 ℃, the reaction pressure is 0.12MPa, and the gas space velocity is 2000h-1The reaction under the conditions, the reaction tail gas is analyzed on line by gas chromatography, the conversion rate of the n-butane is 89.8 percent, the selectivity of the maleic anhydride is 58.1 percent, and the yield of the maleic anhydride is 52.1 percent.
Comparative example 4
Preparing a vanadyl phosphate catalyst:
(1) weighing 10g V2O5Placing the mixture into a three-neck flask with the diameter of 250m L, adding a mixed solution of 80m L isobutyl alcohol and 20m L benzyl alcohol, mechanically stirring and uniformly mixing, refluxing for 3 hours at the temperature of 135 ℃, and cooling to 110 ℃.
(2) Maintaining at 110 deg.C, 21.15m L40% H was added dropwise over 5min3PO4And the temperature is increased to 135 ℃ and the reflux is continued for 12 h. Filtering the product, washing with absolute ethyl alcohol to obtain a blue precipitate, and drying in air at 120 ℃ for 24h to obtain the vanadyl phosphate precursor.
(3) Tabletting the obtained vanadyl phosphate precursor powder under the pressure of 15MPa, crushing, screening to obtain 20-40 mesh catalyst particles, and roasting the catalyst particles at the temperature of 430 ℃ from room temperature at the heating rate of 2 ℃/min for 12h under the atmosphere of n-butane/oxygen/nitrogen reaction gas with the volume ratio of 1.5:17:81.5 to obtain the vanadyl phosphate catalyst.
And (3) detection:
weighing 2.6g of vanadyl phosphate catalyst, placing the vanadyl phosphate catalyst in a fixed bed reactor with the inner diameter of 14mm for catalyst performance evaluation, and forming a component C with the feed gas4H10/O2/N21.4/19.5/79(v/v/v), the reaction temperature is 420 ℃, the reaction pressure is 0.12MPa, and the gas space velocity is 2000h-1The reaction under the conditions, the reaction tail gas is analyzed on line by gas chromatography, the conversion rate of the n-butane is 59.6 percent, the selectivity of the maleic anhydride is 25.1 percent, and the yield of the maleic anhydride is 14.9 percent.
Comparative example 5
Preparing a vanadyl phosphate catalyst:
(1) weighing 10g V2O5Placing into a three-neck flask with the diameter of 250m L, adding a mixed solution of 80m L isobutyl alcohol and 20m L benzyl alcohol, and stirringMechanically stirring and uniformly mixing, refluxing for 3h at 135 ℃, and cooling to 110 ℃.
(2) Maintaining at 110 deg.C, 12.63m L60% H was added dropwise over 7min3PO4And the temperature is increased to 135 ℃ and the reflux is continued for 12 h. Filtering the product, washing with absolute ethyl alcohol to obtain a blue precipitate, and drying in air at 120 ℃ for 24h to obtain the vanadyl phosphate precursor.
(3) Tabletting the obtained vanadyl phosphate precursor powder under the pressure of 15MPa, crushing, screening to obtain 20-40 mesh catalyst particles, and roasting the catalyst particles at the temperature of 430 ℃ from room temperature at the heating rate of 2 ℃/min for 12h under the atmosphere of n-butane/oxygen/nitrogen reaction gas with the volume ratio of 1.5:17:81.5 to obtain the vanadyl phosphate catalyst.
And (3) detection:
weighing 2.6g of vanadyl phosphate catalyst, placing the vanadyl phosphate catalyst in a fixed bed reactor with the inner diameter of 14mm for catalyst performance evaluation, and forming a component C with the feed gas4H10/O2/N21.4/19.5/79(v/v/v), the reaction temperature is 420 ℃, the reaction pressure is 0.12MPa, and the gas space velocity is 2000h-1The reaction under the conditions, the reaction tail gas is analyzed on line by gas chromatography, the conversion rate of normal butane is 59.8 percent, the selectivity of maleic anhydride is 62.5 percent, and the yield of the maleic anhydride is 37.4 percent.
Comparative example 6
Preparing a vanadyl phosphate catalyst:
(1) weighing 10g V2O5Placing the mixture into a three-neck flask with the diameter of 250m L, adding a mixed solution of 80m L isobutyl alcohol and 20m L benzyl alcohol, mechanically stirring and uniformly mixing, refluxing for 3 hours at the temperature of 135 ℃, and cooling to 110 ℃.
(2) Maintaining at 110 deg.C, 5.57m L100% H was added dropwise over 5min3PO4And the temperature is increased to 135 ℃ and the reflux is continued for 12 h. Filtering the product, washing with absolute ethyl alcohol to obtain a blue precipitate, and drying in air at 120 ℃ for 24h to obtain the vanadyl phosphate precursor.
(3) Tabletting the obtained vanadyl phosphate precursor powder under the pressure of 15MPa, crushing, screening to obtain 20-40 mesh catalyst particles, and roasting the catalyst particles at the temperature of 430 ℃ from room temperature at the heating rate of 2 ℃/min for 12h under the atmosphere of n-butane/oxygen/nitrogen reaction gas with the volume ratio of 1.5:17:81.5 to obtain the vanadyl phosphate catalyst.
And (3) detection:
weighing 2.6g of vanadyl phosphate catalyst, placing the vanadyl phosphate catalyst in a fixed bed reactor with the inner diameter of 14mm for catalyst performance evaluation, and forming a component C with the feed gas4H10/O2/N21.4/19.5/79(v/v/v), the reaction temperature is 420 ℃, the reaction pressure is 0.12MPa, and the gas space velocity is 2000h-1The reaction under the conditions, the reaction tail gas is analyzed on line by gas chromatography, the conversion rate of normal butane is 96.8 percent, the selectivity of maleic anhydride is 52.1 percent, and the yield of the maleic anhydride is 50.4 percent.
