CN101722017A - Molybdenum-vanadium-tellurium-niobium catalytic agent for preparing acrylic acid by propane oxidation and preparation method thereof - Google Patents
Molybdenum-vanadium-tellurium-niobium catalytic agent for preparing acrylic acid by propane oxidation and preparation method thereof Download PDFInfo
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- CN101722017A CN101722017A CN200810228225A CN200810228225A CN101722017A CN 101722017 A CN101722017 A CN 101722017A CN 200810228225 A CN200810228225 A CN 200810228225A CN 200810228225 A CN200810228225 A CN 200810228225A CN 101722017 A CN101722017 A CN 101722017A
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Abstract
The invention relates to a molybdenum-vanadium-tellurium-niobium catalytic agent for preparing acrylic acid by propane oxidation, comprising Mo, V, Te, Nb and O elements, and the relative mole ratio of all elements is as follows: rMo is more than 0.25 and is less then 0.98, rV is more than 0.003 and is less than 0.5, rTe is more than 0.003 and is less than 0.5, and rNb is more than 0.003 and is less than 0.5; the chemical composition of the catalytic agent is Mo1V0.3Te0.23Nb0.12Ox.The invention further comprises a preparation method of the catalytic agent, firstly, the precursor of the catalytic agent is prepared, and then the final catalytic agent is obtained by two-section roasting; firstly, roasting is carried out at 200-350 DEG C for 30min-6h; and then the second section roasting process is carried out, the roasting temperature is 400-700 DEG C. The catalytic agent has good technical effect, the propane conversion percent and the acrylic acid selectivity can reach 40.4 percent and 66.7 percent respectively, and the once through yield of the acrylic acid can reach 26.9 percent.
Description
Technical field
The present invention relates to organic chemical industry's acrylic acid technology of preparing, a kind of acrylic acid molybdenum-vanadium-tellurium-niobium catalytic agent of oxidation of propane system and preparation method thereof that is used for is provided especially, specifically is molybdenum-vanadium-tellurium-niobium catalytic agent that is used for the reaction of selective oxidation of propane system acrylic acid and preparation method thereof.
Background technology
Acrylic acid and ester class series of products thereof are crucial Organic Chemicals, and they are widely used in industries such as coating, chemical fibre, weaving, light industry, and oil exploitation, oil dope etc.At present also continually developing new application.
A plurality of developing stage have been experienced in acrylic acid production.1843, Josepl Redtenbach got acrylic acid by acrolein oxidation under the condition that silver oxide exists.Offo Rohm in 1901 has found that the polymer of acrylic acid and ester thereof has important industrial use, and so far acrylic acid and ester thereof have been subjected to people and have paid close attention to nineteen twenty-seven Rohm﹠amp widely; Hass company is that raw material makes cyanoethanol with chlorethanol and Cymag, obtains methyl acrylate through dehydration, hydrolysis and methanol esterification again, thereby has begun suitability for industrialized production.Developed other the acrylic acid and the process route of ester thereof afterwards successively, at present industrial based on the propylene two-step oxidizing process.But the propylene cost is higher, approximately is 1～2 times of propane prices, and along with the exhaustion day by day of petroleum resources and a large amount of development and use of natural gas resource, the propane direct oxidation of employing relative low price prepares acrylic acid and has very tempting application prospect.Because n butane oxidation production of maleic anhydride process route is obtained immense success, so people also expect to replace direct oxidation of propylene to prepare important organic chemicals such as acrylic acid by propane.Propane is a main component of casing-head gas, natural gas, refinery gas, and the source is abundant, and the relative propylene of price is cheap, simultaneously because process route weak point, energy consumption reduction etc. all will bring huge economic benefit, and environmental friendliness more.
In sum, because enrich in cheap, the source of propane, for preparing acrylic acid, the raw material oxidation step has remarkable economic efficiency and practical significance with propane.
