CN109305901A - Method for producing propenoic acid - Google Patents
Method for producing propenoic acid Download PDFInfo
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- CN109305901A CN109305901A CN201710628185.4A CN201710628185A CN109305901A CN 109305901 A CN109305901 A CN 109305901A CN 201710628185 A CN201710628185 A CN 201710628185A CN 109305901 A CN109305901 A CN 109305901A
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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
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol 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
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
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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 relates to method for producing propenoic acid, mainly solve the problems, such as that existing catalyst acrolein conversion rate is low low with acrylic acid yield, by using method for producing propenoic acid, including in the presence of a catalyst, methacrylaldehyde reacts to obtain acrylic acid with oxygenous oxidizing gas；Wherein the catalyst includes carrier and the active component that is carried on carrier, and the active component general formula indicates are as follows: VMoaTibXcYdOeWherein X is to include selected from one of Sc, Nb, Cr, W or a variety of, Y be include the technical solution selected from least one of Fe, Co, Ni, Ru, Os, Ag, Sn, Sb, Bi, La, Ce, preferably solve the technical problem, can be used in the industrial production of acrylic acid.
Description
Technical field
The present invention relates to method for producing propenoic acid.
Background technique
Methacrylaldehyde is simplest unsaturated aldehyde, is a kind of important chemical industry synthesis intermediate, be widely used in picoline,
The synthesis of the important chemical products such as pyridine, glutaraldehyde and acrylic acid.Acrylic acid is important Organic Chemicals, is mainly used to make
The multifunctional macromolecules material such as esters of acrylic acid is made, is widely used in papermaking, leather, coating, weaving, plastics, rubber, oil product add
Add the fields such as agent and oil exploitation.In recent years, the market demand of acrylic acid is worldwide continuously increased, the production of acrylic acid
Also it has been a hot spot of research.
Pass through acrolein oxidation method acrylic acid synthesizing industrially large-scale use at present.Acrolein oxidation method synthesis third
Catalyst used in olefin(e) acid is generally the oxide of Mo-V series, which is Mo, V, and is added to other use
In the element, such as Nb, Sn, Cr, W, Fe, Co, Ni, Sb etc. that improve catalyst performance.US Pat7220698B2 is described one
The micro catalyst poison of kind is introduced into catalyst preparation process, is inhibited the thermal degradation of catalyst, is provided the stabilization of catalyst
Property.US Pat7456129B2 is described changes acid content, control acid strength in catalyst carrier preparation, improves catalyst
Performance.CN1697701, CN1210511 propose a kind of preparation method of composite oxide catalysts, are to mix each element component
Liquid (containing Fe, Co, Mo, V, Bi, Ni etc.) co-precipitation is closed, is dried to powder, then by tabletting, extrusion molding, finally roasting is obtained
Composite oxide catalysts.Acrylic acid catalyst can be successfully prepared by the above several method, and improves catalyst performance, but
Catalytic mechanical intensity difference, catalytic activity is relatively low, thus practical application will receive limitation.
Catalyst activity component is loaded on the carrier of large specific surface area, the mechanical strength of catalyst can be increased, greatly
It is big to increase activity component load quantity, and make to obtain performance largely by synergistic effect between catalyst activity component.
CN1130172 (method for producing acrylic acid) describes a kind of preparation method of ball shape catalyst, and carrier is added to active group
Divide in mixed liquor, evaporation drying, so that active component is deposited on the surface of carrier.But the acrylic acid catalyst that the prior art obtains
Catalytic activity, selectivity and yield needs further increase.
Summary of the invention
The technical problem to be solved by the present invention is to the low problem low with acrylic acid yield of existing catalyst acrolein conversion rate,
A kind of new method for producing propenoic acid is provided, this method has the characteristics that acrolein conversion rate height and acrylic acid high income.
In order to solve the above technical problems, technical scheme is as follows:
Method for producing propenoic acid, including in the presence of a catalyst, methacrylaldehyde is reacted with oxygenous oxidizing gas
To acrylic acid；Wherein the catalyst includes carrier and the active component that is carried on carrier, and the active component general formula indicates
Are as follows: VMoaTibXcYdOe, wherein X to be that include selected from one of Sc, Nb, Cr, W or a variety of, Y be include selected from Fe, Co, Ni,
At least one of Ru, Os, Ag, Sn, Sb, Bi, La, Ce；A is the molar ratio of Mo and V, a value 2.0~8.0；B is Ti's and V
Molar ratio, b value 0.2~0.8；C is the molar ratio of X and V, c value 0.2~1.0；D is the molar ratio of Y and V, d value 0.05
~1.2；E is to meet oxygen atom molal quantity needed for each element chemical valence in active component.
