CN109304157A - The catalyst of prepared by acrolein oxidation acrylic acid - Google Patents

The catalyst of prepared by acrolein oxidation acrylic acid Download PDF

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Publication number
CN109304157A
CN109304157A CN201710628198.1A CN201710628198A CN109304157A CN 109304157 A CN109304157 A CN 109304157A CN 201710628198 A CN201710628198 A CN 201710628198A CN 109304157 A CN109304157 A CN 109304157A
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catalyst
acrylic acid
solution
follows
mole
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王伟华
宋卫林
徐文杰
杨斌
汪国军
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • 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
    • B01J23/28—Molybdenum
    • 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
    • B01J23/6525—Molybdenum
    • 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
    • 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

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to the catalyst of prepared by acrolein oxidation acrylic acid, mainly solve the problems, such as that existing catalyst acrolein conversion rate is low low with acrylic acid yield, by using the catalyst of prepared by acrolein oxidation acrylic acid, including carrier and the active component being carried on carrier, the active component general formula is indicated are as follows: VMoaMgbXcYdOeWherein X is to include selected from one of Sc, Ti, 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

The catalyst of prepared by acrolein oxidation acrylic acid
Technical field
The present invention relates to the catalyst preparation method of prepared by acrolein oxidation acrylic acid and in prepared by acrolein oxidation propylene Application in 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 in the present invention first is that existing catalyst acrolein conversion rate is low low with acrylic acid yield Problem, provides a kind of catalyst of new prepared by acrolein oxidation acrylic acid, which has acrolein conversion rate high and propylene The characteristics of sour high income.
The second technical problem to be solved by the present invention is the preparation method of catalyst described in one of above-mentioned technical problem.
The third technical problem to be solved by the present invention is the application of catalyst described in one of above problem.
One of to solve above-mentioned technical problem, technical scheme is as follows:
The catalyst of prepared by acrolein oxidation acrylic acid, including carrier and the active component being carried on carrier, the activity Component general formula indicates are as follows: VMoaMgbXcYdOe, wherein X be include selected from one of Sc, Ti, Nb, Cr, W or a variety of, Y is to include Selected from least one of Fe, Co, Ni, Ru, Os, Ag, Sn, Sb, Bi, La, Ce；A be Mo and V molar ratio, a value 2.0~ 8.0；B is the molar ratio of Mg and V, b value 0.2~0.8；C is the molar ratio of X and V, c value 0.2~1.0；D is rubbing for Y and V That ratio, d value 0.05~1.2；E is to meet oxygen atom molal quantity needed for each element chemical valence in active component.
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 Mg 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:
VMo2.0~8.0Mg0.2~0.8Cr0.2~1.0Os0.05~0.60Sn0.05~0.60Oe；
VMo2.0~8.0Mg0.2~0.8Cr0.2~1.0Os0.05~0.60Ru0.05~0.60Oe；
VMo2.0~8.0Mg0.2~0.8Cr0.2~1.0Os0.05~0.60La0.05~0.60Oe；
VMo2.0~8.0Mg0.2~0.8Cr0.2~1.0Os0.05~0.45Sn0.05~0.3Ru0.05~0.45Oe；
VMo2.0~8.0Mg0.2~0.8Cr0.2~1.0Os0.05~0.45La0.05~0.3Ru0.05~0.45Oe；
VMo2.0~8.0Mg0.2~0.8Cr0.2~1.0Os0.05~0.45La0.05~0.3Sn0.05~0.45Oe；
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.
To solve above-mentioned technical problem two, technical scheme is as follows:
The preparation method of catalyst described in any one of technical solution of one of above-mentioned technical problem, comprising:
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.
To solve above-mentioned technical problem three, technical scheme is as follows: the technical side of one of above-mentioned technical problem Application of the catalyst described in any one of case in prepared by acrolein oxidation acrylic acid.
Key problem in technology of the invention is the selection of catalyst, method and process conditions art technology for concrete application Personnel can reasonably select and be not required to make the creative labor, such as may is that
For prepared by acrolein oxidation acrylic acid, including any one of the technical solution in one of above-mentioned technical problem In the presence of the catalyst, methacrylaldehyde reacts to obtain acrylic acid with oxygenous oxidizing gas.
It is more stable controllable in order to make to react in above-mentioned technical proposal, preferably carried out in the presence of dilution property gaseous phase materials.
