CN109569668A - The preparation method and application of Mo-V-Te-Nb-O catalyst - Google Patents
The preparation method and application of Mo-V-Te-Nb-O catalyst Download PDFInfo
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- CN109569668A CN109569668A CN201910036626.0A CN201910036626A CN109569668A CN 109569668 A CN109569668 A CN 109569668A CN 201910036626 A CN201910036626 A CN 201910036626A CN 109569668 A CN109569668 A CN 109569668A
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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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0576—Tellurium; Compounds thereof
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The present invention provides a kind of preparation method and applications of Mo-V-Te-Nb-O catalyst, are related to catalyst technical field.The preparation method uses the reducing metal tellurium obtained through reducing agent reduction high price tellurium compound as tellurium source, then reducing metal tellurium is mixed again with molybdenum source, vanadium source, niobium source and is reacted, it is dry, roasting, obtain Mo-V-Te-Nb-O catalyst, compared to telluric acid is used in prior art, as tellurium source, the Mo-V-Te-Nb-O catalyst obtained using preparation method provided by the invention is with higher catalytic activity；In addition, reducing agent property selected in preparation process is relatively stable, operation processing is easy, and will not generate murder by poisoning to laboratory staff and environment, and cheap, is suitable for commercial scale.The present invention also provides Mo-V-Te-Nb-O catalyst made from above-mentioned preparation method is applied in the reaction of oxidation of propane acrylic acid.
Description
Technical field
The present invention relates to catalyst preparation technical fields, in particular to the preparation side of Mo-V-Te-Nb-O catalyst
Method and application.
Background technique
Acrylic acid is a kind of important petrochemical industry, light industry and medical material, can be used to produce adsorbent, cleanser, fibre
Dimension, pulp additive, adhesive, plastics, coating etc., and its application range is still constantly expanding.
Currently, the main production process of acrylic acid be propylene two-stage method, i.e. propylene and oxygen in the presence of a catalyst
Reaction generates methacrylaldehyde, and methacrylaldehyde generates acrylic acid under another catalyst action with oxygen again.For cost of material, third
Alkene price is higher than propane, and with the expansion of propylene purposes, the price of propylene will continue to go up, and the gap in the two price will
It can further increase.In recent years, due to the price difference of propane and propylene and in order to solve many in propylene two-stage method oxidizing process
Challenge, propane are that initial feed gradually causes the attention of vast scientific research institution and enterprise, and has done in related fields
Extensive work already becomes one of the research hotspot of low-carbon alkanes development and utilization.It is such as able to achieve using propane as raw material acrylic acid
Process industrialization will greatly reduce cost of material, and propane abundance, be casing-head gas, natural gas, in refinery gas it is main at
Point, such as the comprehensive utilization of the cheap alkane of propane is able to achieve with significant economic significance and realistic meaning.
But in actual operation, there is several big difficult points in the reaction of selective oxidation of propane acrylic acid: specifically, propane
As saturated alkane, reactivity is very low, and product propylene, acetone, methacrylaldehyde, acetic acid and acrylic acid etc. in oxidation reaction
Reactivity is much higher, and there are competitive relations with acrylic acid for the generation of other products, therefore need to select a kind of appropriate catalytic
Agent can activate the strong c h bond in propane to show high reactivity, while can prevent and inhibit the life of by-product again
The selectivity to acrylic acid is improved at excessive oxidation occurs.The key for solving the above difficult point be find it is a kind of efficient, practical
And stable catalyst realizes propane to propylene feedstocks to realize that propane one-step method acrylic acid reaches industrial requirement
Substitution reduces cost, increases economic efficiency and social effect.
Currently, the research for directly preparing acrylic acid catalyst about propane is typically all multicomponent, multifunction catalyst, master
Concentrate on V-P-O catalyst, Mn-P-O catalyst, Bi-V-Mo-O catalyst, Bi-V-Nb-Sb-Mo-O catalyst and Mo-V-
Te-Nb-O catalyst.Wherein, Mo-V-Te-Nb-O catalyst receives the extensive concern of researcher.But use existing side
Method is prepared in Mo-V-Te-Nb-O catalyst process, often requires to use high poison substance, this is to laboratory staff and environment
There may be larger murders by poisoning, are unfavorable for the industrialization amplification of method, and the Mo-V-Te-Nb- being prepared using existing method
The catalytic performance of O catalyst need further to be promoted.
In view of this, the present invention is specifically proposed at least one of to solve the above technical problems.
Summary of the invention
The first purpose of this invention is to provide a kind of preparation method of Mo-V-Te-Nb-O catalyst, using through restoring
The reducing metal tellurium that agent reduction high price tellurium compound obtains is as tellurium source, so that the Mo-V-Te-Nb-O catalyst being prepared is urged
Change is had excellent performance, in addition, used reducing agent property is relatively stable, operation processing is easy, equal to laboratory staff and environment
Murder by poisoning will not be generated, commercial scale is suitable for.
