CN101039748A - Process for producing metal oxide catalyst - Google Patents
Process for producing metal oxide catalyst Download PDFInfo
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- CN101039748A CN101039748A CNA2005800352508A CN200580035250A CN101039748A CN 101039748 A CN101039748 A CN 101039748A CN A2005800352508 A CNA2005800352508 A CN A2005800352508A CN 200580035250 A CN200580035250 A CN 200580035250A CN 101039748 A CN101039748 A CN 101039748A
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Abstract
A process fro producing fro producing a high-performance catalyst for use in a reaction for acrylic acid production from propane or propylene through air oxidation, is provided. A process for producing a metal oxide catalyst having the following composition formula, the process comprising the following steps (1) and (2): Composition formula MoV i A j B k C x O y (wherein A is Te or Sb; B is at least one element selected from the group consisting of Nb, Ta, and Ti; C is Si or Ge; i and j each are 0.01-1.5 and j/i is from 0.3 to 1.0; k is 0.001-3.0; x is 0.002-0.1; and y is a number determined by the oxidized states of the other elements), Step (1): a step in which an aqueous liquid containing Mo, V, metal A and metal B is evaporated to dryness and the solid matter obtained is calcined at a high temperature to thereby obtain a metal oxide; and Step (2): a step in which in an atmosphere containing substantially no water, a compound containing metallic element C is adhered to the metal oxide obtained in step (1) to form an oxide of metal C on the surface of the metal oxide.
Description
Technical field
The present invention relates to a kind of method for producing metal oxidation catalyst, the metal oxidation catalyst is used to produce acrylic acid by the gas phase contact oxidation of propane or propylene, and for producing acrylonitrile by the ammoxidation reaction of propane.
Background technique
In general, acrylic acid is produced by two-stage oxidizing reaction process, the technique, which is included in, generates methacrylaldehyde with the presence of propylene in the case of catalyst and oxygen haptoreaction, then product methacrylaldehyde and oxygen haptoreaction.However, recently, studying and using pentane as starting material and produce acrylic acid in one section, and many has been proposed about the suggestion in the catalyst wherein used.Its typical example includes metal oxide catalyst, such as [Mo, Te, V, Nb] system (patent document 1) and [Mo, Sb, V, Nb] system (patent document 2 and 3).
In addition, having applied for some process patent applications for having compared with metal oxide catalyst about production and mentioning high performance catalyst recently.Such as, patent document 4 discloses a kind of method for producing catalyst, including making molybdenum compound, vfanadium compound and antimonial are in water-bearing media, it reacts under 70 DEG C or higher temperature, the reacting solution made is mixed with niobium compound, and obtained mixture is then evaporated to drying, roasts the solid matter at high temperature.
Patent document 5 discloses a kind of method of catalyst modification, including with comprising being selected from W, Mo, Cr, Zr, Ti, Nb, Ta, V, B, Bi, Te, Pd, Co, Ni, Fe, P, the solution of one or more elements of Si, rare earth element, alkali metal and alkaline-earth metal impregnates [Mo, Te, V] catalyst or [Mo, Sb, V] catalyst, thus over the catalyst by other Metal depositions.Catalytic performance of the modified catalyst in propane ammoxidation reaction is had rated in the publication.
Patent document 1:JP-A-7-010801 (claim)
Patent document 2:JP-A-9-312063 (claim)
Patent document 3:JP-A-10-036311 (claim)
Patent document 4:JP-A-10-137585 (claim)
Patent document 5:JP-A-10-28862 (claim)
Summary of the invention
The problem to be solved in the present invention
In order to obtain high acrylic acid selectivity in one section of oxidation reaction of propane with any catalyst used before, it is necessary to improve the ratio of vapor and propane in reaction gas.Particularly, using 8.0 moles of every mole of propane and higher vapor ratio.However, having a problem that, when using including the condition of such high water vapor ratio, subsequent rectification step and waste water treatment step need considerable cost, and the totle drilling cost of acrylic acid production increases.
On the other hand, the industrial process from production of propylene acrylic acid is had been set up.However, existing technique is two-step process, so that propylene is converted to the reaction of methacrylaldehyde including the first step, and methacrylaldehyde is converted to the reaction of the second step of acrylic acid, which is complicated.Still leave some room for improvement.
The object of the present invention is to provide a kind of methods for producing catalyst, using the catalyst, even if every mole of propane vapor ratio be about 3.3 moles reaction condition under, can also with high yield produce acrylic acid.
Other purpose is to provide a kind of method for producing catalyst, can be in one-step method by production of propylene acrylic acid using the catalyst.