In above-mentioned technical proposal, the reaction is preferably carried out in the presence of dilution property gaseous phase materials.
In above-mentioned technical proposal, the oxidizing gas preferably is selected from pure oxygen, oxygen-enriched or air.
In above-mentioned technical proposal, the dilution property gaseous phase materials are preferably vapor.
In above-mentioned technical proposal, reaction temperature is preferably 100~500 DEG C.
It take the material that methacrylaldehyde, air and water vapour form as the unstripped gas of reaction, with volume ratio in above-mentioned technical proposal
Meter, preferably methacrylaldehyde: air: water vapour=1:(1~6): (0.5~5).
In above-mentioned technical proposal, the volume space velocity of unstripped gas is preferably 800~2000 hours-1。
One of in above-mentioned technical proposal, as a preferred technical scheme, Y preferably includes that Os and Sn, Os and Sn are being mentioned simultaneously
There is synergistic effect in terms of high acrylic acid yield.
In above-mentioned technical proposal, two, Y as a preferred technical scheme preferably includes that Os and Ru, Os and Ru are being mentioned simultaneously
There is synergistic effect in terms of high acrylic acid yield.
In above-mentioned technical proposal, three, Y as a preferred technical scheme preferably includes that Os and La, Os and La are being mentioned simultaneously
There is synergistic effect in terms of high acrylic acid yield.
In above-mentioned technical proposal, as more preferred one of technical solution, Y includes Os, Sn and Ru simultaneously, and three is mentioning
There is triple combination synergistic effect in terms of high acrylic acid yield.
In above-mentioned technical proposal, two, the Y as more preferred technical solution includes simultaneously Os, La and Ru, and three is mentioning
There is triple combination synergistic effect in terms of high acrylic acid yield.
In above-mentioned technical proposal, three, the Y as more preferred technical solution includes simultaneously Os, La and Sn, and three is mentioning
There is triple combination synergistic effect in terms of high acrylic acid yield.
In above-mentioned technical proposal, the molar ratio of Mo and V can such as be but not limited to 2.5,3.0,3.5,4.0,4.5,
5.0,5.5,6.0,7.0 etc..
In above-mentioned technical proposal, the molar ratio of Ti and V can such as be but not limited to 0.25,0.30,0.35,0.40,
0.45,0.50,0.55,0.60,0.70 etc..
In above-mentioned technical proposal, the molar ratio of Cr and V can such as be but not limited to 0.25,0.30,0.35,0.40,
0.45,0.50,0.55,0.60,0.70 etc..
In above-mentioned technical proposal, the molar ratio of Os and V can such as be but not limited to 0.05,0.10,0.15,0.20,
0.25,0.30,0.35,0.40,0.45,0.50,0.55,0.60 etc..
In above-mentioned technical proposal, the molar ratio of Sn and V can such as be but not limited to 0.05,0.10,0.15,0.20,
0.25,0.30,0.35,0.40,0.45,0.50,0.55,0.60 etc..
In above-mentioned technical proposal, the molar ratio of Ru and V can such as be but not limited to 0.05,0.10,0.15,0.20,
0.25,0.30,0.35,0.40,0.45,0.50,0.55,0.60 etc..
In above-mentioned technical proposal, the molar ratio of La and V can such as be but not limited to 0.05,0.10,0.15,0.20,
0.25,0.30,0.35,0.40,0.45,0.50,0.55,0.60 etc..