By propane oxidation step system acrylic acid some basic research reports have been arranged, the catalyst of employing mainly comprises vanadium phosphorus oxygen (V-P-O), heteropoly acid and salt (HPCs) thereof and composite metal oxide three class systems such as (MMO).Vanadium phosphorus oxygen system catalyst as the butane oxidation production of maleic anhydride that is used for suitability for industrialized production, it is unsatisfactory to be used for the acrylic acid effect of selective oxidation of propane system, once through yield often is no more than 10%, though and heteropoly acid and salt catalyst thereof have the controlled advantage of structure, but since its preparation process in without roasting, therefore the structure of catalyst is stable inadequately, be higher than under 400 ℃ the operating temperature easily because of the structure inactivation that caves in, except the relatively poor shortcoming of heat endurance, it is also undesirable that it is used for the acrylic acid effect of propane oxidation step system, and the highest acrylic acid yield only is 13%.Since nineteen ninety, catalyst based with MoV is that the mixed metal oxide catalyst system of representative has obtained extensive studies, in the reaction of selective oxidation of propane system acrylic acid, also obtained very good catalytic effect, described in Japan Patent, Mitsubishi Kasai company is at the Mo-V-Te-Nb-O catalyst, acrylic acid yield is up to 52.3%, and U.S. Rohm﹠amp; The yield of acrylic acid as a result that Hass company is reported can reach 42%, but many research groups of US and European all do not repeat out the result of study of Mitsubishi Kasai company, and this is because the rapid property of multistep of many components of its complexity, preparation process and for the sensitiveness of preparation parameter to a great extent.
People expect to obtain a kind of technique effect and better are used for molybdenum-vanadium-tellurium-niobium catalytic agent of selective oxidation of propane system acrylic acid reaction and preparation method thereof.
Summary of the invention
The purpose of this invention is to provide a kind of technique effect and obviously better be used for molybdenum-vanadium-tellurium-niobium catalytic agent of selective oxidation of propane system acrylic acid reaction and preparation method thereof.Briefly: we replace the one-part form method of roasting with the two-segment calcining method, and the catalytic performance of Mo-V-Te-Nb-O catalyst in the reaction of selective oxidation of propane system acrylic acid is improved.
Through our discovering, different with heteropoly acid and salt catalyst system thereof, in order to obtain the stability of corresponding active phase and raising catalyst, mixed-metal oxides often needs the such treatment step of high-temperature roasting.In addition, because the raw material difference of using at the Mo-V-Te-Nb-O catalyst, the valence state that can use Te as the Te source is+4 TeO
2, the valence state that also can use Te is+6 H
6TeO
6, and the structure of active phase needs the metal ion framework of specific valence state, so just may need to adopt different roasting modes according to different synthetic routes.
In research process, we at first are to be raw material with ammonium molybdate, ammonium metavanadate, telluric acid and niobium oxalate, and the mode by rotary evaporation in vacuo obtains the Mo-V-Te-Nb-O catalyst precursor, then at static N
2In the atmosphere, 550～650 ℃ of sintering temperatures, roasting time 1～3h, obtain fresh Mo-V-Te-Nb-O catalyst, but the catalyst that this method of roasting obtains is used for the reaction of oxidation of propane system acrylic acid, effect is unsatisfactory, yield only is 5.4%, institute's results reported in the patent also not as results reported in most of document, illustrates that the method for roasting that is adopted may not be to be well suited for the prepared catalyst precursor of rotary evaporation mode.In order further to improve the catalytic performance of Mo-V-Te-Nb-O catalyst, we have developed a new synthetic route, utilize the Mo-V-Te-Nb-O catalyst of the method acquisition of two-segment calcining to be used for the reaction of oxidation of propane system acrylic acid, catalytic performance is significantly improved.
The invention provides a kind of acrylic acid molybdenum-vanadium-tellurium-niobium catalytic agent of oxidation of propane system that is used for, include Mo, V, Te, Nb, these several elements of O in the described catalyst, the relative mol ratio of each element is as follows: 0.25＜rMo＜0.98,0.003＜rV＜0.5,0.003＜rTe＜0.5,0.003＜rNb＜0.5; It is characterized in that: the described chemical composition that is used for the acrylic acid molybdenum-vanadium-tellurium-niobium catalytic agent of oxidation of propane system is specially Mo
1V
0.3Te
0.23Nb
0.12O
x; Wherein, the size of x value is relevant with the valence state of Mo, V and three kinds of elements of Te.
The present invention is used for the acrylic acid molybdenum-vanadium-tellurium-niobium catalytic agent of oxidation of propane system and also includes following preferred content:
Described catalyst precursor prepares by the rotary evaporation method, and then obtains through two-segment calcining: promptly at first at 200～350 ℃ roasting temperature, atmosphere is air, and roasting time 30min～6h reduces to room temperature after the roasting; Second section calcination procedure is at N
2Carry out 400～700 ℃ of sintering temperatures, roasting time 30min～6h in the atmosphere.
Above-mentioned concrete preferred requirement of process that catalyst precursor is handled by the two-segment calcining mode is:
At first roasting under 250～330 ℃ of conditions, atmosphere is air, roasting time 30min～6h reduces to room temperature then;
Enter second section roasting process afterwards, 550～650 ℃ of sintering temperatures, calcination atmosphere are N
2Atmosphere.