Means to solve the problem
To solve the problem above-mentioned, inventor is had conducted a thorough research.As a result, it has been found that, in the absence of water, when use and specific metallic compound is adhered to thereon by [Mo, Te, V] metal composite oxide, or [Mo, Sb, V] metal composite oxide obtain metal composite oxide when, even if then under the relatively low reaction condition of the ratio of vapor and propane, can also with high yield produce acrylic acid.Inventor can produce acrylic acid it has furthermore been found that with the metal composite oxide in one-step method using propylene as raw material.Therefore the present invention is completed.
That is, the described method comprises the following steps (1) and (2) the present invention provides a kind of method that production has the metal oxide catalyst of consisting of general formula:
Form formula M oViAjBkCxOy
(wherein A is Te or Sb；B is at least one element for being selected from Nb, Ta and Ti；C is Si or Ge；I and j is individually 0.01-1.5, j/i 0.3-1.0；K is 0.001-3.0；X is 0.002-0.1；Y is the numerical value determined by the oxidation state of other elements)
Step (1): in this step, the waterborne liquid comprising Mo, V, metal A and metal B is evaporated to drying, the solid matter of acquisition is roasted at high temperature, to obtain metal oxide；With
Step (2): in this step, in the atmosphere for substantially not including water, the compound comprising metallic element C is attached on the metal oxide obtained in step (1), to form the oxide of metal C on metal oxide surface.
Invention further provides a kind of methods for producing acrylic acid or acrylonitrile comprising when the metal oxide catalyst obtained by above-mentioned method exists, propane or propylene aoxidize by gas phase haptoreaction or ammoxidation.
Advantages of the present invention
In accordance with the present production process, it is easy to obtain metal oxide catalyst, using the metal oxide catalyst, acrylic acid can be produced from propane or propylene high productivity.The metal oxide catalyst has such excellent properties, that is, even if the reaction condition will lead to wastewater treatment and purifying cost is reduced when using low-water-vapour-phase reaction condition, does not also damage the selectivity to acrylic acid.When using so-called cyclic process, wherein propane is especially separated and recovered from as raw material, is obtained so highly selective catalyst and is particularly advantageous.
Other production method according to the present invention, can be in one-step method from production of propylene acrylic acid.
In addition, the metal oxide catalyst can be used for the ammoxidation reaction of propane.Preferred embodiment of the present invention
What it is for step of the present invention (1) includes Mo, V, the aqueous liquid of metal A and metal B, the aqueous liquid obtained preferably through following methods.
That is, preferably the aqueous liquid comprising Mo, V, metal A and metal B is the aqueous liquid that then will obtain in aqueous liquid that metal B compound is added to by being prepared as follows first comprising Mo, the aqueous liquid of V and metal A.Comprising Mo, the aqueous liquid of V and metal A can be by being mixed together Mo compound in an aqueous medium, and V compound and metal A compound, example will be described hereinafter, and stir the liquid mixture for heating obtain down and obtain.It is preferably 40 DEG C or higher for heating the temperature of liquid mixture, and more preferably 40-100 DEG C.Heating time is preferably 1-10 hours, more preferably 2-5 hours.Metal A is Te or Sb as described above.The example of the Te compound includes metallic tellurium, tellurium dioxide, orthotelluric acid, inclined telluric acid and ammonium tellurate.The metallic tellurium is preferably the broken metallic tellurium of experience wet-milling in advance, either by being used in water-bearing media the metallic tellurium with reducing agent restore that tellurium dioxide and telluric acid obtain 5.0 μm or smaller particulate form.The preferred example of Sb compound is metallic antimony and antimony trioxide.
The example of Mo compound includes ammonium molybdate, molybdenum oxide and molybdic acid.Ammonium molybdate is in these compounds preferably as it is water soluble.The preferred example of V compound includes ammonium metavanadate and vanadic anhydride.
The additional amount of Mo compound, metal A compound and V compound is as follows.The atomic ratio that the atomic ratio of V and metal A (i and j) and Mo is respectively 0.01-1.5, metal A and V (j/i) is 0.3-1.0.If any one ratio of Mo, V and metal A cannot then obtain the metal target oxide catalyst with high catalytic performance in the outside.
By being added metal B compound (metal B is at least one element for being selected from Nb, Ta and Ti) in the reaction liquid obtained by process described above, obtaining includes Mo, V, the aqueous liquid of metal A and metal B.From the viewpoint of the performance for the metal oxide catalyst to be obtained, ammonium hydroxide more preferably is added when metal B compound is added.