In above-mentioned technical proposal, the more specific example of active component general formula can be but not limited to:
VMo2.0~8.0Ti0.2~0.8Cr0.2~1.0Os0.05~0.60Sn0.05~0.60Oe；
VMo2.0~8.0Ti0.2~0.8Cr0.2~1.0Os0.05~0.60Ru0.05~0.60Oe；
VMo2.0~8.0Ti0.2~0.8Cr0.2~1.0Os0.05~0.60La0.05~0.60Oe；
VMo2.0~8.0Ti0.2~0.8Cr0.2~1.0Os0.05~0.45Sn0.05~0.3Ru0.05~0.45Oe；
VMo2.0~8.0Ti0.2~0.8Cr0.2~1.0Os0.05~0.45La0.05~0.3Ru0.05~0.45Oe；
VMo2.0~8.0Ti0.2~0.8Cr0.2~1.0Os0.05~0.45La0.05~0.3Sn0.05~0.45Oe；
Wherein e is to meet oxygen atom molal quantity needed for each element chemical valence in active component.
In above-mentioned technical proposal, by weight, active component content is preferably 10~60w% in catalyst.
In above-mentioned technical proposal, by weight, vector contg is preferably 40~90w% in catalyst.
In above-mentioned technical proposal, the shape and size of carrier are not particularly limited, can obtain comparable technology effect
Fruit, in this regard, those skilled in the art can reasonably select.For convenient for year-on-year, specific embodiment of the invention carrier is spherical shape.
In above-mentioned technical proposal, the preferred self-alumina of the carrier, lithia, magnesia, silica and titanium dioxide
At least one of.
In above-mentioned technical proposal, the catalyst is using the method preparation included the following steps:
The preparation of active component element mixed liquor；
Active component element mixed liquor is mixed with carrier；
Roasting.
In above-mentioned technical proposal, the dispersion liquid can be the mixture of solution, suspension or solution and suspension.
In above-mentioned technical proposal, the condition of roasting is not particularly limited, as long as can be institute present in above-mentioned dispersion liquid
The particular compound form of active element is fired into the condition of the form of oxide, and those skilled in the art can be with to this
The condition of roasting reasonably select and need not make the creative labor.
In above-mentioned technical proposal, only as an example, maturing temperature is 300~550 DEG C.
In above-mentioned technical proposal, only as an example, calcining time is 1~12 hour.
In above-mentioned technical proposal, only as an example, calcination atmosphere is inert atmosphere or contains O2Atmosphere.But economically
Consider, the atmosphere of roasting is preferably air.If non-specifically indicating, the atmosphere roasted in the present invention is air.
In above-mentioned technical proposal, the catalyst is prepared in the following way, specific as follows:
A1, the preparation of active element solution
It dissolves the compound of required active component element to obtain the aqueous solution of active element；The dissolving step is not special
Limitation, the program specifically dissolved and process conditions those skilled in the art can reasonably select.
A2, active element introducted
Carrier granular is mixed into (the wherein dosage of active element mixture with active element mixture obtained by step a1
It is dry for the desired amount of 5~50w% of catalyst), obtain catalyst precarsor I.Dry temperature can be but not limited to 60~
100 DEG C, the dry time can for example be but not limited to 2~8 hours.
A3, roasting
Calcined catalyst precursor II obtains the catalyst.Catalyst precarsor II can also include dry before firing
Step, dry temperature are such as, but not limited to 60~100 DEG C, and the dry time is such as, but not limited to 2~12 hours.The temperature of roasting
Such as, but not limited to 300~550 DEG C of degree, the time of roasting is such as, but not limited to 1~12 hour.
The catalyst of aforesaid way preparation is unusually good in terms of acrolein conversion rate and acrylic acid yield.
Evaluating catalyst method of the invention is as follows:
Reactor: fixed bed reactors, 25 millimeters of internal diameter, 750 millimeters of reactor length；
Catalyst filling amount: 200 grams；
Reaction temperature: 280 DEG C；
Reaction time: 4 hours；
Volume feed: methacrylaldehyde: air: water vapour=1:3.5:2；
Raw material total volume air speed: 1400 hours-1。
Acrolein conversion rate and acrylic acid yield are defined as follows:
Acrolein conversion rate=(mole that mole/methacrylaldehyde of acrolein reaction is always added) × 100%；
Acrylic acid yield=(mole that mole/methacrylaldehyde that acrylic acid generates always is added) × 100%.
Using the method for the present invention, up to 98% or more, acrylic acid yield achieves acrolein conversion rate up to 95% or more
Preferable technical effect, can be used in the industrial production of acrylic acid.