The also claimed a kind of preparation method who is used for the acrylic acid molybdenum-vanadium-tellurium-niobium catalytic agent of oxidation of propane system as mentioned above of the present invention is characterized in that: at first prepare catalyst precursor, obtain final catalyst through two-segment calcining then; Wherein: the process specific requirement that catalyst precursor is handled by the two-segment calcining mode is:
At first roasting under 200～350 ℃ of conditions, roasting time 30min～6h;
Enter second section roasting process afterwards, 400～700 ℃ of sintering temperatures.
The preferred requirement of the process that catalyst precursor is handled by the two-segment calcining mode is: at first roasting under 250～330 ℃ of conditions, and atmosphere is air, roasting time 30min～6h reduces to room temperature then; Enter second section roasting process afterwards, 550～650 ℃ of sintering temperatures, calcination atmosphere are N
2Atmosphere.
The further preferred specific requirement that catalyst precursor is handled by the two-segment calcining mode is:
(1) phase I roasting: with the catalyst precursor calcination vessel of packing into, in air atmosphere, rise to the phase I sintering temperature that presets, after keeping 0.5～6h under this temperature, reduce to room temperature naturally with the heating rate of 1 ℃/min～10 ℃/min;
(2) second stage roasting: will be through the product of the first section roasting calcination vessel of packing into, at N
2In the atmosphere, rise to the sintering temperature of the second stage that presets, after keeping 0.5～6h under this temperature, reduce to room temperature naturally with 1 ℃/min～10 ℃/heating rate of min.
Described catalyst precursor preferably utilizes the preparation of rotary evaporation method; Its employed equipment is Rotary Evaporators.
For the ease of using, we can fully grind products therefrom and molding, granulating with the presoma of described catalyst after the two-part high-temperature roasting, and to sieve into particle diameter be 20～30 purpose catalyst granules.
The present invention's emphasis required for protection relates to a kind of Mo-V-Te-Nb-O catalyst of selective oxidation of propane system acrylic acid reaction and method of roasting of preparation process thereof of being used for, with and application in selective oxidation of propane system acrylic acid reacts.It specifically is the Mo-V-Te-Nb-O catalyst precursor that utilizes the rotary evaporation in vacuo preparation, handle through two-segment calcining, the technique effect excellence of its prepared catalyst: can make conversion of propane and acrylic acid selectivity reach 40.4% and 66.7% respectively, the acrylic acid once through yield reaches 26.9%.
Description of drawings
The present invention is further detailed explanation below in conjunction with drawings and the embodiments:
Fig. 1 is the Mo-V-Te-Nb-O catalyst precursor XRD figure of gained sample after two-segment calcining and one-part form roasting respectively that utilizes rotary evaporation method preparation, specifically is the XRD figure of Mo-V-Te-Nb-O catalyst in corresponding embodiment 3 and the comparative example 1;
The XRD figure of contrast L300-H600 and Onestep-600 as can be known, the crystalline phase that two kinds of different roasting modes obtain has evident difference, according to a lot of documents as can be known, the characteristic diffraction peak of catalyst activity phase M1 (6.6 °, 7.8 °, 9.0 °, 22.1 °, 27.2 °) obviously is better than Onestep-600 in the XRD figure of L300-H600, on the contrary, represent the diffraction maximum of dephasign as 24.9 ° of ((V
0.07Mo
0.93)
5O
14) and 27.5 ° of (MoO
3) wait the corresponding diffraction maximum that then obviously is weaker than among the Onestep-600, illustrate that the two-segment calcining mode has promoted the generation of active phase M1 greatly;
Fig. 2 is the H of L300-H600 and Onestep-600
2-TPR figure specifically is the H of Mo-V-Te-Nb-O catalyst in corresponding embodiment 3 and the comparative example 1
2-TPR figure;
As can see from Figure 2, all be lower than corresponding three the main reduction peak of Onestep-600 (550 ℃, 612 ℃, 681 ℃) of one-part form roasting through three main reduction peak of L300-H600 of two-segment calcining (540 ℃, 588 ℃, 627 ℃); According to document as can be known, 540 ℃ and 588 ℃ of H that (or 550 ℃ and 612 ℃) are located
2Reduction peak is relevant with the reducing power of V species, and propane system acrylic acid at first occurs on the V species in the reaction on the catalyst, because L300-H600 has lower reduction temperature and shows that promptly V species wherein have strong reducing power, in addition, lower reduction temperature is hinting that also the mobility of Lattice Oxygen is stronger, and these may be the key factors that L300-H600 has higher propane conversion capability.
