CN1795987A - Catalyst of Mo, V, Te, Nb in use for reaction of producing crylic acid by selective oxidation of propane - Google Patents
Catalyst of Mo, V, Te, Nb in use for reaction of producing crylic acid by selective oxidation of propane Download PDFInfo
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Abstract
The invention relates to a Mo-V-Te-Nb catalyst for making propane undergo the process of selective oxidation reaction for preparing acrylic acid and its preparation method. It is characterized by that said invention utilizes a chemical method to make the fresh catalyst undergo the process of high-temperature activation treatment. Said high-temperature activation treatment is implemented under the reaction atmosphere, the volume ratio of reaction gas V(C3H8)/V(air)/V(vapor)=1/5-25/1-24, reaction space velocity is 500-1500 mL/g-cat/h, the activation temperature is 400-700deg.C and activation time is 2-20hr. said invention can make propane conversion rate and acrylic acid selectivity respectively be up to 59% and 64%.
Description
Technical field:
The present invention relates to a kind of Mo-V-Te-Nb-O catalyst that is used for the reaction of selective oxidation of propane system acrylic acid, its preparation method, and the application in the reaction of selective oxidation of propane system acrylic acid.
Background technology:
Methacrylaldehyde, acrylic acid and ester class series of products thereof generally are used for industries such as coating, chemical fibre, weaving, light industry, also are used for oil exploitation, oil dope etc.The process route of making methacrylaldehyde, acrylic acid and ester thereof is more, and is now industrial based on propylene oxidation.But the propylene cost is higher, approximately is 1～2 times of propane prices, therefore adopts propane cheap and easy to get to replace direct oxidation of propylene acrolein and acrylic acid to become one of research focus of low-carbon alkanes development and use.The source of propane is abundant simultaneously, and it is a main component in casing-head gas, natural gas, the refinery gas.It is about 6% to contain propane in casing-head gas such as the grand celebration of China, Tarim Basin, contains propane 3～6% in the condensate, and it is about 60% to contain propane in the liquefied petroleum gas, contains propane about 15% in the natural gas moisture.In the past, propane generally all is used for fuel, produces ethene and propylene on a small quantity as solvent, or as the raw material of steam cracking.In recent years, added value high middle chemical products or industrial chemicals are processed in propane catalysis are subject to people's attention day by day, wherein preparing propylene by propane selective oxidization, acrylic acid are one of directions in exploration.
In sum, because enrich in cheap, the source of propane, make direct synthesis of acrolein of propane oxidation step or acrylic acid have remarkable economic efficiency and practical significance.
Yet in the acrylic acid reaction of selective oxidation of propane system, exist two big difficult points:
The one, propane is as saturated hydrocarbons, and its c h bond is very strong.Under most reaction conditions, the reactivity of propane is all very low.The methyl c h bond institute energy requirement of activation propane is enough broken the C-C key in the partial oxidation products, causes the generation of low carbon product.So one of difficult point is how to utilize catalytic process to select to activate strong c h bond on the propane, makes the comparatively propane generation partial oxidation reaction of inertia; Avoid breaking C-C key weak in the C3 product simultaneously, protect active C3 intermediate product, stop its deep oxidation.
The 2nd, acrylic acid is the purpose product of propane partial oxidation reaction, in all C3 products, further oxidation generation acrylic acid of some intermediate products is arranged, as propylene or methacrylaldehyde; And the other intermediate product can regeneration acrylic acid, as acetone.So facing two of a difficult problem is the generations that how to stop and suppress the accessory substance approach, improve the acrylic acid selectivity.
The key that solves above two difficult points is to seek a kind of catalyst of highly effective, and reaction is carried out to the direction that generates the purpose product, improves the conversion ratio and the purpose product selectivity of reactant.
Being used for selective oxidation of propane system acrylic acid catalyst for reaction at present generally all is multicomponent, multifunction catalyst.V-P-O catalyst (Catalysis Today, Vol.13, p679 (1992)), Mn-P-O catalyst (Chemistry Letter, p1733 (1989)), Bi-V-Mo-O catalyst (Catalysis Today, Vol.13, p673 (1992)), Bi-V-Nb-Sb-Mo-O catalyst (US Patent No.5198580) etc. all once was used for this reaction, but acrylic acid yield does not all have to surpass 10%.