Second object of the present invention is to provide the application of the preparation method of above-mentioned Mo-V-Te-Nb-O catalyst.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
The present invention provides a kind of preparation methods of Mo-V-Te-Nb-O catalyst, comprising the following steps:
The reducing metal tellurium obtained through reducing agent reduction high price tellurium compound is provided；
Reducing metal tellurium is placed in solvent and is reacted with molybdenum source, vanadium source, niobium source, the product that reaction is obtained is dry,
Roasting, obtains Mo-V-Te-Nb-O catalyst；
Wherein, the reducing agent includes in sodium borohydride, potassium borohydride, ascorbic acid, sodium citrate or potassium citrate
Any one or at least two combination；The high price tellurium compound is Te4+Compound or Te6+Compound.
Further, on the basis of technical solution of the present invention, the molar ratio of the reducing agent and high price tellurium compound
For (1~10): 1, preferably (1.5~6): 1.
Further, on the basis of technical solution of the present invention, reducing agent restores reduction temperature when high price tellurium compound
Degree is 30~200 DEG C, preferably 50~150 DEG C；
And/or recovery time when reducing agent reduction high price tellurium compound is 0.5~72h, preferably 3~12h.
Further, used when reducing agent restores high price tellurium compound on the basis of technical solution of the present invention
Medium is water；
And/or the Te4+Compound includes tellurium dioxide and/or sodium tellurite；
And/or the Te6+Compound includes telluric acid or/or llurate；
And/or the total mol concentration for reacting molybdenum in obtained product, vanadium, tellurium and niobium metal ion be 0.05~
1.2mol/L, preferably 0.1~1.0mol/L.
Further, on the basis of technical solution of the present invention, the chemical composition of the Mo-V-Te-Nb-O catalyst
General formula is MoVaTebNbcOx, wherein a be 0.1~0.5, b be 0.1~0.5, c be 0.01~0.3, x depend on other elements
Valence state.
Further, on the basis of technical solution of the present invention, the molybdenum source includes ammonium dimolybdate, ammonium tetramolybdate or secondary
In ammonium molybdate any one or at least two combination；
And/or the vanadium source includes vanadic sulfate and/or ammonium metavanadate；
And/or the niobium source includes niobium oxalate and/or ammonium niobium oxalate.
Further, on the basis of technical solution of the present invention, the preparation method of the Mo-V-Te-Nb-O catalyst,
The following steps are included:
Reducing agent, high price tellurium compound are mixed with water, 0.5~72h is restored at 30~200 DEG C, obtains reducing metal
Tellurium；
Reducing metal tellurium is mixed with molybdenum source, vanadium source with water, primary first-order equation is carried out, obtains mixed solution；By mixed solution
It is mixed with the solution containing niobium source, carries out secondary response, the product that reaction is obtained is dry, and roasting obtains Mo-V-Te-Nb-O
Catalyst.
Further, on the basis of technical solution of the present invention, the temperature of the primary first-order equation is 30~200 DEG C, excellent
It is selected as 40~130 DEG C；
Preferably, the time of the primary first-order equation is 0.5~72h, preferably 1~8h；
Preferably, ultrasound is carried out simultaneously when carrying out primary first-order equation；
Preferably, the temperature of the secondary response is 30~200 DEG C, preferably 40~130 DEG C；
Preferably, the time of the secondary response is 0.5~72h, preferably 1~8h.
Further, on the basis of technical solution of the present invention, the drying is revolving drying or spray drying；
Preferably, the roasting includes level-one roasting and second level roasting；
Preferably, the maturing temperature of the level-one roasting is 250~350 DEG C, and calcining time is 1~3h, and calcination atmosphere is
Any one in nitrogen, argon gas, helium or air；
Preferably, the maturing temperature of the second level roasting is 550~650 DEG C, and calcining time is 1~3h, and calcination atmosphere is
Any one in nitrogen, argon gas or helium.
The present invention also provides Mo-V-Te-Nb-O made from a kind of preparation method using Mo-V-Te-Nb-O catalyst
The Mo-V-Te-Nb-O catalyst is used for propane catalysis oxidation and prepares acrylic acid by the application of catalyst；
The technological parameter of preparation process includes: that 1g Catalyst packing is entered fixed bed reactors；The base stock of reaction is
The volume ratio of propane and oxygen, propane and oxygen is (0.1~1.0): 1；Reaction temperature is 360~420 DEG C, and reaction pressure is normal
Pressure, flow of inlet water are 0.3~3mL/h, and reaction velocity is 800~6000L/ (Kg.h).
Compared with prior art, the preparation method and application of Mo-V-Te-Nb-O catalyst provided by the invention has following
Advantage:
(1) the present invention provides a kind of preparation methods of Mo-V-Te-Nb-O catalyst, restore high price using through reducing agent
Then the reducing metal tellurium that tellurium compound obtains again reacts reducing metal tellurium with molybdenum source, vanadium source, niobium source as tellurium source,
Dry, roasting obtains Mo-V-Te-Nb-O catalyst, uses telluric acid as tellurium source compared in prior art, is mentioned using the present invention
The Mo-V-Te-Nb-O catalyst that the preparation method of confession obtains has higher catalytic activity；In addition, selected in preparation process
Reducing agent be one or more of sodium borohydride, potassium borohydride, ascorbic acid, sodium citrate or potassium citrate, it is this kind of also
Former agent is relatively stable, and operation processing is easy, and will not generate murder by poisoning to laboratory staff and environment, and cheap, is applicable in
In commercial scale.