The specific embodiment
Embodiment 1
In the reaction of selective oxidation of propane system acrylic acid, product is divided into gas, liquid two-phase.Gas-phase product comprises CO, CO
2, C
2H
4And C
2H
6, liquid product comprises purpose product acrylic acid, a spot of by-product acetic acid and acetone.
Conversion ratio and selectivity and productive rate calculate with following formula:
Conversion ratio (%)=(∑ Mi * ni)/(amount of substance of propane in the charging) * 100%
Selectivity (%)=(Mi * ni)/(∑ Mi * ni) * 100%
Productive rate (%)=conversion ratio * selectivity * 100
(Mi: the amount of substance of certain product i; Ni: institute's carbon atom quantity in certain product i molecule)
Embodiment 1
Adopting ammonium paramolybdate, ammonium metavanadate, telluric acid and niobium oxalate is raw material, and the ratio of the amount of substance between Mo, V, Te and four kinds of metallic elements of Nb is 1.0: 0.30: 0.23: 0.12.Prepare catalyst precursor with the Rotary Evaporators of being furnished with vavuum pump.At first 13.15g ammonium paramolybdate, 2.62g ammonium metavanadate and 3.93g telluric acid are added in the 250mL rotary flask, add the 55.0mL deionized water, in temperature is to be cooled to 40 ℃ behind the rotation mixing 120min in the water-bath in 60 ℃, and fully dissolving gets wine-colored Mo-V-Te solution; Take by weighing 5.17g niobium oxalate powder in the 100mL conical flask, deionized water water-bath rotation in 60 ℃ of adding 20.0mL mixes 30min and is cooled to 40 ℃, obtains colourless settled solution; Niobium oxalate solution is joined in the above-mentioned wine-colored Mo-V-Te solution, produce a large amount of precipitations at this moment, continuation is cooled to room temperature after rotating and mixing 120min, vacuumizes the beginning rotary evaporation then to dried, gets the Mo-V-Te-Nb-O catalyst precursor.The catalyst precursor of drying at 250 ℃, is reduced to room temperature naturally behind the roasting 120min in the air, continue at N
2600 ℃ of roasting 120min in the atmosphere.With catalyst grinding, moulding, the granulation after the roasting, sieve into 20～30 purpose catalyst granules, the gained catalyst is designated as L250-H600.380 ℃ of reaction temperatures, reaction velocity 785L/g-cat/h, V (C
3H
8)/V (air)/V (H
2O)=1: 15: 12, gas overall flow rate 28mL/min the results are shown in Table 1.
The preparation of Mo-V-Te-Nb-O catalyst precursor is with embodiment 1.The gained catalyst precursor at 275 ℃, is reduced to room temperature naturally behind the roasting 120min in the air, continue at N
2600 ℃ of roasting 120min in the atmosphere.With catalyst grinding, moulding, the granulation after the roasting, sieve into 20～30 purpose catalyst granules, the gained catalyst is designated as L275-H600.Reaction condition the results are shown in Table 1 with embodiment 1.
Embodiment 3
The preparation of Mo-V-Te-Nb-O catalyst precursor is with embodiment 1.The gained catalyst precursor at 300 ℃, is reduced to room temperature naturally behind the roasting 120min in the air, continue at N
2600 ℃ of roasting 120min in the atmosphere.With catalyst grinding, moulding, the granulation after the roasting, sieve into 20～30 purpose catalyst granules, the gained catalyst is designated as L300-H600.Reaction condition the results are shown in Table 1 with embodiment 1.
Embodiment 4
The preparation of Mo-V-Te-Nb-O catalyst precursor is with embodiment 1.The gained catalyst precursor at 330 ℃, is reduced to room temperature naturally behind the roasting 120min in the air, continue at N
2600 ℃ of roasting 120min in the atmosphere.With catalyst grinding, moulding, the granulation after the roasting, sieve into 20～30 purpose catalyst granules, the gained catalyst is designated as L330-H600.Reaction condition the results are shown in Table 1 with embodiment 1.
Embodiment 5
The preparation of Mo-V-Te-Nb-O catalyst precursor is with embodiment 1.The gained catalyst precursor at 300 ℃, is reduced to room temperature naturally behind the roasting 120min in the air, continue at N
2550 ℃ of roasting 120min in the atmosphere.With catalyst grinding, moulding, the granulation after the roasting, sieve into 20～30 purpose catalyst granules, the gained catalyst is designated as L300-H550.Reaction condition the results are shown in Table 1 with embodiment 1.