Specific embodiment
[embodiment 1]
1, prepared by active element solution
By the ammonium metavanadate (molecular formula are as follows: NH containing 0.1 mole of V4VO3) be dissolved in 80 DEG C of hot water 200g.It will contain
Ammonium molybdate (the molecular formula are as follows: (NH of 0.4 mole of Mo4)2MoO4) be added thereto, then it is separately added into the chromic acid containing 0.04 mole of Cr
Ammonium (molecular formula are as follows: (NH4)2CrO4), the osmium tetroxide (molecular formula are as follows: OsO containing 0.04 mole of Os4), stirring keeps it all molten
Solution obtains solution I.Titanium Nitrate (the molecular formula are as follows: Ti (NO of 0.04 mole of Ti will be contained3)4) aqueous solution is added separately to above-mentioned solution
In, it is uniformly mixed, is evaporated at 80 DEG C in mixed material solution and is equivalent to VMo containing active component4Ti0.4Cr0.4Os0.4OeIt is dense
Degree is 0.4g/g, obtains solution II.
2, active element introducted
The spherical alumina support 200g that diameter is 5mm is uniformly mixed with 200g solution II, is obtained within dry 4 hours at 80 DEG C
To catalyst precarsor I.
3, it roasts
Catalyst precarsor II is 6 hours dry through 90 DEG C, roasts 3 hours at 400 DEG C and obtains forming following catalyst:
29w%VMo4Ti0.4Cr0.4Os0.4Oe+ 71w%Al2O3。
4, evaluating catalyst
Investigate acrolein conversion rate and acrylic acid yield.
For the evaluation result of load step in catalyst and catalyst is listed in table 1 convenient for comparing.
[embodiment 2]
1, prepared by active element solution
By the ammonium metavanadate (molecular formula are as follows: NH containing 0.1 mole of V4VO3) be dissolved in 80 DEG C of hot water 200g.It will contain
Ammonium molybdate (the molecular formula are as follows: (NH of 0.4 mole of Mo4)2MoO4) be added thereto, then it is separately added into the chromic acid containing 0.04 mole of Cr
Ammonium (molecular formula are as follows: (NH4)2CrO4), the nitric acid tin (molecular formula are as follows: Sn (NO containing 0.04 mole of Sn3)2), stirring makes its whole
Dissolution obtains solution I.Titanium Nitrate (the molecular formula are as follows: Ti (NO of 0.04 mole of Ti will be contained3)4) aqueous solution be added separately to it is above-mentioned molten
In liquid, it is uniformly mixed, is evaporated at 80 DEG C in mixed material solution and is equivalent to VMo containing active component4Ti0.4Cr0.4Sn0.4Oe's
Concentration is 0.4g/g, obtains solution II.
2, active element introducted
The spherical alumina support 200g that diameter is 5mm is uniformly mixed with 200g solution II, is obtained within dry 4 hours at 80 DEG C
To catalyst precarsor I.
3, it roasts
Catalyst precarsor II is 6 hours dry through 90 DEG C, roasts 3 hours at 400 DEG C and obtains forming following catalyst:
29w%VMo4Ti0.4Cr0.4Sn0.4Oe+ 71w%Al2O3。
4, evaluating catalyst
Investigate acrolein conversion rate and acrylic acid yield.
For the evaluation result of load step in catalyst and catalyst is listed in table 1 convenient for comparing.
[embodiment 3]
1, prepared by active element solution
By the ammonium metavanadate (molecular formula are as follows: NH containing 0.1 mole of V4VO3) be dissolved in 80 DEG C of hot water 200g.It will contain
Ammonium molybdate (the molecular formula are as follows: (NH of 0.4 mole of Mo4)2MoO4) be added thereto, then it is separately added into the chromic acid containing 0.04 mole of Cr
Ammonium (molecular formula are as follows: (NH4)2CrO4), the ruthenium hydrochloride ammonium (molecular formula are as follows: (NH containing 0.04 mole of Ru4)2RuCl6), stirring makes it
All dissolution obtains solution I.Titanium Nitrate (the molecular formula are as follows: Ti (NO of 0.04 mole of Ti will be contained3)4) aqueous solution is added separately to
It states in solution, is uniformly mixed, is evaporated in mixed material solution and is equivalent to containing active component at 80 DEG C
VMo4Ti0.4Cr0.4Ru0.4OeConcentration be 0.4g/g, obtain solution II.
2, active element introducted
The spherical alumina support 200g that diameter is 5mm is uniformly mixed with 200g solution II, is obtained within dry 4 hours at 80 DEG C
To catalyst precarsor I.