The preparation method process flow is simple and with good stability and repeatable, is suitable for industrialization amount
It produces.
(2) the present invention provides a kind of applications of the preparation method of above-mentioned Mo-V-Te-Nb-O catalyst, in view of above-mentioned Mo-
Advantage possessed by the preparation method of V-Te-Nb-O catalyst, therefore by Mo-V-Te-Nb-O catalyst made from the preparation method
In reaction applied to oxidation of propane acrylic acid, conversion of propane, acrylic acid selectivity, acrylic acid yield etc. can be significantly improved
Index parameter provides more references for industrial oxidation of propane acrylic acid.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
It should be understood that in the present invention, if without particularly illustrating, all embodiments mentioned in this article and
Preferred implementation method can be combined with each other to form new technical solution.
In the present invention, if without particularly illustrating, all technical characteristics and preferred feature mentioned in this article can be with
Intercombination forms new technical solution.
In the present invention, if percentage (%) or part refer to the weight relative to composition without particularly illustrating
Percentage or parts by weight.
In the present invention, if related each component or its preferred ingredient can be combined with each other shape without particularly illustrating
The technical solution of Cheng Xin.
In the present invention, unless otherwise indicated, numberical range " a~b " indicates the contracting of any real combinings between a to b
Sketch form shows that wherein a and b is real number.Such as numberical range " 6~22 " indicate herein all listed " 6~22 " it
Between whole real numbers, " 6~22 " be these combinations of values breviary indicate.
" range " disclosed in this invention can be respectively one or more lower limits and one in the form of lower and upper limit
A or multiple upper limits.
In the present invention, unless otherwise indicated, it is each reaction or operating procedure can sequentially carry out, can also in sequence into
Row.Preferably, reaction method herein is that sequence carries out.
Unless otherwise indicated, profession used herein and meaning phase known to scientific term and one skilled in the art
Together.In addition, any method similar to or equal to what is recorded or material can also be applied in the present invention.
According to an aspect of the invention, there is provided the preparation method of Mo-V-Te-Nb-O catalyst, comprising the following steps:
The reducing metal tellurium obtained through reducing agent reduction high price tellurium compound is provided；
Reducing metal tellurium is placed in solvent and is reacted with molybdenum source, vanadium source, niobium source, the product that reaction is obtained is dry,
Roasting, obtains Mo-V-Te-Nb-O catalyst；
Wherein, reducing agent includes any in sodium borohydride, potassium borohydride, ascorbic acid, sodium citrate or potassium citrate
It is a kind of or at least two combination；High price tellurium compound is Te4+Compound or Te6+Compound.
Specifically, from the preparation method of existing Mo-V-Te-Nb-O catalyst use telluric acid as tellurium source different, this hair
It is bright it is middle using through the obtained reducing metal tellurium of reducing agent reduction high price tellurium compound as tellurium source, then again by reducing metal tellurium and
Molybdenum source, vanadium source, niobium source are reacted, dry, and roasting obtains Mo-V-Te-Nb-O catalyst.Compared to prior art, using this hair
The Mo-V-Te-Nb-O catalyst catalytic activity with higher that the preparation method of bright offer obtains.
It should be noted that the reducing metal tellurium obtained through reducing agent reduction high price tellurium compound, the gold with conventional commercial
It is different to belong to tellurium particle, the reducing metal tellurium restored will more commercially available metallic tellurium particle reaction it is high, this is mainly due to also
The reducing metal tellurium surface that original obtains is almost without the presence of tellurium oxide, and particle is small, easily carries out redox reaction with Mo, V
And M1 phase is easily generated, thus catalytic activity with higher.
In addition, reducing agent selected in preparation process be sodium borohydride, potassium borohydride, ascorbic acid, sodium citrate or
One or more of potassium citrate, this kind of reducing agent is relatively stable, and operation processing is easy, equal to laboratory staff and environment
Murder by poisoning will not be generated, commercial scale is suitable for.
Molybdenum source, vanadium source, tellurium source and niobium source in preparation process can be used molybdenum salt commonly used in the art, vanadic salts, tellurium salt and
Niobium salt is not construed as limiting the selected specific type of substance, can be selected according to real reaction system.
Drying employed in preparation process, roasting and etc. be technical means commonly used by such a person skilled in the art, herein
It is not especially limited.
As a kind of optional embodiment of the present invention, the molar ratio of reducing agent and high price tellurium compound is (1~10): 1, it is excellent
It is selected as (1.5~6): 1.The molar ratio of typical but non-limiting reducing agent and high price tellurium compound is 1:1,1.5:1,2:1,
2.5:1,3:1,4:1,4.5:1,5:1,6:1,7:1,8:1,9:1 or 10:1.
The number of reducing agent dosage directly affects the reducing degree of high price tellurium compound.The dosage of reducing agent is very few, then
Will lead to reduction it is insufficient, with the presence of high price tellurium compound, the dosage of reducing agent is excessive, then wastes reducing agent and increase into without reason
This, therefore the molar ratio of reducing agent and high price tellurium compound should be limited in suitable numberical range.