In mixed metal oxide catalyst, the Mo-V-Te-Nb-O catalyst has good catalytic performance to this reaction, and the possibility that replaces the acrylic acid traditional catalyst of propylene two-step method Selective Oxidation in the current industrial production is arranged.The relevant Mo that is reported in Japanese Mitsubishi Kasei company and U.S. Rohm and Haas company
1V
0.3Te
0.23Nb
0.12O
nIn the patent of catalyst (European Patent No.0608838 and EuropeanPatent No.0962253), acrylic acid yield is respectively up to 48% and 42%, but many research groups of US and European all do not repeat out this result.In most research results (Topics in Catalysis, Vol.23, p39 (2003) and Journal of Catalysis, Vol.200, p222 (2001)), acrylic acid productive rate is only between 14%～23%.
Mo-V-Te-Nb-O Preparation of catalysts method is very big to its crystal structure and the catalytic performance influence in the reaction of selective oxidation of propane system acrylic acid, and this is that this catalyst performance is difficult to one of major reason of repetition.Simultaneously, the Mo-V-Te-Nb-O catalyst needs before use through special activation process, just can make this catalyst generate necessary active phase and select mutually.But in numerous patents and the document published, activation methods of not mentioned catalyst all.And to the long reaction stability of this catalyst in reaction all do not have the report.
Summary of the invention:
The objective of the invention is to,, the catalytic performance of Mo-V-Te-Nb-O catalyst in the reaction of selective oxidation of propane system acrylic acid is improved by activation process.
Another purpose of the present invention is, by activation process, the stability of Mo-V-Te-Nb-O catalyst in the reaction of selective oxidation of propane system acrylic acid is improved.
For achieving the above object, the invention provides a kind of molybdenum-vanadium-tellurium-niobium catalytic agent that is used for the reaction of selective oxidation of propane system acrylic acid, the relative mol ratio of each element is as follows in the catalyst:
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: described catalyst is handled acquisition by fresh catalyst is carried out high-temperature activation with chemical method; High-temperature activation is handled and carry out the volume ratio V (C of reaction gas under reaction atmosphere
3H
8)/V (air)/V (vapor)=1/5～25/0～24, reaction velocity is 500～1500mL/g-cat/h, and activation temperature is 400～700 ℃, and soak time is 2～20h.
Wherein, rMo, rV, rTe, rNb are respectively metallic element Mo, V, Te, the relative mol ratio of Nb is that the cubage of other all elements of basis except that element O forms.For example, use Mo
aV
bTe
cNb
dO
nRepresent the molecular formula of Mo-V-Te-Nb-O catalyst, the relative mol ratio of each metallic element is calculated as follows:
rMo＝a/(a+b+c+d)
rV＝b/(a+b+c+d)
rTe＝c/(a+b+c+d)
rNb＝d/(a+b+c+d)
The present invention is used for the molybdenum-vanadium-tellurium-niobium catalytic agent of selective oxidation of propane system acrylic acid reaction, and refering in particular to chemical composition is Mo
1V
0.3Te
0.23Nb
0.12O
xCatalyst, x=4.5～4.8 wherein.
The present invention also provides a kind of preparation method who is used for the molybdenum-vanadium-tellurium-niobium catalytic agent of selective oxidation of propane system acrylic acid reaction, it is characterized in that: fresh catalyst is carried out high-temperature activation with chemical method handle; High-temperature activation is handled and carry out the volume ratio V (C of reaction gas under reaction atmosphere
3H
8)/V (air)/V (vapor)=1/5～25/0～24, reaction velocity is 500～1500mL/g-cat/h, and activation temperature is 400～700 ℃, and soak time is 2～20h.
The present invention is used for the preparation method of the molybdenum-vanadium-tellurium-niobium catalytic agent of selective oxidation of propane system acrylic acid reaction, the volume ratio V (C of described reaction gas
3H
8)/V (air)/V (vapor)=1/12～15/10～15, reaction velocity is 600～900mL/g-cat/h.Activation temperature is 450～600 ℃ preferably, and soak time is 10～14h.