Embodiment 6
The preparation of Mo-V-Te-Nb-O catalyst precursor is with embodiment 1.The gained catalyst precursor at 300 ℃, is reduced to room temperature naturally behind the roasting 120min in the air, continue at N
2580 ℃ of roasting 120min in the atmosphere.With catalyst grinding, moulding, the granulation after the roasting, sieve into 20～30 purpose catalyst granules, the gained catalyst is designated as L300-H580.Reaction condition the results are shown in Table 1 with embodiment 1.
Embodiment 7
The preparation of Mo-V-Te-Nb-O catalyst precursor is with embodiment 1.The gained catalyst precursor at 300 ℃, is reduced to room temperature naturally behind the roasting 120min in the air, continue at N
2630 ℃ of roasting 120min in the atmosphere.With catalyst grinding, moulding, the granulation after the roasting, sieve into 20～30 purpose catalyst granules, the gained catalyst is designated as L300-H630.Reaction condition the results are shown in Table 1 with embodiment 1.
Comparative example 1
The preparation of Mo-V-Te-Nb-O catalyst precursor is with embodiment 1.The gained catalyst precursor is warming up to 200 ℃ keeps 60min under N2 protection, continue to be warming up to 600 ℃ again and keep lowering the temperature naturally behind the 120min, this kind or similar therewith roasting mode are referred to as the one-part form roasting.The gained catalyst is designated as Onestep-600.Experimental result: conversion of propane and acrylic acid selectivity are respectively 20.1% and 58.1%.Reaction condition the results are shown in Table 2 with embodiment 1.Through the catalyst of one-part form calcination process except the catalytic effect that is better than the L300-H550 catalyst sample, all not as the catalyst sample of two-segment calcining.
Comparative example 2
Lin Luo etc. is " Comparison of Reaction Pathways for thePartial Oxidation of Propane over Vanadyl Ion-Exchanged Zeolite Beta andMo at title of article
1V
0.3Te
0.23Nb
0.12O
x", in J.Catal.200 (2001) 222 1 literary compositions to Mo
1V
0.3Te
0.23Nb
0.12O
xCatalyst has carried out the research of oxidation of propane system acrylic acid.The catalyst process is at N
2In the roasting of 600 ℃ of roasting 120min one-part forms obtain.Catalyst amount is 0.70g, and reactor feed gas is than V (C
3H
8)/V (O
2)/V (H
2O)/and V (He)=4/2/4/5, the gas overall flow rate is 15mL/min,, 350 ℃ of reaction temperatures.Experimental result: conversion of propane and acrylic acid selectivity are respectively 27.2% and 64.7%, acrylic acid yield 17.6%.
Comparative example 3
P.Botella etc. are " Selective oxidation of propane to acrylic acidon MoVNbTe mixed oxides catalysts prepared by hydrothermal synthesis " at title of article, MoVNbTe catalyst to Hydrothermal Preparation in Catal.Lett.74 (2001) 149 1 literary compositions has carried out the research of oxidation of propane system acrylic acid, and catalyst is through at N
2In 600 ℃ of roasting 120min one-part form roastings and get reactor feed gas ratio V (C
3H
8)/V (O
2)/V (H
2O)/and V (He)=4/8/30/58, reaction velocity 409g
Cat.h.mol
-1, 380 ℃ of reaction temperatures.Experimental result: conversion of propane and acrylic acid selectivity are respectively 31.1% and 56.5%, acrylic acid yield 17.6%.
Comparative example 4
D.Vitry etc. are " Mo-V-Te-(Nb)-O mixed metal oxides preparedby hydrothermal synthesis for catalytic selective oxidations of propane andpropene to acrylic acid " at title of article, the MoVNbTe catalyst of (2003) 411 pairs of Hydrothermal Preparation of Appl.Catal.A:Gen.251 has carried out the research of oxidation of propane system acrylic acid, and the catalyst process is at N
2In 600 ℃ of roasting 120min one-part form roastings and getting.Catalyst amount is 0.500g, and the reactor feed gas ratio is: V (C
3H
8)/V (O
2)/V (H
2O)/V (N
2)=8/10/45/37, gas overall flow rate 20mL/min, 380 ℃ of reaction temperatures.Experimental result: conversion of propane and acrylic acid selectivity are respectively 33.4% and 62.4%, acrylic acid yield 20.8%.