The temperature of the liquid of ammonium hydroxide to be added and metal B compound is not particularly limited.In general, its temperature can be room temperature.By the way that ammonium hydroxide and metal B compound is added, subtle particulate deposits object is formed in reaction liquid.
The example of metal B compound includes oxide, nitrate, carboxylate, oxysalt and oxalate.Insoluble metal B compound can be used in the form of dispersion in water.However, in this case, the compound can be dissolved in water by using the mode in connection such as oxalic acid.In the metal oxide catalyst that the amount that metal B compound is added will make, when Mo ratio is 1, the atomic ratio of metal B is 0.001-3.0.When Mo ratio is 1, in the case that the ratio of metal B is lower than 0.001 in the catalyst, the catalyst of acquisition tends to deteriorate.On the other hand, in the case where its ratio is more than 3.0, the catalyst activity of acquisition is reduced, and leads to the conversion of propane of difference.
The ammonia vol of addition will make the molar ratio 0.4 or higher of the ammonia and metal B, preferably 0.8-3.0.In the case where ammonia amount and the molar ratio of metal B are less than 0.4, there is no effect.On the other hand, even if the dosage when ammonia is more than 3.0, the effect is not improved, and the exhaust-gas treatment of cost is necessary.
It is preferred that being further added to nitric acid or ammonium nitrate in the dispersion by the way that the fine particle sediment that ammonium hydroxide and metal B compound obtain is added.The nitric acid or ammonium nitrate amount of addition will make the molar ratio of nitrate ion and metal B be preferably 2.0-6.0, more preferable 2.2-4.0.If the effect of addition is very low except the additional amount of nitrate ion is more than the range.
It heats the aqueous liquid (usually pulpous state) obtained and is evaporated to drying.The dry matter of acquisition in the case that it is aerobic there are, at 250-38 DEG C, preferably 280-360 DEG C of roasting temperature 0.5-10 hours, preferably 1-3 hours.
By it is described roasting obtain solid in absence of oxygen, at 480-640 DEG C, preferably 570-620 DEG C roasting temperature 0.1-5 hours, preferably 0.2-1.5 hours.Step (1) is terminated with the roasting.
It will include that the compound (following the compound be known as metal C compound) of metallic element C (it is Si or Ge) is attached on the metal oxide (generally referred to as catalyst precarsor) of the step of being described above (1) acquisition in the atmosphere that wherein water is not present.The example of adhesive bonding method includes: wherein evaporated metal C compound, the method which contacts with the metal oxide；Wherein by the metal oxide impregnated in the anhydrous organic solvent solution of metal C compound and organic solvent, the method then evaporated.The catalyst precarsor of the attachment processing of pending metal C compound is preferably the particulate forms that partial size is about 0.1 millimeter Dao several millimeters.Catalyst precarsor with such particle size can be the catalyst precarsor obtained by sieving the metal oxide powder obtained in step (1), or it can be by the way that the metal oxide powder to be deposited on carrier, the catalyst precarsor that then is obtained by uniform particle size and is obtained for its classification.
As metal C compound, the form that can be used is chloride, organo-metallic compound, the metal C compound of alkoxide etc..However, from the preferred alkoxide of viewpoint of operating characteristics.Its example includes silicon tetrachloride, tetramethoxy-silicane, tetraethoxysilane, trimethoxy silane, triethoxysilane, trimethylsilane, triethylsilane, hexamethyldisilane, hexamethyldisilazane, hexamethyl siloxane and tetraethoxy germanium.More preferably tetraethoxysilane, triethoxysilane, triethylsilane and tetraethoxy germanium.
Wherein the steam of metal C compound, which is attached to the method on catalyst precursor particles, can be method known to any one, as long as the bonding can carry out in the atmosphere that water wherein is not present.
Available straightforward procedure includes: the method for wherein passing through the liquid for passing the gas through and being placed in cylindrical groove using drexel bottle (equipped with filter) for removing grit etc. from gas on a laboratory scale.I.e., it is a kind of such method, it includes that liquid metal C compound is previously positioned in cylindrical drexel bottle, dry inert gas (generally referred to as carrier gas) such as drying nitrogen is passed through by the liquid, to generate dry inert gas, the inert gas flow includes the steam for being equivalent to the metal C compound of vapour pressure amount, and the logistics is made to contact the catalyst precursor particles.
In the method described above, the vapour pressure of metal C compound depends on the temperature and pressure of atmosphere.The straightforward procedure for increasing the vapour pressure is to improve the temperature for the metal C compound being placed in hydrostatic column.For selecting the temperature of the heating, it is advantageous that refer to the boiling point of metal C compound.It is 121.8 DEG C that the example of metal C compound boiling point, which includes for tetramethoxy-silicane, it is 166.8 DEG C for tetraethoxysilane, it is 133.5 DEG C for triethoxysilane, is 107 DEG C for triethylsilane, is 253 DEG C for tetraethoxy germanium and is 57.6 DEG C for silicon tetrachloride.