The present invention is used for the preparation method of the molybdenum-vanadium-tellurium-niobium catalytic agent of selective oxidation of propane system acrylic acid reaction, and the catalyst after described high-temperature activation can being handled grinds to form the powder of particle diameter less than 20um, and molding, granulating sieves into 20～30 purpose catalyst granules.
The present invention is used for the preparation method of the molybdenum-vanadium-tellurium-niobium catalytic agent of selective oxidation of propane system acrylic acid reaction, and described high-temperature activation processing procedure is:
---with the fresh catalyst reactor of packing into, the N that is flowing
2Under the atmosphere protection, be warming up to 380 ℃ with the heating rate of 6 ℃/min
---with N
2Atmosphere switches to reaction atmosphere, and behind the stable reaction 10min, the heating rate with 2 ℃/min slowly is warming up to activation temperature again, keep certain hour after, be cooled to 380 ℃ with the speed of 2 ℃/min;
---change reaction atmosphere into N
2Atmosphere is at N
2The protection of atmosphere drops to room temperature.
The present invention is used for the preparation method of the molybdenum-vanadium-tellurium-niobium catalytic agent of selective oxidation of propane system acrylic acid reaction, and during activating catalyst, oxygen concentration needs between 2%～10% in the tail gas under reaction atmosphere; Preferably between 3%～5%.
The present invention is used for the preparation method of the molybdenum-vanadium-tellurium-niobium catalytic agent of selective oxidation of propane system acrylic acid reaction, and described fresh catalyst is to utilize Rotary Evaporators to prepare catalyst precursor to obtain through roasting again, and roasting is at static N
2Carry out under the protection of gas, temperature is 550～650 ℃, time 1～3h.
The molybdenum-vanadium-tellurium-niobium catalytic agent that is used for the reaction of selective oxidation of propane system acrylic acid provided by the present invention can make conversion of propane and acrylic acid selectivity respectively up to 59% and 64%.In the reaction of 100h, reaction stability is fine, and promptly reaches stable reactiveness in the starting stage of reaction.
Description of drawings:
Fig. 1 is the reaction stability of fresh Mo-V-Te-Nb-O catalyst; Wherein, zero hydrocarbon selectivity, ● acrylic acid selectivity, ■ conversion of propane;
Fig. 2 is the reaction stability of the Mo-V-Te-Nb-O catalyst after activating; Wherein, △ acrylic acid selectivity, ◆ conversion of propane, the ◇ acrylic acid yield, zero hydrocarbon selectivity, ● propylene selectivity, ▲ acetic acid selectivity, other compound selective of;
Fig. 3 is the XRD figure of Mo-V-Te-Nb-O catalyst before and after activation; Wherein, a is for before activating, and b is for after activating;
Fig. 4 is the XRD figure of Mo-V-Te-Nb-O catalyst fresh and that activate, a. fresh catalyst under various different atmospheres; B. the catalyst that under air atmosphere, activates; C. the catalyst that under the atmosphere that contains air and steam, activates; D. the catalyst that under the atmosphere that contains nitrogen and steam, activates; E. the catalyst that under reaction atmosphere, activates.
Fig. 5 is the XRD figure of Mo-V-Te-Nb-O catalyst after the activation of reacting under the different condition; Mo-V-Te-Nb-O catalyst after a activation; B is reacted catalyst under anhydrous condition; C adds the water catalyst for reaction again after reacting under anhydrous condition.
The specific embodiment:
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
2And C
3H
6Liquid product comprises purpose product acrylic acid, a spot of by-product acetic acid, and accessory substance methacrylaldehyde, acetone, the propionic acid of trace.
Conversion ratio and selectivity and productive rate calculate with following formula:
Productive rate (%)=conversion ratio * selectivity * 100
(Mi: the molal quantity of certain product; Ni: institute's carbon atom quantity in certain product molecule)
Embodiment 1
Adopt ammonium paramolybdate, ammonium metavanadate, telluric acid and niobium oxalate as raw material, the mol ratio between the metallic atom is 1: 0.3: 0.23: 0.12.Prepare catalyst with Rotary Evaporators.At first 6.425g ammonium paramolybdate, 1.275g ammonium metavanadate and 1.925g telluric acid together are put in the rotary evaporation bottle, add 105mL distilled water, be heated to 80 ℃ it is dissolved fully, obtain orange-yellow settled solution.Behind the rotation 2h, be cooled to 40 ℃.Add 41.1mL (C again
Nb5+=9.8mg/mL) niobium oxalate solution, at this moment solution becomes muddy gradually, has sediment to occur.Rotate 2h again.Under 40 ℃, vacuumize drying sample then.Dry good presoma sieves into 20～30 purpose particles, at static N through grinding, moulding, granulation
2The following 600 ℃ of roasting 2h of atmosphere protection.With catalyst grinding, moulding, the granulation after the roasting, sieve into 20～30 purpose catalyst granules, promptly get fresh Mo
1V
0.3Te
0.23Nb
0.12O
xCatalyst, XRD figure is seen Fig. 3.