Comparative example 5
People such as M.Baca are " Propane oxidation on MoVTeNbO mixedoxide catalysts:study of the phase composition of active and selectivecatalysts " at title of article, synthetic MoV in Top.Catal.23 (2003) 39 1 literary compositions
0.33Te
0.22Nb
0.11O
xThe time, at first at the slurries of 150 ℃ of dry Mo, V, Te and Nb, promptly obtain the presoma of Mo-V-Te-Nb-O catalyst, then in 300 ℃ of air and 600 ℃ of N by the mode of conventional drying
2Roasting 120min gets the Mo-V-Te-Nb-O catalyst.
V (C
3H
8)/V (O
2)/V (H
2O)/V (N
2)/V (He)=6/10/43/36/5, air speed 2500h
-1, 380 ℃ of reaction temperatures.Experimental result: conversion of propane and acrylic acid selectivity are respectively 34.9% and 53%, acrylic acid yield 18.5%.
Comparative example 6
People such as J.M.L ó pez Nieto utilize hydro-thermal method to synthesize the Mo-V-Te-Nb-O catalyst at title of article in for " The selective oxidation of propaneon Mo-V-Te-Nb-O catalysts:The influence of Te-precursor " Catal.Today 81 (2003) 87 1 literary compositions, and being used for the reaction of oxidation of propane system acrylic acid, the catalyst process is at N
2In 600 ℃ of roasting 120min one-part form roastings and get reactor feed gas ratio V (C
3H
8)/V (O
2)/V (H
2O)/and V (He)=4/8/30/58, reaction velocity 510g
Cat.h.mol
-1, 380 ℃ of reaction temperatures.Experimental result: conversion of propane and acrylic acid selectivity are respectively 21.9% and 51.7%, acrylic acid yield 11.3%.
Comparative example 7
People such as J.M.Oliver are " The effect of pH on structural and catalyticproperties of MoVTeNbO catalysts " at title of article, utilize the rotary evaporation method to synthesize the Mo-V-Te-Nb-O catalyst precursor in Appl.Catal.A:Gen.257 (2004) 67 1 literary compositions, through at N
2In the roasting of 600 ℃ of roasting 120min one-part forms get the Mo-V-Te-Nb-O catalyst, and be used for oxidation of propane system acrylic acid reaction, reactor feed gas ratio V (C
3H
8)/V (O
2)/V (H
2O)/and V (He)=4/8/30/58, reaction velocity 500g
Cat.h.mol
-1, 380 ℃ of reaction temperatures.Experimental result: conversion of propane and acrylic acid selectivity are respectively 2.7% and 0%, acrylic acid yield 0%.
Reaction result among table 1 embodiment
Reaction result in table 2 comparative example
Claims (9)
1. be used for the acrylic acid molybdenum-vanadium-tellurium-niobium catalytic agent of oxidation of propane system, in the described catalyst, the relative mol ratio of Mo, V, Te, these several elemental compositions of Nb is Mo: V: Te: Nb=(0.25～0.98): (0.003～0.5): (0.003～0.5): (0.003～0.5); It is characterized in that: the chemical composition of described catalyst is Mo
1V
0.3Te
0.23Nb
0.12O
x
2. according to the described acrylic acid molybdenum-vanadium-tellurium-niobium catalytic agent of oxidation of propane system that is used for of claim 1, it is characterized in that:
Described catalyst precursor prepares by the rotary evaporation method, and then obtains through two-segment calcining: promptly at first at 200～350 ℃ roasting temperature, atmosphere is air, and roasting time 30min～6h reduces to room temperature after the roasting; Second section calcination procedure is at N
2Carry out 400～700 ℃ of sintering temperatures, roasting time 30min～6h in the atmosphere.
3. according to the described acrylic acid molybdenum-vanadium-tellurium-niobium catalytic agent of oxidation of propane system that is used for of claim 2, it is characterized in that:
The described process specific requirement that catalyst precursor is handled by the two-segment calcining mode is: at first roasting under 250～330 ℃ of conditions, and atmosphere is air, roasting time 30min～6h reduces to room temperature then;
Enter second section roasting process afterwards, 550～650 ℃ of sintering temperatures, calcination atmosphere are N
2Atmosphere.
4. the described preparation method who is used for the acrylic acid molybdenum-vanadium-tellurium-niobium catalytic agent of oxidation of propane system of claim 1 is characterized in that: at first prepare catalyst precursor, obtain final catalyst through two-segment calcining then; Wherein: the process specific requirement that catalyst precursor is handled by the two-segment calcining mode is:
At first roasting under 200～350 ℃ of conditions, roasting time 30min～6h;
Enter second section roasting process afterwards, 400～700 ℃ of sintering temperatures.