In addition to the temperature of the metal C compound, the flow velocity of the carrier gas also influences the amount to be bonded to the metal C compound on catalyst precarsor.Flow rate of carrier gas appropriate is that air speed is 1,800-5,000h-1.It is preferred that forming metal C compound steam concentration by using the combination of flow rate of carrier gas appropriate and metal C compound vapor pressure is 0.1-10,000ppm, the admixture of gas of more preferable 1-1,000ppm.
The carrier gas of metal C compound comprising the concentration and the catalyst precarsor are kept in contact reasonable time section, thus the amount that metal C can be described is attached in the metal oxide catalyst, it determines that is, each mole of Mo is in an amount of from 0.002-0.1 moles by composition general formula given herein above.
Absorption of the metal C compound on the catalyst precursor particles is carried out preferably within the container of isolation atmosphere by fixing layer absorption or fluosolids absorption.During the absorption of metal C compound, the temperature of catalyst precursor particles is preferably from room temperature to 350 DEG C, more preferably 50-300 DEG C.When the steam of metal C compound starts to contact with the catalyst precarsor for being maintained at the temperature, the metal C compound adsorbed on precursor surface is changed into rapidly metal oxide and must be fixed on precursor surface.
In the case where wherein fixing layer being used to adsorb, such as using such method, this method includes that hydrostatic column is filled with the catalyst precursor particles, external in advance to heat the container, and makes the carrier gas comprising the metal C compound steam by the container.To which the oxide of metal C can be formed on the precursor surface.
The metal oxide catalyst with same performance can also be produced by the following method, this method includes with the solution impregnation catalyst precursor comprising metal C compound, to which metal C compound to be attached on catalyst precarsor, the metal C compound of the attachment is then changed into oxide.
In the case where wherein catalyst precarsor brought into temporary contact outside air to impregnated processing, the catalyst precarsor absorbs the moisture in outside air.It is therefore preferable that dehydration should carry out before impregnation.The temperature of the dehydration is 50-300 DEG C, preferably 70-250 DEG C.In the case where wherein dehydration temperaturre is lower than 50 DEG C, there is no dehydrating effect.In the case where the wherein dehydration temperaturre is more than 300 DEG C, the surface nature of the catalyst precarsor changes, and is difficult to carry out to deposit the chemical reaction of the metal C compound.
The organic solvent used is not particularly limited.It is however preferred to use hydrocarbon, such as toluene or hexane.Water content in the organic solvent is preferably 0.005 mass % perhaps lower more preferably 0.002 mass % or lower.In the case where the water content of wherein organic solvent is more than 0.005 mass %, preferably by known method, preferred molecular sieve drying means implements dehydration.
The amount of organic solvent for dipping is 0.5-100 times, preferably 1-20 times of the amount of the catalyst volume.In the case where the usage amount of wherein organic solvent is less than 0.5 times, modified effect is poor, because the metal C compound cannot equably be attached to entire catalyst.On the other hand, even if effect does not improve, and increases solvent cost for limited effect when the organic solvent amount used is more than the amount of 100 times of catalyst.The concentration of the compound of metal C described in organic solvent is within the scope of 0.5-300 μm of ol/mL, preferably 5-150 μm of ol/mL.In the case where the concentration of the wherein compound of metal C described in organic solvent is lower than 0.5 μm of ol/mL, it is difficult to deposit metal C, the effect of deposition is very low.On the other hand, in the case where wherein its concentration is more than 300 μm of ol/mL, deposition becomes uneven, and without showing original modified effect.
After the solution dipping of the catalyst precarsor compound of C containing metal, is then taken out from the solution, evaporate and remove the organic solvent from the precursor.The organic solvent can directly be evaporated.It is preferable, however, that the catalyst precarsor described in dry organic solvent washing evaporates the organic solvent to remove unreacted surplus stock C compound later.This method can be further improved modified effect.
In order to remove the organic solvent after wash, known method can be used, such as distill, be centrifugated or filter.Hereafter, catalyst precarsor is heated to 50-300 DEG C, the metal C compound for being thus attached to the catalyst precarsor can be converted into metal oxide and be fixed on precursor surface.The content of metal component described in the metal oxide catalyst of the present invention obtained by the oxide of fixed metal C can be determined by fluorescence X-ray analysis.