With the embodiment 1 fresh catalyst 2.14g reaction tube of packing into, the N that is flowing
2Under the atmosphere protection, be warming up to 380 ℃ with the heating rate of 6 ℃/min; Then with N
2Atmosphere switches to reaction atmosphere, reaction condition: feed gas volume is than V (C
3H
8)/V (air)/V (vapor)=1/15/12, reaction velocity is 800mL/g-cat/h, and reaction temperature is 400 ℃, and the heating rate with 2 ℃/min slowly is warming up to activation temperature again.After keeping certain hour under this condition, the speed with 2 ℃/min under same reaction atmosphere is cooled to 380 ℃.Switch to N again
2Atmosphere is at N
2The protection of atmosphere drops to room temperature.Obtain catalyst activated.XRD figure is seen Fig. 3.
Embodiment 3
Embodiment 4
Embodiment 5
2.45g embodiment 2 catalyst after overactivation are contained in carrying out the reaction of selective oxidation of propane system acrylic acid in the reactor of embodiment 3.Reactor feed gas ratio V (C
3H
8)/V (air)/V (Vapor)=1/15/12, reaction temperature is 400 ℃, reaction velocity is 700mL/g-cat/h.The results are shown in table 1.
Embodiment 6
Embodiment 7
2.45g embodiment 2 catalyst after overactivation are contained in carrying out the reaction of selective oxidation of propane system acrylic acid in the reactor of embodiment 3.Reactor feed gas ratio V (C
3H
8)/V (air)/V (Vapor)=1/20/12, reaction temperature is 400 ℃, reaction velocity is 800mL/g-cat/h.The results are shown in table 1.
Comparative example 1
Fresh embodiment 1 catalyst that 3.0g is not activated is used for the reaction of selective oxidation of propane system acrylic acid, carries out stability experiment.Reactor feed gas ratio V (C
3H
8)/V (air)/V (Vapor)=1/15/12, reaction temperature is 400 ℃, reaction velocity is 560mL/g-cat/h.Between the stage of reaction of the 200h that is investigated, conversion of propane keeps 19%, and acrylic acid selectivity rises to 50% by 32%, CO
xSelectivity reduce to 34% by 51%.Reactivity worth is lower, and plays pendulum always.As shown in Figure 1.
Comparative example 2
Not activated fresh embodiment 1 catalyst is used for the reaction of selective oxidation of propane system acrylic acid.Reaction condition: feed gas volume is than V (C
3H
8)/V (air)/V (vapor)=1/15/12, air speed is 800mL/g-cat/h, catalyst amount is 2.14g.Between the stage of reaction of the 200h that is investigated, conversion of propane keeps 19%, and acrylic acid selectivity rises to 50% by 32%, CO
xSelectivity reduce to 34% by 51%.Reactivity worth plays pendulum always.
Comparative example 3
Fresh embodiment 1 catalyst is carried out activation processing under air atmosphere, operating process is identical with embodiment 2 usefulness reaction gas activation processs.Catalyst after a period of time, grinds moulding at high temperature under this atmosphere again, sieves into 20～30 purpose catalyst granules.This catalyst of 2.14g is contained in carrying out the reaction of selective oxidation of propane system acrylic acid in the reactor of embodiment 2.Reactor feed gas ratio V (C
3H
8)/V (air)/V (Vapor)=1/15/12, reaction temperature is 400 ℃, reaction velocity is 800mL/g-cat/h.In the reaction result, conversion of propane is 1.23%, and no acrylic acid generates.