As a kind of optional embodiment of the present invention, reduction temperature when reducing agent restores high price tellurium compound is 30~
200 DEG C, preferably 50~150 DEG C；Typical but non-limiting reduction temperature is 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 80 DEG C, 100
DEG C, 120 DEG C, 140 DEG C, 150 DEG C, 180 DEG C or 200 DEG C.
And/or recovery time when reducing agent reduction high price tellurium compound is 0.5~72h, preferably 3~12h.It is typical
But the unrestricted recovery time be 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 8h, 10h, 12h, 20h, for 24 hours, 28h, 30h, 36h,
40h, 48h, 50h, 60h, 70h or 72h.
By the specific restriction to reduction temperature in reduction process and recovery time, so that reduction reaction progress is more filled
Point.
According to the characteristic of reducing agent itself, suitable reducing medium is selected.As a kind of optional embodiment of the present invention, also
When former agent reduction high price tellurium compound, used medium is water.Using water as reducing medium, cleanliness without any pollution.
In the present invention, high price tellurium compound is mainly Te4+Compound and Te6+Compound.As of the invention a kind of optional
Embodiment, Te4+Compound includes tellurium dioxide and/or sodium tellurite；And/or Te6+Compound includes telluric acid or/or telluric acid
Sodium.
As a kind of optional embodiment of the present invention, the chemical composition general formula of Mo-V-Te-Nb-O catalyst is
MoVaTebNbcOx。
Wherein, a is 0.1~0.5, preferably 0.2~0.4, further preferably 0.3；Typical but non-limiting a is
0.1,0.15,0.2,0.25,0.3,0.35,0.4,0.45 or 0.5；
B is 0.1~0.5, preferably 0.2~0.4, further preferably 0.23；Typical but non-limiting b be 0.1,
0.15,0.2,0.25,0.3,0.35,0.4,0.45 or 0.5；
C is 0.01~0.3, preferably 0.1~0.2, further preferably 0.12；Typical but non-limiting c be 0.01,
0.05,0.08,0.1,0.15,0.2,0.25 or 0.3.
X depends on the valence state of other elements.
Mo-V-Te-Nb-O catalyst is mainly the O composite metallic oxide catalyst being made of Mo, V, Te, Nb, O.Mo,
V, the catalytic performance of the relative mole ratios between Te, Nb, O these types element and final Mo-V-Te-Nb-O catalyst has direct shadow
It rings, therefore limits a, b, c in suitable numberical range, x is calculated according to the valence state of other elements.
As a kind of optional embodiment of the present invention, molybdenum source includes appointing in ammonium dimolybdate, ammonium tetramolybdate or ammonium paramolybdate
It anticipates a kind of or at least two combinations；
And/or vanadium source includes vanadic sulfate and/or ammonium metavanadate；
And/or niobium source includes niobium oxalate and/or ammonium niobium oxalate.
By to molybdenum source, the specific kind of restriction in vanadium source and niobium source, so that there is good matching relationship between each raw material,
To make the performance for the Mo-V-Te-Nb-O catalyst being prepared be in preferably horizontal.
As a kind of optional embodiment of the present invention, the preparation method of Mo-V-Te-Nb-O catalyst, comprising the following steps:
Reducing agent, high price tellurium compound are mixed with water, 0.5~72h is restored at 30~200 DEG C, obtains reducing metal
Tellurium；
Reducing metal tellurium is mixed with molybdenum source, vanadium source with water, primary first-order equation is carried out, obtains mixed solution；By mixed solution
It is mixed with the solution containing niobium source, carries out secondary response, the product that reaction is obtained is dry, and roasting obtains Mo-V-Te-Nb-O
Catalyst.
By the restriction to specific steps in preparation method, so that Mo-V-Te-Nb-O catalyst obtained is with more excellent
Different catalytic performance.
As a kind of optional embodiment of the present invention, the temperature of primary first-order equation is 30~200 DEG C, preferably 40~130 DEG C；
The temperature of typical but non-limiting primary first-order equation be 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 80 DEG C, 100 DEG C, 120 DEG C, 140 DEG C,
150 DEG C, 180 DEG C or 200 DEG C.
As a kind of optional embodiment of the present invention, the time of primary first-order equation is 0.5~72h, preferably 1~8h；It is typical
But the time of unrestricted primary first-order equation be 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 8h, 10h, 12h, 20h, for 24 hours, 28h,
30h, 36h, 40h, 48h, 50h, 60h, 70h or 72h.
Reducing metal tellurium is mixed with molybdenum source, vanadium source with water, carries out primary first-order equation, clear mixed solution can be obtained.To promote
Into reducing metal tellurium and molybdenum source, vanadium source in water react progress, as a kind of optional embodiment of the present invention, carry out it is primary
Ultrasound is carried out when reaction simultaneously.
The power of ultrasound is not especially limited, and is set according to real reaction situation.When ultrasonic time is with primary first-order equation
Between it is consistent.
The progress of addition niobium source is secondary after reducing metal tellurium and molybdenum source, vanadium source carry out primary first-order equation in water, then thereto
Reaction.