The mechanism that metal C compound is attached to the catalyst precarsor raising selectivity illustrates not yet.However, it is assumed that the position for participating in side reaction is blocked by the chemical reaction between metal C compound ligand and the catalyst precursor surface functional group, therefore side reaction is suppressed, so as to cause selectivity modification.Simultaneously, it is assumed that metal C compound is attached in the presence of water wherein, and the metal C compound is hydrolyzed, then is not affixed only to participate in the position of side reaction, and be attached to effective active site, therefore considerably reduce activity.
It is preferred that the metal oxide catalyst particle obtained is with particulate form use.Sized particles can lead to the reduction of catalytic performance.Although the metal oxide catalyst can use in the state of no carrier, it can be used after being deposited on the known carrier with appropriate particle size, the carrier such as silica, aluminium oxide, silica-alumina, silicon carbide etc..Deposition is not particularly limited, it can be advantageous to use known deposition.
For wherein using the propane flammable gas oxidation reaction that is in contact of the metal oxide catalyst produced by method described above to give explanation.Propane and molecular oxygen (hereinafter referred to as oxygen) are introduced into the reactor for loading the metal oxide catalyst as the raw material of production acrylic acid, and are kept at high temperature to generate acrylic acid.Propane and oxygen can be introduced separately into the reactor, mutually be mixed in the reactor.Alternatively, described two raw materials can be pre-mixed, and it is introduced into the reactor with mixed state.In order to control reaction, nitrogen, steam are preferably used in combination with reactant, carbon dioxide etc. is used as carrier gas.
In the case where wherein propane and air are used as raw material, preferably up to 30 times of the ratio of the air and propane, more preferable 0.2-20 times of volume ratio.The ratio of the steam and propane is preferably 0.8-8.In the case where the wherein ratio of the steam and propane is lower than 0.8, it is continuously present combustion reaction, leads to very low acrylic acid selectivity.In the case where wherein its ratio is more than 8 times, the increased costs of rectification step and waste water treatment step lead to unfavorable rentability.The reaction temperature is within the scope of 300-460 DEG C, and preferably 350-420 DEG C.Unstrpped gas air speed appropriate is 1,000-8,000hr-1.Its air speed is lower than 1,000h wherein-1In the case where, the space time yield of the acrylic acid as target compound is reduced.Its air speed is more than 8,000h wherein-1In the case where, conversion ratio is reduced.
Remaining unreacted propane and include that intermediate product propylene in the reaction gas being discharged by reactor outlet can be directly used as fuel.However, the propane and propylene can be separated with ingredients other in the reaction gas, Returning reactor is reused.As the method for separating unreacted propane flammable gas from other ingredients including reaction product and inert gas, known pressure swing absorption process (PSA method), organic solvent adsorption method etc. can be used.Metal oxide catalyst produced by the invention can also be applied to the ammoxidation reaction of propylene oxidation and propane, can be with high yield acrylic acid synthesizing or acrylonitrile.The condition of propylene oxidation or propane ammoxidation reaction can be almost the same with the condition of propane gas phase contact oxidation described above.
Reference implementation example and comparing embodiment, will be clarified in more detail the present invention below.The catalytic performance of the metal oxide catalyst in the embodiment and comparative example acquisition is evaluated by the following method.The average particle diameter that 1.0g (0.8-1.0ml) is loaded into the reaction tube of 10 mm dias made of quartz is the catalyst of 0.5-1mm.370 DEG C are set by the reaction temperature (with the thermocouple measuring temperature being fixed on catalyst layer central part) in the reaction tube.By by the propane of 7.6vol%, the oxygen of 14.2vol%, the mixed gas of the vapor composition of the nitrogen and 24.7vol% of 53.5vol% is with air speed 2,200/hr-1It is sent in reaction tube, therefore generates acrylic acid.
Analyze the composition of reaction product.Based on these analyses, the acrylic acid selectivity represented by following formula and conversion of propane (each in mol) are calculated.
Conversion of propane (%)=100 × [(propane of addition)-(unreacted propane)]/(propane of addition)
Acrylic acid selectivity (%)=100 × (acrylic acid yield)/[propane of addition)-(unreacted propane)]
Acrylic acid yield (%)=[(conversion of propane) × (acrylic acid selectivity)]/100
Under propylene oxidization condition, following formula is used.