5. according to the described preparation method who is used for the acrylic acid molybdenum-vanadium-tellurium-niobium catalytic agent of oxidation of propane system of claim 4, it is characterized in that: the process specific requirement that catalyst precursor is handled by the two-segment calcining mode is:
At first roasting under 250～330 ℃ of conditions, atmosphere is air, roasting time 30min～6h reduces to room temperature then;
Enter second section roasting process afterwards, 550～650 ℃ of sintering temperatures, calcination atmosphere are N
2Atmosphere.
6. according to the described preparation method who is used for the acrylic acid molybdenum-vanadium-tellurium-niobium catalytic agent of oxidation of propane system of claim 5, it is characterized in that: the process specific requirement that catalyst precursor is handled by the two-segment calcining mode is:
(1) phase I roasting: with the catalyst precursor calcination vessel of packing into, in air atmosphere, rise to the phase I sintering temperature that presets, after keeping 30min～6h under this temperature, reduce to room temperature naturally with the heating rate of 1 ℃/min～10 ℃/min;
(2) second stage roasting: will be through the product of the first section roasting calcination vessel of packing into, at N
2In the atmosphere, rise to the sintering temperature of the second stage that presets, after keeping 30min～6h under this temperature, reduce to room temperature naturally with 1 ℃/min～10 ℃/heating rate of min.
7. according to claim 4 or the 5 or 6 described preparation methods that are used for the acrylic acid molybdenum-vanadium-tellurium-niobium catalytic agent of oxidation of propane system, it is characterized in that: described catalyst precursor utilizes the preparation of rotary evaporation method.
8. according to the described preparation method who is used for the acrylic acid molybdenum-vanadium-tellurium-niobium catalytic agent of oxidation of propane system of claim 7, it is characterized in that: described catalyst precursor is to utilize Rotary Evaporators to prepare.
9. according to the described preparation method who is used for the acrylic acid molybdenum-vanadium-tellurium-niobium catalytic agent of oxidation of propane system of claim 7, it is characterized in that: with the presoma of described catalyst after the two-part high-temperature roasting, products therefrom is fully ground and molding, granulating, and to sieve into particle diameter be 20～30 purpose catalyst granules.
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| CN200810228225A Pending CN101722017A (en) | 2008-10-22 | 2008-10-22 | Molybdenum-vanadium-tellurium-niobium catalytic agent for preparing acrylic acid by propane oxidation and preparation method thereof |
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| CN102476057A (en) * | 2010-11-25 | 2012-05-30 | 中国科学院大连化学物理研究所 | Preparation method of MoVTeNbO catalyst for reaction of preparing acrylic acid by propane oxidation |
| CN102989487A (en) * | 2012-12-17 | 2013-03-27 | 中国科学院大连化学物理研究所 | After-treatment method for molybdenum vanadium tellurium niobium catalyst |
| CN103721727A (en) * | 2014-01-06 | 2014-04-16 | 沈阳化工大学 | Mo-V-Te-Nb-Cr composite metal oxide catalyst and preparation method thereof |
| CN105582964A (en) * | 2014-11-18 | 2016-05-18 | 中触媒有限公司 | Composite metal oxide catalyst, preparation method and application thereof |
| CN110833828A (en) * | 2018-08-16 | 2020-02-25 | 中国科学院大连化学物理研究所 | Mixed phase catalyst for one-step ammoxidation of propane to prepare acrylonitrile acid |
| CN111468136A (en) * | 2020-05-19 | 2020-07-31 | 西南化工研究设计院有限公司 | Catalyst for preparing acrylic acid by oxidizing propane and preparation method thereof |
| CN112547062A (en) * | 2019-09-25 | 2021-03-26 | 中国石油化工股份有限公司 | Catalyst for preparing acrylic acid from acrolein and preparation method and application thereof |