As a kind of optional embodiment of the present invention, the temperature of secondary response is 30~200 DEG C, preferably 40~130 DEG C；
The temperature of typical but non-limiting secondary response be 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 80 DEG C, 100 DEG C, 120 DEG C, 140 DEG C,
150 DEG C, 180 DEG C or 200 DEG C.
As a kind of optional embodiment of the present invention, the time of secondary response is 0.5~72h, preferably 1~8h；It is typical
But the time of unrestricted secondary response be 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 8h, 10h, 12h, 20h, for 24 hours, 28h,
30h, 36h, 40h, 48h, 50h, 60h, 70h or 72h.
After carrying out secondary response, the total ion of molybdenum, vanadium, tellurium and niobium metal ion in water in the product that reacts
Molar concentration is 0.05~1.2mol/L, preferably 0.1~1.0mol/L；The total moles of typical but infinite metal ion are dense
Degree is 0.05mol/L, 0.08mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/
L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1.0mol/L, 1.1mol/L or 1.2mol/L.
By the restriction to metal ion total mol concentration in obtained product is reacted, so that the Mo-V-Te-Nb-O is catalyzed
The performance and preparation efficiency of agent are in preferable level.
The product that reaction obtains first is aged, is then dried again.As a kind of optional embodiment of the present invention,
Aging Temperature is 40~130 DEG C, and digestion time is 1~5h；Typical but non-limiting Aging Temperature be 40 DEG C, 50 DEG C, 60 DEG C,
80 DEG C, 100 DEG C, 120 DEG C or 130 DEG C, typical but non-limiting digestion time is 1h, 2h, 3h, 4h or 5h.
It is dry for revolving drying or spray drying as a kind of optional embodiment of the present invention；Pass through specifically drying side
The restriction of formula disperses also more uniform so that the grain diameter of catalyst precursor generated is more uniform.
Product (catalyst precursor) after drying is roasted, to obtain Mo-V-Te-Nb-O catalyst.
As a kind of optional embodiment of the present invention, roasting includes level-one roasting and second level roasting；
Preferably, level-one roasting maturing temperature be 250~350 DEG C, calcining time be 1~3h, calcination atmosphere be nitrogen,
Any one in argon gas, helium or air；Typical but non-limiting maturing temperature is 250 DEG C, 260 DEG C, 270 DEG C, 280
DEG C, 290 DEG C, 300 DEG C, 310 DEG C, 320 DEG C, 330 DEG C, 340 DEG C or 350 DEG C, typical but non-limiting calcining time be 1h,
1.5h, 2h, 2.5h or 3h.
Preferably, second level roasting maturing temperature be 550~650 DEG C, calcining time be 1~3h, calcination atmosphere be nitrogen,
Any one in argon gas or helium.Typical but non-limiting second level maturing temperature be 550 DEG C, 560 DEG C, 570 DEG C, 580 DEG C,
590 DEG C, 595 DEG C, 600 DEG C, 610 DEG C, 620 DEG C, 630 DEG C, 640 DEG C or 650 DEG C, typical but non-limiting second level calcining time
For 1h, 1.5h, 2h, 2.5h or 3h.
The catalyst powder obtained after roasting is subjected to compression molding, is crushed after making certain mesh number to get arriving Mo-V-Te-
Nb-O catalyst.
Due in the preparation process of Mo-V-Te-Nb-O catalyst, raw material type, reaction condition, drying and roasting side
Formula etc. has a major impact each element valence distribution in its crystal phase structure, pattern and catalyst etc., this is also the catalyst
One of more difficult the reason of repeating, needs to generate necessary activity phase and selection phase by strict control.
According to the second aspect of the invention, it is obtained to provide a kind of preparation method using Mo-V-Te-Nb-O catalyst
Mo-V-Te-Nb-O catalyst application, Mo-V-Te-Nb-O catalyst is used for propane catalysis oxidation and prepares acrylic acid；
The technological parameter of preparation process includes: that 1g Catalyst packing is entered fixed bed reactors；The base stock of reaction is
The volume ratio of propane and oxygen, propane and oxygen is (0.1~1.0): 1；Reaction temperature is 360~420 DEG C, and reaction pressure is normal
Pressure, flow of inlet water are 0.3~3mL/h, and reaction velocity is 800~6000L/ (Kg.h).
Propane and the typical but non-limiting volume ratio of oxygen are 0.1:1,0.2:1,0.3:1,0.4:1,0.5:1,0.6:
1,0.7:1,0.8:1,0.9:1 or 1:1；Typical but non-limiting reaction temperature be 360 DEG C, 370 DEG C, 380 DEG C, 390 DEG C,
400 DEG C, 410 DEG C or 420 DEG C；Typical but non-limiting flow of inlet water be 0.3mL/h, 0.5mL/h, 0.8mL/h, 1.0mL/h,
1.5mL/h, 2.0mL/h, 2.5mL/h or 3.0mL/h；Typical but non-limiting reaction velocity be 800L/ (Kgh),
1000L/ (Kgh), 2000L/ (Kgh), 3000L/ (Kgh), 4000L/ (Kgh), 5000L/ (Kgh) or 6000L/
(Kg·h)。
By preparing the restriction of specific process parameter during acrylic acid to propane catalysis oxidation, so that conversion of propane,
Acrylic acid selectivity and acrylic acid yield are in higher level.