Comparative example 4
Fresh embodiment 1 catalyst is carried out activation processing under the atmosphere that contains air and steam, operating process is with identical with embodiment 2 reaction gas activation processs.Catalyst after a period of time, grinds moulding in high-temperature process under this atmosphere again, sieves into 20～30 purpose catalyst granules.This catalyst of 2.14g is contained in carrying out the reaction of selective oxidation of propane system acrylic acid in the reactor of embodiment 2.Reactor feed gas ratio V (C
3H
8)/V (air)/V (Vapor)=1/15/12, reaction temperature is 400 ℃, reaction velocity is 800mL/g-cat/h.In the reaction result, conversion of propane is 0.32%, and no acrylic acid generates.
Comparative example 5
Fresh embodiment 1 catalyst is carried out activation processing under the atmosphere that contains nitrogen and steam, operating process is with identical with embodiment 2 reaction gas activation processs.Catalyst after a period of time, grinds moulding in high-temperature process under this atmosphere again, sieves into 20～30 purpose catalyst granules.This catalyst of 2.14g is contained in carrying out the reaction of selective oxidation of propane system acrylic acid in the reactor of embodiment 2.Reactor feed gas ratio V (C
3H
8)/V (air)/V (Vapor)=1/15/12, reaction temperature is 400 ℃, reaction velocity is 800mL/g-cat/h.In the reaction result, conversion of propane is 58.4%, and the acrylic acid selectivity is 41.4%.
Comparative example 6
Mo-V-Te-Nb-O catalyst after the 2.14g activation is carried out the reaction of selective oxidation of propane system acrylic acid under anhydrous condition.Reactor feed gas is than V (C
3H
8)/V (air)=1/15, air speed is 450mL/g-cat/h, reaction temperature is 400 ℃.Behind the reaction 5h, add steam in unstripped gas, the unstripped gas ratio becomes V (C
3H
8)/V (air)/V (vapor)=1/15/12, air speed becomes 800mL/g-cat/h, and reaction temperature still is 400 ℃.At this moment conversion of propane and acrylic acid selectivity are respectively 57.4% and 64.5%.Identical with the reaction result among the embodiment 3.As seen, even under anhydrous condition, reacted, can the reactivity worth of catalyst not exerted an influence through the reaction atmosphere catalyst activated yet.Illustrate, can hold out against the fluctuation of reactor feed gas ratio in a big way, and can not cause the inactivation of catalyst through the reaction atmosphere catalyst activated.
Comparative example 7
Manhua Lin etc. are at title of article " Reaction pathways in the selective oxidation ofpropane over a mixed metal oxide catalyst ", Catalysis Today has investigated the catalytic performance of Mo-V-Te-Nb-O catalyst in the reaction of selective oxidation of propane system acrylic acid in 61 (2000) 223-229, one literary composition.The 20g catalyst is contained in the stainless steel tube reactor that internal diameter is 11mm.Reactor feed gas is than V (C
3H
8)/V (air)/V (vapor)=3/50/47, air speed is 1200h
-1, reaction pressure is 7psig, reaction temperature is 391 ℃.Experimental result: conversion of propane and acrylic acid selectivity are respectively 18.0% and 26.0%.Acrylic acid shared molar concentration in product liquid is 68.4% (seeing Table 2).
Comparative example 8
Lin Luo etc. is " Comparison of Reaction Pathways for the PartialOxidation 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) 222-231 one literary composition to Mo
1V
0.3Te
0.23Nb
0.12O
xCatalyst has carried out the repercussion study of selective oxidation of propane system acrylic acid.Catalyst amount is 1.75g, and reactor feed gas is than V (C
3H
8)/V (O
2)/V (He)=1/3.15/11.85, gas overall flow rate are 36.2mL/min, and reaction temperature is 400 ℃.Experimental result: conversion of propane and acrylic acid selectivity are respectively 58.3% and 39.2%.Acrylic acid shared molar concentration in product liquid is 85.0% (seeing Table 2).
Comparative example 9
Prepared Mo in this patent
1V
0.3Te
0.23Nb
0.12O
xReactivity worth after catalyst activates through reaction atmosphere sees Table 2.Reaction condition such as embodiment 3 introduce.Acrylic acid in product liquid shared molar concentration up to 93.3%.Be higher than other document result (as comparative example 7 and comparative example 8) far away.