3, it roasts
Catalyst precarsor II is 6 hours dry through 90 DEG C, roasts 3 hours at 400 DEG C and obtains forming following catalyst:
29w%VMo4Ti0.4Cr0.4Ru0.4Oe+ 71w%Al2O3。
4, evaluating catalyst
Investigate acrolein conversion rate and acrylic acid yield.
For the evaluation result of load step in catalyst and catalyst is listed in table 1 convenient for comparing.
[embodiment 4]
1, prepared by active element solution
By the ammonium metavanadate (molecular formula are as follows: NH containing 0.1 mole of V4VO3) be dissolved in 80 DEG C of hot water 200g.It will contain
Ammonium molybdate (the molecular formula are as follows: (NH of 0.4 mole of Mo4)2MoO4) be added thereto, then it is separately added into the chromic acid containing 0.04 mole of Cr
Ammonium (molecular formula are as follows: (NH4)2CrO4), the lanthanum nitrate (molecular formula are as follows: La (NO containing 0.04 mole of La3)3), stirring makes its whole
Dissolution obtains solution I.Titanium Nitrate (the molecular formula are as follows: Ti (NO of 0.04 mole of Ti will be contained3)4) aqueous solution be added separately to it is above-mentioned molten
In liquid, it is uniformly mixed, is evaporated at 80 DEG C in mixed material solution and is equivalent to VMo containing active component4Ti0.4Cr0.4La0.4Oe's
Concentration is 0.4g/g, obtains solution II.
2, active element introducted
The spherical alumina support 200g that diameter is 5mm is uniformly mixed with 200g solution II, is obtained within dry 4 hours at 80 DEG C
To catalyst precarsor I.
3, it roasts
Catalyst precarsor II is 6 hours dry through 90 DEG C, roasts 3 hours at 400 DEG C and obtains forming following catalyst:
29w%VMo4Ti0.4Cr0.4La0.4Oe+ 71w%Al2O3。
4, evaluating catalyst
Investigate acrolein conversion rate and acrylic acid yield.
For the evaluation result of load step in catalyst and catalyst is listed in table 1 convenient for comparing.
[embodiment 5]
1, prepared by active element solution
By the ammonium metavanadate (molecular formula are as follows: NH containing 0.1 mole of V4VO3) be dissolved in 80 DEG C of hot water 200g.It will contain
Ammonium molybdate (the molecular formula are as follows: (NH of 0.4 mole of Mo4)2MoO4) be added thereto, then it is separately added into the chromic acid containing 0.04 mole of Cr
Ammonium (molecular formula are as follows: (NH4)2CrO4), the osmium tetroxide (molecular formula are as follows: OsO containing 0.02 mole of Os4), contain 0.02 mole of Sn
Nitric acid tin (molecular formula are as follows: Sn (NO3)2), stirring makes it, and all dissolution obtains solution I.The Titanium Nitrate of 0.04 mole of Ti will be contained
(molecular formula are as follows: Ti (NO3)4) aqueous solution is added separately in above-mentioned solution, it is uniformly mixed, is evaporated to mixed material at 80 DEG C
VMo containing active component is equivalent in solution4Ti0.4Cr0.4Os0.2Sn0.2OeConcentration be 0.4g/g, obtain solution II.
2, active element introducted
The spherical alumina support 200g that diameter is 5mm is uniformly mixed with 200g solution II, is obtained within dry 4 hours at 80 DEG C
To catalyst precarsor I.
3, it roasts
Catalyst precarsor II is 6 hours dry through 90 DEG C, roasts 3 hours at 400 DEG C and obtains forming following catalyst:
29w%VMo4Ti0.4Cr0.4Os0.2Sn0.2Oe+ 71w%Al2O3。
4, evaluating catalyst
Investigate acrolein conversion rate and acrylic acid yield.
For the evaluation result of load step in catalyst and catalyst is listed in table 1 convenient for comparing.