Combined with specific embodiments below and comparative example, the invention will be further described.
Embodiment 1
Present embodiments provide a kind of preparation method of Mo-V-Te-Nb-O catalyst, comprising the following steps:
(a) 0.74g reducing agent, 1.50g high price tellurium compound are mixed with water, washs, obtains after restoring 5h at 40 DEG C
Reducing metal tellurium；Wherein, reducing agent is sodium borohydride, and high price tellurium compound is telluric acid, and the molar ratio of sodium borohydride and telluric acid is
3:1；
(b) reducing metal tellurium is mixed with 5.00g ammonium paramolybdate, 1.39g vanadic sulfate and water and is placed in oscillating ultrasonic instrument
Then ultrasonic 0.5h carries out primary first-order equation 8h under 130 DEG C of stirring conditions, obtains mixed solution；
Mixed solution is mixed with 1.83g niobium oxalate, secondary response 5h is carried out under 130 DEG C of stirring conditions, will be reacted
The product arrived is spray-dried after 50 DEG C of ageing 5h, and level-one roasting and second level roasting are then successively carried out in nitrogen atmosphere
It burns, obtains product of roasting；Wherein, level-one maturing temperature is 300 DEG C, and level-one calcining time is 2h, and second level maturing temperature is 600
DEG C, second level calcining time is 2h；
By product of roasting compression molding, it is crushed to 20-40 mesh, obtains MoV0.3Te0.23Nb0.12O catalyst.
Embodiment 2
Present embodiments provide a kind of preparation method of Mo-V-Te-Nb-O catalyst, the reducing agent used in step (a)
For 2.4g ascorbic acid, remaining step and parameter are same as Example 1.
Embodiment 3
Present embodiments provide a kind of preparation method of Mo-V-Te-Nb-O catalyst, the reducing agent used in step (a)
For 4.01g sodium citrate, remaining step and parameter are same as Example 1.
Embodiment 4
Present embodiments provide a kind of preparation method of Mo-V-Te-Nb-O catalyst, the reducing agent used in step (a)
The quality of sodium borohydride is 1.23g, and the molar ratio of sodium borohydride and telluric acid is 5:1, remaining step and parameter and 1 phase of embodiment
Together.
Embodiment 5
Present embodiments provide a kind of preparation method of Mo-V-Te-Nb-O catalyst, the reducing agent used in step (a)
The quality of sodium borohydride is 1.47g, and the molar ratio of sodium borohydride and telluric acid is 6:1, remaining step and parameter and 1 phase of embodiment
Together.
Embodiment 6
Present embodiments provide a kind of preparation method of Mo-V-Te-Nb-O catalyst, comprising the following steps:
(a) 1.65 reducing agents, 1.05g high price tellurium compound are mixed with water, washs, obtains after restoring 8h at 120 DEG C
Reducing metal tellurium；Wherein, reducing agent is ascorbic acid, and high price tellurium compound is tellurium dioxide, ascorbic acid and tellurium dioxide
Molar ratio is 1.43:1；
(b) reducing metal tellurium is mixed with 5.55g ammonium tetramolybdate, 1.00g ammonium metavanadate and water and is placed in oscillating ultrasonic instrument
Ultrasonic 0.5h obtains mixed solution then in the lower progress primary first-order equation 5h of 50 DEG C of stirrings；
Mixed solution is mixed with 1.21g niobium oxalate, in the lower progress secondary response 3h of 50 DEG C of stirrings, the production that reaction is obtained
Object is spray-dried after 50 DEG C of ageing 5h, is then successively carried out level-one roasting in air and is carried out second level under a nitrogen
Roasting, obtains product of roasting；Wherein, level-one maturing temperature is 300 DEG C, and level-one calcining time is 3h, and second level maturing temperature is 600
DEG C, second level calcining time is 2h；
By product of roasting compression molding, it is crushed to 20-40 mesh, obtains MoV0.3Te0.23Nb0.12O catalyst.
Embodiment 7
Present embodiments provide a kind of preparation method of Mo-V-Te-Nb-O catalyst, the reduction temperature used in step (a)
Degree is 50 DEG C, remaining step and parameter are same as Example 6.
Embodiment 8
Present embodiments provide a kind of preparation method of Mo-V-Te-Nb-O catalyst, the reduction temperature used in step (a)
Degree is 100 DEG C, remaining step and parameter are same as Example 6.
Embodiment 9
Present embodiments provide a kind of preparation method of Mo-V-Te-Nb-O catalyst, comprising the following steps:
(a) 3.00g reducing agent, 2.30g high price tellurium compound are mixed with water, washs, obtains after restoring 8h at 120 DEG C
Reducing metal tellurium；Wherein, reducing agent is sodium citrate, and high price tellurium compound is llurate, mole of sodium citrate and llurate
Than for 1.05:1；
(b) reducing metal tellurium is mixed with 5.00g ammonium paramolybdate, 1.00g ammonium metavanadate and water and is placed in oscillating ultrasonic instrument
Ultrasonic 0.5h obtains mixed solution then in the lower progress primary first-order equation 4h of 70 DEG C of stirrings；
Mixed solution is mixed with 1.83g niobium oxalate, in the lower progress secondary response 4h of 70 DEG C of stirrings, the production that reaction is obtained
Object carries out rotary evaporation after 80 DEG C of ageing 5h, then successively carries out level-one roasting in air and carries out second level under a nitrogen
Roasting, obtains product of roasting；Wherein, level-one maturing temperature is 300 DEG C, and level-one calcining time is 1h, and second level maturing temperature is 600
DEG C, second level calcining time is 3h；
By product of roasting compression molding, it is crushed to 20-40 mesh, obtains MoV0.3Te0.23Nb0.12O catalyst.