Because according to the relevant patent report (European Patent No.0962253 and EuropeanPatent No.0608838) in Europe, selective oxidation of propane system acrylic acid is being reacted in the crystal structure diffraction maximum of Mo-V-Te-Nb-O catalyst with good catalytic, at the angle of diffraction 2 θ is 22.1 °, 28.2 °, 36.2 °, locate to have five characteristic diffraction peaks for 45.2 ° and 50.0 °.From Fig. 3 as seen, embodiment 1 catalyst before the activation is 36.2 ° and 50.0 ° in the angle of diffraction and locates to lack two characteristic diffraction peaks, is 22.1 ° in the angle of diffraction, located three characteristic diffraction peaks for 28.2 ° and 45.2 °, and the relative intensity of diffraction maximum a little less than.This is the relatively poor main cause of reactivity worth that causes fresh embodiment 1 catalyst.Catalyst activated has possessed five whole characteristic diffraction peaks, and relative peak intensity is than meeting with patent.So activating the reactivity worth of later catalyst improves greatly.
Fig. 4 is the XRD figure of the catalyst that activates under four kinds of different atmospheres such as the mixed atmosphere of reaction atmosphere, air, air and steam and the mixed atmosphere of nitrogen and steam.As can be seen, having only the catalyst of reaction atmosphere activation is 22.1 ° at the angle of diffraction 2 θ, 28.2 °, 36.2 °, locates to have five characteristic diffraction peaks for 45.2 ° and 50.0 °.And the catalyst of other atmosphere activation all not exclusively possesses five characteristic peaks all.So, have good catalytic performance through the catalyst of reaction atmosphere activation, and be not so good as the former with the catalytic performance of the catalyst of other several atmosphere activation.
Fig. 5 has provided the XRD figure of several catalyst, and a represents through the reaction atmosphere catalyst activated; B representative activation rear catalyst reacts 5h under anhydrous condition after, use N
2The catalyst of protecting; C representative was reacted under anhydrous condition to be had under the water condition behind the reaction 5h again, uses N
2The catalyst of protecting.Contrast finds that XRD curve map and a of b and c are identical.As seen, even under anhydrous condition, reacted, can the crystal phase structure of catalyst not exerted an influence through the reaction atmosphere catalyst activated yet.Illustrate, can hold out against the fluctuation of reactor feed gas ratio in a big way, and can not cause the variation of catalyst structure through the reaction atmosphere catalyst activated.
Partial reaction result among table 1 embodiment
| Conversion of propane (%) | Acrylic acid selectivity (%) | Acrylic acid yield (%) | |
| Embodiment 4 | 45.6 | 71.8 | 32.7 |
| Embodiment 5 | 65.0 | 61.8 | 40.1 |
| Embodiment 6 | 55.0 | 68.8 | 37.9 |
| Embodiment 7 | 58.4 | 58.0 | 33.9 |
Partial reaction result in table 2 comparative example
| T(℃) | Conversion of propane (%) | Acrylic acid selectivity (%) | Acrylic acid yield (%) | Acrylic acid molar concentration (%) in the product liquid | |
| Comparative example 7 | 391 | 18.0 | 26.0 | 4.7 | 68.4 |
| Comparative example 8 | 400 | 58.3 | 39.2 | 22.9 | 85.0 |
| Comparative example 9 | 400 | 59.1 | 63.6 | 37.6 | 93.3 |
Claims (10)
1, a kind of molybdenum-vanadium-tellurium-niobium catalytic agent that is used for the reaction of selective oxidation of propane system acrylic acid, the relative mol ratio of each element is as follows in the catalyst:
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: described catalyst is handled acquisition by fresh catalyst is carried out high-temperature activation with chemical method; High-temperature activation is handled and carry out the volume ratio V (C of reaction gas under reaction atmosphere
3H
8)/V (air)/V (vapor)=1/5～25/0～24, reaction velocity is 500～1500mL/g-cat/h, and activation temperature is 400～700 ℃, and soak time is 2～20h.
2, according to the described molybdenum-vanadium-tellurium-niobium catalytic agent that is used for the reaction of selective oxidation of propane system acrylic acid of claim 1, it is characterized in that: the chemical composition of catalyst is Mo
1V
0.3Te
0.23Nb
0.12O
x, x=4.5～4.8 wherein.