[embodiment 6]
1, prepared by active element solution
By the ammonium metavanadate (molecular formula are as follows: NH containing 0.1 mole of V4VO3) be dissolved in 80 DEG C of hot water 200g.It will contain
Ammonium molybdate (the molecular formula are as follows: (NH of 0.4 mole of Mo4)2MoO4) be added thereto, then it is separately added into the chromic acid containing 0.04 mole of Cr
Ammonium (molecular formula are as follows: (NH4)2CrO4), the osmium tetroxide (molecular formula are as follows: OsO containing 0.02 mole of Os4), contain 0.02 mole of Ru
Ruthenium hydrochloride ammonium (molecular formula are as follows: (NH4)2RuCl6), stirring makes it, and all dissolution obtains solution I.The nitre of 0.04 mole of Ti will be contained
Sour titanium (molecular formula are as follows: Ti (NO3)4) aqueous solution is added separately in above-mentioned solution, it is uniformly mixed, mixing is evaporated at 80 DEG C
VMo containing active component is equivalent in material solution4Ti0.4Cr0.4Os0.2Ru0.2OeConcentration be 0.4g/g, obtain solution II.
2, active element introducted
The spherical alumina support 200g that diameter is 5mm is uniformly mixed with 200g solution II, is obtained within dry 4 hours at 80 DEG C
To catalyst precarsor I.
3, it roasts
Catalyst precarsor II is 6 hours dry through 90 DEG C, roasts 3 hours at 400 DEG C and obtains forming following catalyst:
29w%VMo4Ti0.4Cr0.4Os0.2Ru0.2Oe+ 71w%Al2O3。
4, evaluating catalyst
Investigate acrolein conversion rate and acrylic acid yield.
For the evaluation result of load step in catalyst and catalyst is listed in table 1 convenient for comparing.
[embodiment 7]
1, prepared by active element solution
By the ammonium metavanadate (molecular formula are as follows: NH containing 0.1 mole of V4VO3) be dissolved in 80 DEG C of hot water 200g.It will contain
Ammonium molybdate (the molecular formula are as follows: (NH of 0.4 mole of Mo4)2MoO4) be added thereto, then it is separately added into the chromic acid containing 0.04 mole of Cr
Ammonium (molecular formula are as follows: (NH4)2CrO4), the osmium tetroxide (molecular formula are as follows: OsO containing 0.02 mole of Os4), contain 0.02 mole of La
Lanthanum nitrate (molecular formula are as follows: La (NO3)3), stirring makes it, and all dissolution obtains solution I.The Titanium Nitrate of 0.04 mole of Ti will be contained
(molecular formula are as follows: Ti (NO3)4) aqueous solution is added separately in above-mentioned solution, it is uniformly mixed, is evaporated to mixed material at 80 DEG C
VMo containing active component is equivalent in solution4Ti0.4Cr0.4Os0.2La0.2OeConcentration be 0.4g/g, obtain solution II.
2, active element introducted
The spherical alumina support 200g that diameter is 5mm is uniformly mixed with 200g solution II, is obtained within dry 4 hours at 80 DEG C
To catalyst precarsor I.
3, it roasts
Catalyst precarsor II is 6 hours dry through 90 DEG C, roasts 3 hours at 400 DEG C and obtains forming following catalyst:
29w%VMo4Ti0.4Cr0.4Os0.2La0.2Oe+ 71w%Al2O3。
4, evaluating catalyst
Investigate acrolein conversion rate and acrylic acid yield.
For the evaluation result of load step in catalyst and catalyst is listed in table 1 convenient for comparing.
[embodiment 8]
1, prepared by active element solution
By the ammonium metavanadate (molecular formula are as follows: NH containing 0.1 mole of V4VO3) be dissolved in 80 DEG C of hot water 200g.It will contain
Ammonium molybdate (the molecular formula are as follows: (NH of 0.4 mole of Mo4)2MoO4) be added thereto, then it is separately added into the chromic acid containing 0.04 mole of Cr
Ammonium (molecular formula are as follows: (NH4)2CrO4), the osmium tetroxide (molecular formula are as follows: OsO containing 0.015 mole of Os4), contain 0.01 mole
Nitric acid tin (the molecular formula are as follows: Sn (NO of Sn3)2), the ruthenium hydrochloride ammonium (molecular formula are as follows: (NH containing 0.015 mole of Ru4)2RuCl6),
Stirring makes it, and all dissolution obtains solution I.Titanium Nitrate (the molecular formula are as follows: Ti (NO of 0.04 mole of Ti will be contained3)4) aqueous solution difference
It is added in above-mentioned solution, is uniformly mixed, is evaporated in mixed material solution and is equivalent to containing active component at 80 DEG C
VMo4Ti0.4Cr0.4Os0.15Sn0.1Ru0.15OeConcentration be 0.4g/g, obtain solution II.