Propylene conversion (%)=100 × [(propylene of addition)-(unreacted propylene)]/(propylene of addition)
Acrylic acid selectivity (%)=100 × (acrylic acid yield)/[(propylene of addition)-(unreacted propylene)]
Acrolein selectivity (%)=100 × (acrolein yield)/[(propylene of addition)-(unreacted propylene)]
Acrylic acid yield (%)=[(conversion of propane) × (acrylic acid selectivity)]/100
Embodiment 1
The ammonium metavanadate of 2.66g, the ammonium molybdate of 15.45g and the distilled water of 50ml are introduced into the 500ml flask made of glass.Solid stirring and dissolving at a temperature of about 80 DEG C.After dissolution is completed, stop heating, it will be added in the solution by restoring the 30ml aqueous dispersion comprising 1.46g tellurium metal particle (average major axis length is 0.3 μm, the rod-shaped particle that average minor axis length is 0.1 μm) that tellurium dioxide obtains with hydrazine.In addition, being dropwisely added the ammonium hydroxide of 1.0g 30% thereto.Described reaction liquid a few minutes are stirred, become 50 DEG C by stirring its temperature.
It is added into these reaction liquids by the way that 5.89g oxalic acid and 2.32g niobic acid are dissolved in the aqueous solution obtained in 160ml distilled water.The liquid mixture of stirring to obtain 5 minutes, additionally incorporates 4.0g ammonium nitrate thereto.Hereafter, the mixture is evaporated to drying with 120 DEG C of drying machine.
The dry matter of acquisition roasts 1.5 hours in 320 DEG C of air.The solid particle being achieved in that is roasted 1.5 hours at 590 DEG C in stainless steel roasting pipe, to obtain metal oxide.In addition, sifting out the particle that partial size is 0.5-1 millimeters with sieve, it to be used for following experiment.As fluorescence x- light composition analysis as a result, discovery metal oxide (hereinafter referred to as four metal oxides) has following atomic ratio: Mo/V/Te/Nb=1.0/0.28/0.14/0.16 (molar ratio).
It is loaded into the space being placed in quartz ampoule on metal mesh by four metal oxides that steps described above obtains with the amount of 1.0g.The pipe is maintained at 200 DEG C about 30 minutes, while making drying nitrogen with the flow velocity of 0.2L/min from wherein passing through.Hereafter, the connection of nitrogen line is maintained to 50 DEG C of the drexel bottle comprising tetraethoxysilane.When nitrogen flow rate is maintained at 0.5L/min, introduces tetraethoxysilane steam and contacted with the metal oxide particle for being maintained at 200 DEG C 5 minutes.To obtain metal oxidation catalyst.
It was found that the metal oxide catalyst has consisting of: Mo/V/Te/Nb/Si=1.0/0.28/0.14/0.16/0.011 (molar ratio).As shown in table 1 using the acrylic acid yield of the catalyst in oxidation of propane reaction etc..
Embodiment 2
Such as identical step of embodiment 1 is carried out, the difference is that only contacts four metal oxides as catalyst precarsor produced in the steam of triethoxysilane and embodiment 1.Therefore, obtaining metal group becomes the metal oxide catalyst of Mo/V/Te/Nb/Si=1.0/0.28/0.14/0.16/0.012 (molar ratio).
Embodiment 3
Such as identical step of embodiment 1 is carried out, the difference is that only contacts four metal oxides as catalyst precarsor produced in the steam of triethylsilane and embodiment 1.Therefore, obtaining metal group becomes the metal oxide catalyst of Mo/V/Te/Nb/Si=1.0/0.28/0.14/0.16/0.033 (molar ratio).
Embodiment 4
Such as identical step of embodiment 1 is carried out, the difference is that only contacts four metal oxides as catalyst precarsor produced in the steam of triethoxy germanium and embodiment 1.Therefore, obtaining metal group becomes the metal oxide catalyst of Mo/V/Te/Nb/Ge=1.0/0.28/0.14/0.16/0.007 (molar ratio).
The metal oxide catalyst obtained in embodiment 2-4 is used to implement the reaction by oxidation of propane acrylic acid synthesizing.The results are shown in Table 1 for it.
Embodiment 5
Four metal oxide particles of the part 1.02g as catalyst precarsor produced in embodiment 1 are then handled in the case where no ingress of air as follows by heating drying in 30 minutes in nitrogen 220 DEG C.In nitrogen atmosphere, the metal oxide particle back to room temperature is added in n-hexane (used n-hexane has used 4A molecular sieve dry) solution that the tetraethoxysilane concentration of 7.5ml is 12 μm of ol/mL, and the mixture is sufficiently stirred.Hereafter, mixture is heated at 80 DEG C in nitrogen stream 30 minutes or the longer time is with evaporation of hexane.