3, the described preparation method who is used for the molybdenum-vanadium-tellurium-niobium catalytic agent of selective oxidation of propane system acrylic acid reaction of a kind of claim 1 is characterized in that: fresh catalyst is carried out high-temperature activation with chemical method handle; High-temperature activation is handled and carry out the volume ratio V (C of reaction gas under reaction atmosphere
3H
8)/V (air)/V (vapor)=1/5～25/0～24, reaction velocity is 500～1500mL/g-cat/h, and activation temperature is 400～700 ℃, and soak time is 2～20h.
4, according to the described preparation method who is used for the molybdenum-vanadium-tellurium-niobium catalytic agent of selective oxidation of propane system acrylic acid reaction of claim 3, it is characterized in that: the volume ratio V (C of described reaction gas
3H
8)/V (air)/V (vapor)=1/12～15/10～15, reaction velocity is 600～900mL/g-cat/h.
5, according to the described preparation method who is used for the molybdenum-vanadium-tellurium-niobium catalytic agent of selective oxidation of propane system acrylic acid reaction of claim 4, it is characterized in that: described activation temperature is 450～600 ℃, and soak time is 10～14h.
6, according to the described preparation method who is used for the molybdenum-vanadium-tellurium-niobium catalytic agent of selective oxidation of propane system acrylic acid reaction of claim 3, it is characterized in that: the catalyst after described high-temperature activation is handled grinds to form the powder of particle diameter less than 20um, molding, granulating sieves into 20～30 purpose catalyst granules.
7, according to the described preparation method who is used for the molybdenum-vanadium-tellurium-niobium catalytic agent of selective oxidation of propane system acrylic acid reaction of claim 3, it is characterized in that described high-temperature activation processing procedure is:
---with the fresh catalyst reactor of packing into, the N that is flowing
2Under the atmosphere protection, be warming up to 380 ℃ with the heating rate of 6 ℃/min
---with N
2Atmosphere switches to reaction atmosphere, and behind the stable reaction 10min, the heating rate with 2 ℃/min slowly is warming up to activation temperature again, keep certain hour after, be cooled to 380 ℃ with the speed of 2 ℃/min;
---change reaction atmosphere into N
2Atmosphere is at N
2The protection of atmosphere drops to room temperature.
8, according to the described preparation method who is used for the molybdenum-vanadium-tellurium-niobium catalytic agent of selective oxidation of propane system acrylic acid reaction of claim 3, it is characterized in that: during activating catalyst, oxygen concentration needs between 2%～10% in the tail gas under reaction atmosphere.
9, according to the described preparation method who is used for the molybdenum-vanadium-tellurium-niobium catalytic agent of selective oxidation of propane system acrylic acid reaction of claim 8, it is characterized in that: during activating catalyst, oxygen concentration is between 3%～5% in the tail gas under reaction atmosphere.
10, according to the described preparation method who is used for the molybdenum-vanadium-tellurium-niobium catalytic agent of selective oxidation of propane system acrylic acid reaction of claim 3, it is characterized in that: described fresh catalyst is to utilize Rotary Evaporators to prepare catalyst precursor to obtain through roasting again, and roasting is at static N
2Carry out under the protection of gas, temperature is 550～650 ℃, time 1～3h.