2, active element introducted
The spherical alumina support 200g that diameter is 5mm is uniformly mixed with 200g solution II, is obtained within dry 4 hours at 80 DEG C
To catalyst precarsor I.
3, it roasts
Catalyst precarsor II is 6 hours dry through 90 DEG C, roasts 3 hours at 400 DEG C and obtains forming following catalyst:
29w%VMo4Ti0.4Cr0.4Os0.15Sn0.1Ru0.15Oe+ 71w%Al2O3。
4, evaluating catalyst
Investigate acrolein conversion rate and acrylic acid yield.
For the evaluation result of load step in catalyst and catalyst is listed in table 1 convenient for comparing.
[embodiment 9]
1, prepared by active element solution
By the ammonium metavanadate (molecular formula are as follows: NH containing 0.1 mole of V4VO3) be dissolved in 80 DEG C of hot water 200g.It will contain
Ammonium molybdate (the molecular formula are as follows: (NH of 0.4 mole of Mo4)2MoO4) be added thereto, then it is separately added into the chromic acid containing 0.04 mole of Cr
Ammonium (molecular formula are as follows: (NH4)2CrO4), the osmium tetroxide (molecular formula are as follows: OsO containing 0.015 mole of Os4), contain 0.01 mole
Lanthanum nitrate (the molecular formula are as follows: La (NO of La3)3), the ruthenium hydrochloride ammonium (molecular formula are as follows: (NH containing 0.015 mole of Ru4)2RuCl6),
Stirring makes it, and all dissolution obtains solution I.Titanium Nitrate (the molecular formula are as follows: Ti (NO of 0.04 mole of Ti will be contained3)4) aqueous solution difference
It is added in above-mentioned solution, is uniformly mixed, is evaporated in mixed material solution and is equivalent to containing active component at 80 DEG C
VMo4Ti0.4Cr0.4Os0.15La0.1Ru0.15OeConcentration be 0.4g/g, obtain solution II.
2, active element introducted
The spherical alumina support 200g that diameter is 5mm is uniformly mixed with 200g solution II, is obtained within dry 4 hours at 80 DEG C
To catalyst precarsor I.
3, it roasts
Catalyst precarsor II is 6 hours dry through 90 DEG C, roasts 3 hours at 400 DEG C and obtains forming following catalyst:
29w%VMo4Ti0.4Cr0.4Os0.15La0.1Ru0.15Oe+ 71w%Al2O3。
4, evaluating catalyst
Investigate acrolein conversion rate and acrylic acid yield.
For the evaluation result of load step in catalyst and catalyst is listed in table 1 convenient for comparing.
[embodiment 10]
1, prepared by active element solution
By the ammonium metavanadate (molecular formula are as follows: NH containing 0.1 mole of V4VO3) be dissolved in 80 DEG C of hot water 200g.It will contain
Ammonium molybdate (the molecular formula are as follows: (NH of 0.4 mole of Mo4)2MoO4) be added thereto, then it is separately added into the chromic acid containing 0.04 mole of Cr
Ammonium (molecular formula are as follows: (NH4)2CrO4), the osmium tetroxide (molecular formula are as follows: OsO containing 0.015 mole of Os4), contain 0.01 mole
Lanthanum nitrate (the molecular formula are as follows: La (NO of La3)3), the nitric acid tin (molecular formula are as follows: Sn (NO containing 0.015 mole of Sn3)2), stirring
Making it, all dissolution obtains solution I.Titanium Nitrate (the molecular formula are as follows: Ti (NO of 0.04 mole of Ti will be contained3)4) aqueous solution is separately added into
Into above-mentioned solution, it is uniformly mixed, is evaporated in mixed material solution and is equivalent to containing active component at 80 DEG C
VMo4Ti0.4Cr0.4Os0.15La0.1Sn0.15OeConcentration be 0.4g/g, obtain solution II.
2, active element introducted
The spherical alumina support 200g that diameter is 5mm is uniformly mixed with 200g solution II, is obtained within dry 4 hours at 80 DEG C
To catalyst precarsor.