| CN113070079A (en) * | 2021-04-13 | 2021-07-06 | 宁波昊祥新材料科技有限公司 | Preparation method and system of Mo-V-Te-Sb-Nb-O catalyst |
| CN113083284A (en) * | 2021-04-13 | 2021-07-09 | 宁波昊祥新材料科技有限公司 | Mo-V-Te-Sb-Nb-O catalyst, and preparation method and application thereof |
| CN114534714A (en) * | 2020-11-26 | 2022-05-27 | 中国科学院大连化学物理研究所 | Molybdenum-vanadium-antimony-oxygen catalyst for co-production of propylene and acrylic acid by oxidation of propane and preparation method thereof |
| CN114618533A (en) * | 2020-12-14 | 2022-06-14 | 中国科学院大连化学物理研究所 | Catalyst forming method |
| CN115518646A (en) * | 2021-06-24 | 2022-12-27 | 中国石油化工股份有限公司 | Catalyst for low-carbon alkane oxidation/ammoxidation and preparation method thereof |
| CN116328796A (en) * | 2021-12-22 | 2023-06-27 | 中国石油天然气股份有限公司 | Mo-V-Te-Nb system catalyst and preparation method thereof |
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| CN102476057A (en) * | 2010-11-25 | 2012-05-30 | 中国科学院大连化学物理研究所 | Preparation method of MoVTeNbO catalyst for reaction of preparing acrylic acid by propane oxidation |
| CN102989487A (en) * | 2012-12-17 | 2013-03-27 | 中国科学院大连化学物理研究所 | After-treatment method for molybdenum vanadium tellurium niobium catalyst |
| CN103721727A (en) * | 2014-01-06 | 2014-04-16 | 沈阳化工大学 | Mo-V-Te-Nb-Cr composite metal oxide catalyst and preparation method thereof |
| CN103721727B (en) * | 2014-01-06 | 2016-03-16 | 沈阳化工大学 | A kind of Mo-V-Te-Nb-Cr O composite metallic oxide catalyst and preparation method thereof |
| CN105582964A (en) * | 2014-11-18 | 2016-05-18 | 中触媒有限公司 | Composite metal oxide catalyst, preparation method and application thereof |
| CN105582964B (en) * | 2014-11-18 | 2018-08-07 | 中触媒有限公司 | A kind of O composite metallic oxide catalyst and its preparation method and application |
| CN110833828B (en) * | 2018-08-16 | 2021-01-15 | 中国科学院大连化学物理研究所 | Mixed phase catalyst for one-step ammoxidation of propane to prepare acrylonitrile |
| CN110833828A (en) * | 2018-08-16 | 2020-02-25 | 中国科学院大连化学物理研究所 | Mixed phase catalyst for one-step ammoxidation of propane to prepare acrylonitrile acid |
| CN112547062A (en) * | 2019-09-25 | 2021-03-26 | 中国石油化工股份有限公司 | Catalyst for preparing acrylic acid from acrolein and preparation method and application thereof |
| CN111468136A (en) * | 2020-05-19 | 2020-07-31 | 西南化工研究设计院有限公司 | Catalyst for preparing acrylic acid by oxidizing propane and preparation method thereof |
| CN114534714A (en) * | 2020-11-26 | 2022-05-27 | 中国科学院大连化学物理研究所 | Molybdenum-vanadium-antimony-oxygen catalyst for co-production of propylene and acrylic acid by oxidation of propane and preparation method thereof |
| CN114534714B (en) * | 2020-11-26 | 2023-08-22 | 中国科学院大连化学物理研究所 | Molybdenum vanadium antimony oxide catalyst for coproducing propylene and acrylic acid by propane oxidation and preparation method thereof |
| CN114618533A (en) * | 2020-12-14 | 2022-06-14 | 中国科学院大连化学物理研究所 | Catalyst forming method |
| CN113070079A (en) * | 2021-04-13 | 2021-07-06 | 宁波昊祥新材料科技有限公司 | Preparation method and system of Mo-V-Te-Sb-Nb-O catalyst |
| CN113083284A (en) * | 2021-04-13 | 2021-07-09 | 宁波昊祥新材料科技有限公司 | Mo-V-Te-Sb-Nb-O catalyst, and preparation method and application thereof |
| CN113070079B (en) * | 2021-04-13 | 2022-01-11 | 宁波昊祥新材料科技有限公司 | Preparation method and system of Mo-V-Te-Sb-Nb-O catalyst |
| CN115518646A (en) * | 2021-06-24 | 2022-12-27 | 中国石油化工股份有限公司 | Catalyst for low-carbon alkane oxidation/ammoxidation and preparation method thereof |
| CN115518646B (en) * | 2021-06-24 | 2024-03-26 | 中国石油化工股份有限公司 | Catalyst for low-carbon alkane oxidation/ammoxidation and preparation method thereof |
| CN116328796A (en) * | 2021-12-22 | 2023-06-27 | 中国石油天然气股份有限公司 | Mo-V-Te-Nb system catalyst and preparation method thereof |
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