Embodiment 10
Present embodiments provide a kind of preparation method of Mo-V-Te-Nb-O catalyst, in step (b) reducing metal tellurium with
It is not ultrasonically treated after ammonium paramolybdate, ammonium metavanadate and water mixing, remaining step and parameter are same as Example 9.
Comparative example 1
This comparative example provides a kind of preparation method of Mo-V-Te-Nb-O catalyst, does not carry out step (a), step (b)
In directly 1.50g telluric acid is mixed with 5.00g ammonium paramolybdate, 1.39g vanadic sulfate and water, remaining step and parameter and embodiment
1 is identical.
Comparative example 2
This comparative example provides a kind of preparation method of Mo-V-Te-Nb-O catalyst, in addition to sodium borohydride in step (a)
Hydrazine hydrate is replaced with, the quality of hydrazine hydrate is 0.90g, remaining step is same as Example 1.
Comparative example 3
This comparative example provides a kind of preparation method of Mo-V-Te-Nb-O catalyst, in addition to sodium borohydride in step (a)
Hydroxylammonium sulfate is replaced with, the quality of hydroxylammonium sulfate is 3.2g, remaining step is same as Example 1.
Comparative example 4
This comparative example provides a kind of preparation method of Mo-V-Te-Nb-O catalyst, does not carry out step (a), step (b)
In directly metallic tellurium particle (commercially available) is mixed with 5.00g ammonium paramolybdate, 1.39g vanadic sulfate and water, the grain of metallic tellurium particle
Diameter is 100 μm, remaining step is same as Example 1.
For the effect for verifying embodiment and comparative example, ad hoc following experimental example.
Experimental example 1
It is anti-that the embodiment 1-10 and comparative example 1-4 Mo-V-Te-Nb-O catalyst prepared is used for oxidation of propane acrylic acid
It answers.It weighs 1g Catalyst packing and enters fixed bed reactors, reaction gas is propane and oxygen, and the volume ratio of propane and oxygen is
0.5:1, reaction temperature are 380 DEG C, and reaction pressure is normal pressure, and reaction velocity is 2000L/ (Kgh), conversion of propane, propylene
Sour selectivity and acrylic acid yield are as shown in table 1:
Table 1
It can be seen from the data in Table 1 that the catalytic performance of Mo-V-Te-Nb-O catalyst provided in an embodiment of the present invention is whole
The catalytic performance of the Mo-V-Te-Nb-O catalyst of comparative example offer is provided on body.
Specifically, embodiment 2 and 3 and comparative example 2 and 3 are the comparative experiments of embodiment 1, data can be with from table 1
Find out, in reducing agent situation identical with the molar ratio of high price tellurium compound, the type of reducing agent directly influences high price tellurium
The reducing degree of compound, to influence the catalytic performance of preparation-obtained Mo-V-Te-Nb-O catalyst, this difference
Finally it is embodied on conversion of propane, acrylic acid selectivity and acrylic acid yield.It should be noted that the use of comparative example 2 is gone back
Former agent is hydrazine hydrate (N2H4·H2O), although it is similar to sodium borohydride to the reducing degree of high price tellurium compound, hydration
Hydrazine is high poison substance, and to laboratory staff and environment, there may be larger murders by poisoning, and has certain risk, meet open fire,
High fever is flammable, it is clear that the use of hydrazine hydrate is unfavorable for the industrialization amplification of this method.
Embodiment 4 and embodiment 5 are the comparative experiments of embodiment 1, and embodiment 7 and embodiment 8 are pair of embodiment 6
Than experiment.It can be seen from the data in Table 1 that the molar ratio and reduction reaction temperature of reducing agent and high price tellurium compound are for also
The reactivity of virgin metal tellurium has a direct impact.
Comparative example 4 is also the comparative experiments of embodiment 1, and the two is the difference is that embodiment 1 is high using reducing agent reduction
The reducing metal tellurium that valence tellurium compound obtains, comparative example 4 is using commercially available metallic tellurium particle.Data can from table 1
Out, the reducing metal tellurium obtained through reducing agent reduction high price tellurium compound is more advantageous to Mo-V-Te-Nb-O catalyst catalytic performance
Promotion, and then the castering action of conversion of propane, acrylic acid selectivity and acrylic acid yield is become apparent.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of preparation method of Mo-V-Te-Nb-O catalyst, which comprises the following steps:
The reducing metal tellurium obtained through reducing agent reduction high price tellurium compound is provided；
Reducing metal tellurium is placed in solvent and is reacted with molybdenum source, vanadium source, niobium source, the product that reaction is obtained is dry, roasting,
Obtain Mo-V-Te-Nb-O catalyst；
Wherein, the reducing agent includes any in sodium borohydride, potassium borohydride, ascorbic acid, sodium citrate or potassium citrate
It is a kind of or at least two combination；The high price tellurium compound is Te4+Compound or Te6+Compound.