The metal oxide catalyst of acquisition is reacted with the method as the above-mentioned embodiment provided for oxidation of propane.Before for oxidation of propane reaction, the metal oxide catalyst is heated to 370 DEG C in the column of its filling, therefore will be converted into oxide from the silicon atom of the tetraethoxysilane adhered to by steps described above.There is following composition: Mo/V/Te/Nb/Si=1.0/0.28/0.14/0.16/0.016 (molar ratio) in the metal oxide catalyst of the state.
Embodiment 6
Four metal oxide particles of the part 1.02g as catalyst precarsor produced in embodiment 1 are then handled in the case where no ingress of air as follows by heating drying in 90 minutes in nitrogen 90 DEG C.
In nitrogen atmosphere, the metal oxide particle for having been returned to room temperature is added in 4.5mL toluene (toluene used has used 4A molecular sieve dry) solution that tetraethoxysilane concentration is 100 μm of ol/mL, and the mixture is sufficiently stirred and then heats 1 hour at 90 DEG C.In the heating, flow back the solvent.After heating is completed, the mixture is cooled to room temperature and filters in air.The particle of recycling is washed with the solvent of 10ml, the solvent is used with several pieces.The metal oxide catalyst of acquisition is with the method as embodiment 1 in oxidation of propane reaction.
Before for oxidation of propane reaction, the metal oxide catalyst is heated to 370 DEG C in the column of its filling, therefore will be converted into oxide from the silicon atom of the tetraethoxysilane adhered to by steps described above.There is following composition: Mo/V/Te/Nb/Si=1.0/0.28/0.14/0.16/0.014 (molar ratio) in the metal oxide catalyst of the state.
Embodiment 7
Identical catalyst is used for reaction evaluating such as in embodiment 6, and wherein propylene rather than propane implement oxidation reaction by reactor with identical flow velocity.The reaction evaluating is carried out at 340 DEG C.Therefore, the conversion ratio for obtaining propylene is 98.4%, and the selectivity of acrylic acid is 84.7%, and the selectivity of methacrylaldehyde is 1.1%.
Comparative example 1
Four metal oxides as catalyst precarsor produced in embodiment 1 are used as catalyst, to implement acrylic acid synthetic reaction by oxidation of propane with the method as the above-mentioned embodiment provided.The results are shown in Table 1 for it.
Comparative example 2
Identical step carries out such as in comparative example 1, the difference is that only that the reaction temperature changes into 360 DEG C.
Comparative example 3
Identical step carries out such as in comparative example 1, the difference is that only that the reaction temperature changes into 350 DEG C.From the oxidation of propane reaction result for the catalyst for using comparative example 2 and comparative example 3 as it can be seen that when reaction temperature is used as unique measurement, reaction temperature is adjusted in the oxidation reaction, the improvement of product selectivity is less effective.
Comparative example 4
Silica sol (trade name, the Snowtex30 of 0.094g Nissan Chemical Industries Ltd. manufacture are placed in beaker；The aqueous dispersion of fine silica powder particle；Silica concentration 30wt%).5.0g distilled water is added thereto and dissolves the colloidal sol.Four metal oxide particles as catalyst precarsor that 2.5g is produced in embodiment 1 are added into the solution.Obtained mixture equably mixes, then 2 hours dry at 120 DEG C.There is the metal oxide catalyst of acquisition following metal to form: Mo/V/Te/Nb/Si=1.0/0.28/0.14/0.16/0.053 (molar ratio).
The catalyst of acquisition is used in the method with the above-mentioned embodiment provided as comparative example, implements acrylic acid synthetic reaction by oxidation of propane.
Comparative example 5
Four metal oxides as catalyst precarsor produced in embodiment 1 are used as catalyst, are aoxidized in the method as embodiment 7 by propylene and implement acrylic acid synthetic reaction.The propylene conversion obtained at 340 DEG C of reaction temperature is 98.1%, and acrylic acid selectivity 73.4% and acrolein selectivity are 3.4%.