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|---|---|---|---|
| CN 200410100456 CN100544821C (en) | 2004-12-23 | 2004-12-23 | A kind of molybdenum-vanadium-tellurium-niobium catalytic agent that is used for the reaction of selective oxidation of propane system acrylic acid and preparation method thereof |
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|---|---|---|---|
| CN 200410100456 CN100544821C (en) | 2004-12-23 | 2004-12-23 | A kind of molybdenum-vanadium-tellurium-niobium catalytic agent that is used for the reaction of selective oxidation of propane system acrylic acid and preparation method thereof |
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| CN100544821C CN100544821C (en) | 2009-09-30 |
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| CN 200410100456 Active CN100544821C (en) | 2004-12-23 | 2004-12-23 | A kind of molybdenum-vanadium-tellurium-niobium catalytic agent that is used for the reaction of selective oxidation of propane system acrylic acid and preparation method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN103041830A (en) * | 2012-12-26 | 2013-04-17 | 新兴能源科技有限公司 | Method for preparing acrylic acid catalyst from propylene by one-step oxidation method |
| CN101612564B (en) * | 2008-06-26 | 2013-05-01 | 中国科学院大连化学物理研究所 | Mo-V-Te-Nb-O catalyst, preparation method and application thereof |
| CN103889942A (en) * | 2011-10-18 | 2014-06-25 | 罗门哈斯公司 | Method for preparing acrylic acid from propane and propylene |
| CN103691457B (en) * | 2013-12-24 | 2016-04-27 | 济南开发区星火科学技术研究院 | The acrylic acid Catalysts and its preparation method of a kind of propane selectivity oxidation preparation |
| CN105849069A (en) * | 2013-12-06 | 2016-08-10 | 国际壳牌研究有限公司 | Alkane oxidative dehydrogenation and/or alkene oxidation |
| CN105983421A (en) * | 2015-02-02 | 2016-10-05 | 中国石油天然气股份有限公司 | Catalyst for catalytically oxidizing propane for preparing acrylic acid, and preparation method thereof |
| CN106944103A (en) * | 2017-04-18 | 2017-07-14 | 中触媒新材料股份有限公司 | A kind of hydro-thermal activation method of oxidation of propane acrylic acid catalyst and application |
| CN108200762A (en) * | 2015-10-26 | 2018-06-22 | 国际壳牌研究有限公司 | Powerful catalyst and catalyst carrier, it is prepared and its purposes |
| US11401220B2 (en) | 2016-02-26 | 2022-08-02 | Shell Usa, Inc. | Alkane oxidative dehydrogenation (ODH) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2271397A1 (en) * | 1998-05-21 | 1999-11-21 | Rohm And Haas Company | A process for preparing a catalyst |
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2004
- 2004-12-23 CN CN 200410100456 patent/CN100544821C/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101612564B (en) * | 2008-06-26 | 2013-05-01 | 中国科学院大连化学物理研究所 | Mo-V-Te-Nb-O catalyst, preparation method and application thereof |
| 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 |
| CN103889942B (en) * | 2011-10-18 | 2016-05-11 | 罗门哈斯公司 | Prepare acrylic acid from propane and propylene |
| CN103889942A (en) * | 2011-10-18 | 2014-06-25 | 罗门哈斯公司 | Method for preparing acrylic acid from propane and propylene |
| 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 |
| CN103041830A (en) * | 2012-12-26 | 2013-04-17 | 新兴能源科技有限公司 | Method for preparing acrylic acid catalyst from propylene by one-step oxidation method |
| CN105849069A (en) * | 2013-12-06 | 2016-08-10 | 国际壳牌研究有限公司 | Alkane oxidative dehydrogenation and/or alkene oxidation |
| US9963412B2 (en) | 2013-12-06 | 2018-05-08 | Shell Oil Company | Alkane oxidative dehydrogenation and/or alkene oxidation |
| CN103691457B (en) * | 2013-12-24 | 2016-04-27 | 济南开发区星火科学技术研究院 | The acrylic acid Catalysts and its preparation method of a kind of propane selectivity oxidation preparation |
| CN105983421A (en) * | 2015-02-02 | 2016-10-05 | 中国石油天然气股份有限公司 | Catalyst for catalytically oxidizing propane for preparing acrylic acid, and preparation method thereof |
| CN108200762A (en) * | 2015-10-26 | 2018-06-22 | 国际壳牌研究有限公司 | Powerful catalyst and catalyst carrier, it is prepared and its purposes |
| CN108200762B (en) * | 2015-10-26 | 2022-02-18 | 国际壳牌研究有限公司 | Strong catalyst and catalyst carrier, preparation and use thereof |
| US11401220B2 (en) | 2016-02-26 | 2022-08-02 | Shell Usa, Inc. | Alkane oxidative dehydrogenation (ODH) |
| CN106944103A (en) * | 2017-04-18 | 2017-07-14 | 中触媒新材料股份有限公司 | A kind of hydro-thermal activation method of oxidation of propane acrylic acid catalyst and application |
| CN106944103B (en) * | 2017-04-18 | 2020-04-24 | 中触媒新材料股份有限公司 | Hydrothermal activation method for preparing acrylic acid catalyst by oxidizing propane and application |
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