2. the preparation method of Mo-V-Te-Nb-O catalyst according to claim 1, which is characterized in that the reducing agent with
The molar ratio of high price tellurium compound is (1~10): 1, preferably (1.5~6): 1.
3. the preparation method of Mo-V-Te-Nb-O catalyst according to claim 1, which is characterized in that reducing agent reduction is high
Reduction temperature when valence tellurium compound is 30~200 DEG C, preferably 50~150 DEG C；
And/or recovery time when reducing agent reduction high price tellurium compound is 0.5~72h, preferably 3~12h.
4. the preparation method of Mo-V-Te-Nb-O catalyst according to claim 1, which is characterized in that reducing agent reduction is high
When valence tellurium compound, used medium is water；
And/or the Te4+Compound includes tellurium dioxide and/or sodium tellurite；
And/or the Te6+Compound includes telluric acid or/or llurate；
And/or the total mol concentration for reacting molybdenum in obtained product, vanadium, tellurium and niobium metal ion is 0.05~1.2mol/
L, preferably 0.1~1.0mol/L.
5. the preparation method of Mo-V-Te-Nb-O catalyst according to claim 1, which is characterized in that the Mo-V-Te-
The chemical composition general formula of Nb-O catalyst is MoVaTebNbcOx, wherein a be 0.1~0.5, b be 0.1~0.5, c be 0.01~
0.3, x depends on the valence state of other elements.
6. the preparation method of Mo-V-Te-Nb-O catalyst described in -5 any one according to claim 1, which is characterized in that institute
State molybdenum source include in ammonium dimolybdate, ammonium tetramolybdate or ammonium paramolybdate any one or at least two combination；
And/or the vanadium source includes vanadic sulfate and/or ammonium metavanadate；
And/or the niobium source includes niobium oxalate and/or ammonium niobium oxalate.
7. the preparation method of Mo-V-Te-Nb-O catalyst described in -5 any one according to claim 1, which is characterized in that packet
Include following steps:
Reducing agent, high price tellurium compound are mixed with water, 0.5~72h is restored at 30~200 DEG C, obtains reducing metal tellurium；
Reducing metal tellurium is mixed with molybdenum source, vanadium source with water, primary first-order equation is carried out, obtains mixed solution；By mixed solution with contain
There is the solution in niobium source to mix, carry out secondary response, the product that reaction is obtained is dry, roasting, obtains Mo-V-Te-Nb-O catalysis
Agent.
8. the preparation method of Mo-V-Te-Nb-O catalyst according to claim 7, which is characterized in that the primary first-order equation
Temperature be 30~200 DEG C, preferably 40~130 DEG C；
Preferably, the time of the primary first-order equation is 0.5~72h, preferably 1~8h；
Preferably, ultrasound is carried out while carrying out primary first-order equation；
Preferably, the temperature of the secondary response is 30~200 DEG C, preferably 40~130 DEG C；
Preferably, the time of the secondary response is 0.5~72h, preferably 1~8h.
9. the preparation method of Mo-V-Te-Nb-O catalyst described in -5 any one according to claim 1, which is characterized in that institute
It states dry for revolving drying or spray drying；
Preferably, the roasting includes level-one roasting and second level roasting；
Preferably, the maturing temperature of level-one roasting is 250~350 DEG C, and calcining time is 1~3h, calcination atmosphere be nitrogen,
Any one in argon gas, helium or air；
Preferably, the maturing temperature of second level roasting is 550~650 DEG C, and calcining time is 1~3h, calcination atmosphere be nitrogen,
Any one in argon gas or helium.
10. Mo-V- made from the preparation method using Mo-V-Te-Nb-O catalyst described in any one of claim 1-9
The application of Te-Nb-O catalyst, which is characterized in that the Mo-V-Te-Nb-O catalyst is used for propane catalysis oxidation preparation third
Olefin(e) acid；
The technological parameter of preparation process includes: that 1g Catalyst packing is entered fixed bed reactors；The base stock of reaction is propane
And oxygen, the volume ratio of propane and oxygen are (0.1~1.0): 1；Reaction temperature is 360~420 DEG C, and reaction pressure is normal pressure,
Flow of inlet water is 0.3~3mL/h, and reaction velocity is 800~6000L/ (Kgh).
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| 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 |
| CN113083283A (en) * | 2021-04-13 | 2021-07-09 | 宁波昊祥新材料科技有限公司 | Mo-V-Te-Nb-O catalyst and preparation method and application thereof |
| 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 |
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| CN1774295A (en) * | 2003-04-16 | 2006-05-17 | 东亚合成株式会社 | Method for producing metal oxide catalyst |
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| CN1774295A (en) * | 2003-04-16 | 2006-05-17 | 东亚合成株式会社 | Method for producing metal oxide catalyst |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113083283A (en) * | 2021-04-13 | 2021-07-09 | 宁波昊祥新材料科技有限公司 | Mo-V-Te-Nb-O catalyst and preparation method and application thereof |
| 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 |
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