[table 1]
| Reaction result | |||||
| The C compound of the C Vapor Deposition of vapor deposition | The molar ratio (M/Mo) of deposition component | Conversion ratio P, % | The selectivity of AA, % | The yield of AA, % | |
| Embodiment 1 | Tetraethoxysilane | Si/Mo=0.011/1.0 | 60.3 | 75.4 | 45.4 |
| Embodiment 2 | Triethoxysilane | Si/Mo=0.012/1.0 | 53.5 | 80.8 | 43.2 |
| Embodiment 3 | Triethylsilane | Si/Mo=0.033/1.0 | 59.2 | 73.8 | 43.7 |
| Embodiment 4 | Tetraethoxy germanium | Ge/Mo=0.045/1.0 | 57.8 | 74.6 | 43.1 |
| Embodiment 5 | Tetraethoxysilane | Si/Mo=0.016/1.0 | 60.8 | 74.4 | 45.2 |
| Embodiment 6 | Tetraethoxysilane | Si/Mo=0.014/1.0 | 56.4 | 81.2 | 45.8 |
| Reaction result | |||||
| The C compound of steeping liq is used for the C compound of steeping liq | Deposit the molar ratio (M/Mo) of molar ratio (M/Mo) deposition component of ingredient | Conversion ratio P, % conversion ratio P, % | The selectivity of AA, % AA selectivity, % | The yield of AA, % AA yield, % | |
| Comparative example 1 | Nothing | 61.0 | 70.1 | 42.7 | |
| Comparative example 2 | Nothing | 54.3 | 71.2 | 35.8 | |
| Comparative example 3 | Nothing | 49.1 | 67.0 | 32.9 | |
| Comparative example 4 | Silica gel silica solution (Snowtex 30) | Si/Mo=0.053/1.0 | 59.0 | 69.6 | 41.1 |
P indicates propane.AA indicates acrylic acid.M is Si or Ge.
Industrial applicibility
The metal oxide catalyst obtained according to the present invention uses propane and air or propylene and air that can produce acrylic acid as raw material with high yield.In addition, using propane and ammonia that can produce acrylonitrile as the raw material catalyst with high yield.
Claims (4)
1. a kind of method that production has the metal oxide catalyst of consisting of general formula, the described method comprises the following steps (1) and (2):
Form formula M oViAjBkCxOy
(wherein A is Te or Sb；B is at least one element for being selected from Nb, Ta and Ti；C is Si or Ge；I and j is individually 0.01-1.5, j/i 0.3-1.0；K is 0.001-3.0；X is 0.002-0.1；Y is the numerical value determined by the oxidation state of other elements),
Step (1): in this step, the aqueous liquid comprising Mo, V, metal A and metal B is evaporated to drying, the solid matter of acquisition is roasted at high temperature, to obtain metal oxide；With
Step (2): in this step, in the atmosphere for substantially not including water, the compound comprising metallic element C is attached on the metal oxide obtained in step (1), to form the oxide of metal C on metal oxide surface.
2. such as the method for claim 1 production metal oxide catalyst, wherein in step (2), it is attached on the metal oxide obtained in step (1) by heating the steam that the compound comprising metallic element C obtains, to form the oxide of metal C on metal oxide surface.
3. a kind of production acrylic acid, including in the case that the metal oxide catalyst produced by claims 1 or 2 the method there are, pass through gas phase haptoreaction propane oxide or propylene.
4. a kind of method for producing acrylonitrile, including in the case that the metal oxide catalyst produced by claims 1 or 2 the method there are, so that propane is carried out ammoxidation reaction.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103071514A (en) * | 2013-01-29 | 2013-05-01 | 新兴能源科技有限公司 | Preparation method of catalyst for preparing acrylic acid with propylene by one-step catalytic oxidation |
| CN103212427A (en) * | 2013-04-18 | 2013-07-24 | 沈阳化工大学 | Boron-containing multi-metallic oxide catalyst and preparation method thereof |
| CN115463672A (en) * | 2022-08-02 | 2022-12-13 | 宁波昊祥新材料科技有限公司 | Method for obtaining catalyst for preparing acrylic acid by using propane as raw material |
| CN115487834A (en) * | 2022-08-02 | 2022-12-20 | 宁波昊祥新材料科技有限公司 | Preparation method of catalyst in reaction process for preparing acrylic acid from propane |
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2005
- 2005-07-13 CN CNB2005800352508A patent/CN100484626C/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103071514A (en) * | 2013-01-29 | 2013-05-01 | 新兴能源科技有限公司 | Preparation method of catalyst for preparing acrylic acid with propylene by one-step catalytic oxidation |
| CN103071514B (en) * | 2013-01-29 | 2015-09-30 | 新兴能源科技有限公司 | A kind of preparation method preparing acrylic acid catalyst for propylene one step catalytic oxidation |
| CN103212427A (en) * | 2013-04-18 | 2013-07-24 | 沈阳化工大学 | Boron-containing multi-metallic oxide catalyst and preparation method thereof |
| CN115463672A (en) * | 2022-08-02 | 2022-12-13 | 宁波昊祥新材料科技有限公司 | Method for obtaining catalyst for preparing acrylic acid by using propane as raw material |
| CN115487834A (en) * | 2022-08-02 | 2022-12-20 | 宁波昊祥新材料科技有限公司 | Preparation method of catalyst in reaction process for preparing acrylic acid from propane |
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