3, it roasts
Catalyst precarsor II is 6 hours dry through 90 DEG C, roasts 3 hours at 400 DEG C and obtains forming following catalyst:
29w%VMo4Ti0.4Cr0.4Os0.15La0.1Ru0.15Oe+ 71w%Al2O3。
4, evaluating catalyst
Investigate acrolein conversion rate and acrylic acid yield.
For the evaluation result of load step in catalyst and catalyst is listed in table 1 convenient for comparing.
Table 1
Claims (10)
1. method for producing propenoic acid, including in the presence of a catalyst, methacrylaldehyde reacts to obtain with oxygenous oxidizing gas
Acrylic acid；Wherein the catalyst includes carrier and the active component that is carried on carrier, and the active component general formula indicates are as follows:
VMoaTibXcYdOe, wherein X to be that include selected from one of Sc, Nb, Cr, W or a variety of, Y be include selected from Fe, Co, Ni, Ru,
At least one of Os, Ag, Sn, Sb, Bi, La, Ce；A is the molar ratio of Mo and V, a value 2.0~8.0；B is rubbing for Ti and V
That ratio, b value 0.2~0.8；C is the molar ratio of X and V, c value 0.2~1.0；D be Y and V molar ratio, d value 0.05~
1.2；E is to meet oxygen atom molal quantity needed for each element chemical valence in active component.
2. method for producing propenoic acid according to claim 1, it is characterized in that the reaction exists in dilution property gaseous phase materials
Lower progress.
3. method for producing propenoic acid according to claim 1, it is characterized in that the oxidizing gas be selected from pure oxygen, it is oxygen-enriched,
Or air.
4. method for producing propenoic acid according to claim 2, it is characterized in that the dilution property gaseous phase materials are vapor.
5. method for producing propenoic acid according to claim 1, it is characterized in that reaction temperature is 100~500 DEG C.
6. method for producing propenoic acid according to claim 1, it is characterized in that the object formed with methacrylaldehyde, air and water vapour
Material is the unstripped gas of reaction, with volume basis, methacrylaldehyde: air: water vapour=1:(1~6): (0.5~5).
7. method for producing propenoic acid according to claim 6, the volume space velocity of feature unstripped gas is 800~2000 small
When-1。
8. method for producing propenoic acid according to claim 1, it is characterized in that by weight, active component content in catalyst
For 10~60w%.
9. method for producing propenoic acid according to claim 1, it is characterized in that the carrier is selected from aluminium oxide, lithia, oxygen
Change at least one of magnesium, silica and titanium dioxide.
10. method for producing propenoic acid described in claim 1, it is characterized in that the catalyst use included the following steps
Method preparation:
The preparation of active component element mixed liquor；
Active component element mixed liquor is mixed with carrier；
Roasting.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710628185.4A CN109305901A (en) | 2017-07-28 | 2017-07-28 | Method for producing propenoic acid |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4042533A (en) * | 1976-06-07 | 1977-08-16 | The Standard Oil Company | Producing unsaturated aliphatic acids |
| US4358608A (en) * | 1976-06-07 | 1982-11-09 | The Standard Oil Company | Process for producing unsaturated aliphatic acids |
| US4414412A (en) * | 1974-11-12 | 1983-11-08 | Montedison S.P.A. | Process for the preparation of unsaturated carboxylic acids by the catalytic oxidation in gaseous phase of the corresponding aldehydes and catalyst used in said process |
| JP2000317309A (en) * | 1999-05-17 | 2000-11-21 | Toagosei Co Ltd | Production of catalyst for producing acrylic acid |
-
2017
- 2017-07-28 CN CN201710628185.4A patent/CN109305901A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4414412A (en) * | 1974-11-12 | 1983-11-08 | Montedison S.P.A. | Process for the preparation of unsaturated carboxylic acids by the catalytic oxidation in gaseous phase of the corresponding aldehydes and catalyst used in said process |
| US4042533A (en) * | 1976-06-07 | 1977-08-16 | The Standard Oil Company | Producing unsaturated aliphatic acids |
| US4358608A (en) * | 1976-06-07 | 1982-11-09 | The Standard Oil Company | Process for producing unsaturated aliphatic acids |
| JP2000317309A (en) * | 1999-05-17 | 2000-11-21 | Toagosei Co Ltd | Production of catalyst for producing acrylic acid |
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