FIG. 1 is a scanning electron micrograph of a vanadyl phosphate precursor obtained in step (2) of example 1; FIG. 2 is a scanning electron micrograph of an activated vanadyl phosphate catalyst obtained in step (4) of example 1; FIG. 3 is a scanning electron micrograph of a vanadyl phosphate catalyst precursor obtained in step (2) of example 2; FIG. 4 is a scanning electron micrograph of the activated vanadyl phosphate catalyst obtained in step (4) of example 2; FIG. 5 is a scanning electron micrograph of a vanadyl phosphate catalyst precursor obtained in step (2) of comparative example 1; FIG. 6 is a scanning electron micrograph of the activated vanadyl phosphate catalyst obtained in step (4) of comparative example 1.
As can be seen from the graphs 1-6, the vanadyl phosphate catalyst precursor layer after the synthesis conditions are optimized is thickened, stacked and gathered, and after the catalyst is activated, the structure can be relatively kept stable and is not easy to break and collapse.
TABLE 1
| Vanadyl phosphate precursor | vas(PO3)(cm-1) | BET(m2g-1) |
| Comparative example 1 | 1052 | 16.47 |
| Comparative example 2 | 1052 | 12.38 |
| Example 1 | 1047 | 2.69 |
| Example 2 | 1048 | 2.09 |
TABLE 2
| Vanadyl phosphate catalyst | Composition of crystalline phase |
| Comparative example 1 | (VO)2P2O7，α-VOPO4，γ-VOPO4 |
| Comparative example 2 | (VO)2P2O7，α-VOPO4，γ-VOPO4 |
| Example 1 | (VO)2P2O7，α-VOPO4 |
| Example 2 | (VO)2P2O7，α-VOPO4 |
Analysis of the results from raman spectroscopy.
As can be seen from the infrared data of the precursors in Table 1, the vanadyl phosphate catalysts in comparative examples 1 and 2 can be compared with the vanadyl phosphate catalysts prepared by reasonably controlling the adding speed and temperature of the phosphorus source and adding the phosphorus source at a lower temperature or extremely fast speed in examples 1 and 2, and the obtained precursor PO3The asymmetric stretching vibration peak of (2) shifts, indicating that there is a slight lattice distortion. Meanwhile, according to the BET result, the vanadyl phosphate precursors obtained in the comparative examples 1 and 2 have larger specific surface areas and are easier to expose the existing lattice defects, while the specific surface areas of the examples 1 and 2 are far smaller than those of the comparative examples 1 and 2, so that the lattice defects are not easy to exist and are not easy to expose. As can be seen from Table 2 from the composition of the crystal phase of the catalyst obtained by Raman spectroscopy, γ -VOPO was present in comparative examples 1 and 24This should be the result of excessive exposure of the lattice defects of the precursor during activation. The absence of this phase in the catalysts obtained in examples 1 and 2 is a result of reasonably controlling the temperature of phosphoric acid addition operation to avoid the occurrence of lattice defects, and proves that the control of the operating conditions affects the crystal structure of the catalyst on the premise and indirectly affects the activated catalyst.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The invention provides a preparation method of a vanadyl phosphate catalyst, which is characterized by comprising the following steps of:
will V2O5Adding the mixture into a mixed solution of isobutanol and benzyl alcohol, stirring and mixing, refluxing for 2-5 h at the temperature of 130-140 ℃, and cooling to 100-120 ℃.
Keeping the temperature at 100-120 ℃, and adding H with the mass concentration of 85-90% at the speed of 0.6-1.5 m L/min3PO4Then heating to 130-140 ℃, continuously refluxing for 10-14 h, filtering and washing the product to obtain a vanadyl phosphate precursor;
and roasting the vanadyl phosphate precursor to obtain the vanadyl phosphate catalyst.
2. The method for preparing the vanadyl phosphate catalyst according to claim 1, wherein the volume ratio of the isobutanol to the benzyl alcohol is (3-5): 1.
3. The method of preparing vanadyl phosphate catalyst of claim 1, wherein V is2O5The concentration of (b) is 0.02g/m L-0.12 g/m L.
4. The method of preparing vanadyl phosphate catalyst of claim 1, wherein the H is3PO4Phosphorus and V in (1)2O5The molar ratio of vanadium in (1) to (0.9-1.2) is 1.
5. The method of preparing vanadyl phosphate catalyst of claim 1, wherein the calcination temperature is 350 ℃ to 550 ℃.
6. The method for preparing vanadyl phosphate catalyst according to claim 1, wherein H with mass concentration of 85-90% is added at a rate of 0.8-1.2 m L/min3PO4。
7. The method for preparing vanadyl phosphate catalyst according to claim 1, wherein the atmosphere of calcination is nitrogen atmosphere, or a mixed atmosphere of n-butane and air, or a mixed atmosphere of n-butane, oxygen and nitrogen.
8. The method for preparing vanadyl phosphate catalyst according to claim 1, wherein the calcination time is 10-24 h.
9. Use of the vanadyl phosphate catalyst obtained according to the process of claim 1 for the selective oxidation of n-butane to maleic anhydride.
10. The use according to claim 9, wherein the reaction conditions for the selective oxidation of n-butane to maleic anhydride are: the reaction temperature is 400-550 ℃, the pressure is 0.1-0.3 MPa, and the space velocity of the n-butane mixed gas is 1000h-1～2500h-1And the concentration of the n-butane is 1.3 to 1.8 weight percent.
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