In above-mentioned technical proposal, the oxidizing gas can be pure oxygen, oxygen-enriched, but preferred empty from the economic viewpoint Gas.
In above-mentioned technical proposal, the preferred vapor of the dilution property gaseous phase materials.
In above-mentioned technical proposal, optional 100~500 DEG C of reaction temperature.
In above-mentioned technical proposal, in the unstripped gas of methacrylaldehyde, air and water vapour composition, with volume basis, methacrylaldehyde: Air: water vapour=1:(1~6): (0.5~5).
In above-mentioned technical proposal, the volume space velocity of unstripped gas is 800~2000 hours-1。
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 catalyst of the present invention, up to 98% or more, acrylic acid yield obtains 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.Magnesium nitrate (the molecular formula are as follows: Mg (NO of 0.04 mole of Mg will be contained3)2) 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 component4Mg0.4Cr0.4Os0.4OeIt 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%VMo4Mg0.4Cr0.4Os0.4Oe+ 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.Magnesium nitrate (the molecular formula are as follows: Mg (NO of 0.04 mole of Mg will be contained3)2) 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 component4Mg0.4Cr0.4Sn0.4Oe'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%VMo4Mg0.4Cr0.4Sn0.4Oe+ 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.Magnesium nitrate (the molecular formula are as follows: Mg (NO of 0.04 mole of Mg will be contained3)2) 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 VMo4Mg0.4Cr0.4Ru0.4OeConcentration 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%VMo4Mg0.4Cr0.4Ru0.4Oe+ 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.Magnesium nitrate (the molecular formula are as follows: Mg (NO of 0.04 mole of Mg will be contained3)2) 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 component4Mg0.4Cr0.4La0.4Oe'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%VMo4Mg0.4Cr0.4La0.4Oe+ 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 magnesium nitrate of 0.04 mole of Mg will be contained (molecular formula are as follows: Mg (NO3)2) 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 solution4Mg0.4Cr0.4Os0.2Sn0.2OeConcentration 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%VMo4Mg0.4Cr0.4Os0.2Sn0.2Oe+ 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 Mg will be contained Sour magnesium (molecular formula are as follows: Mg (NO3)2) 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 solution4Mg0.4Cr0.4Os0.2Ru0.2OeConcentration 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%VMo4Mg0.4Cr0.4Os0.2Ru0.2Oe+ 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 magnesium nitrate of 0.04 mole of Mg will be contained (molecular formula are as follows: Mg (NO3)2) 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 solution4Mg0.4Cr0.4Os0.2La0.2OeConcentration 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%VMo4Mg0.4Cr0.4Os0.2La0.2Oe+ 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.Magnesium nitrate (the molecular formula are as follows: Mg (NO of 0.04 mole of Mg will be contained3)2) 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 VMo4Mg0.4Cr0.4Os0.15Sn0.1Ru0.15OeConcentration 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%VMo4Mg0.4Cr0.4Os0.15Sn0.1Ru0.15Oe+ 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.Magnesium nitrate (the molecular formula are as follows: Mg (NO of 0.04 mole of Mg will be contained3)2) 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 VMo4Mg0.4Cr0.4Os0.15La0.1Ru0.15OeConcentration 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%VMo4Mg0.4Cr0.4Os0.15La0.1Ru0.15Oe+ 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.Magnesium nitrate (the molecular formula are as follows: Mg (NO of 0.04 mole of Mg will be contained3)2) 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 VMo4Mg0.4Cr0.4Os0.15La0.1Sn0.15OeConcentration 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%VMo4Mg0.4Cr0.4Os0.15La0.1Ru0.15Oe+ 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. the catalyst of prepared by acrolein oxidation acrylic acid, including carrier and the active component being carried on carrier, the active group General formula is divided to indicate are as follows: VMoaMgbXcYdOe, wherein X be include be selected from one of Sc, Ti, Nb, Cr, W or a variety of, Y include choosing From at least one of Fe, Co, Ni, Ru, Os, Ag, Sn, Sb, Bi, La, Ce；A be Mo and V molar ratio, a value 2.0~ 8.0；B is the molar ratio of Mg and V, b value 0.2~0.8；C is the molar ratio of X and V, c value 0.2~1.0；D is rubbing for Y and V That 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. catalyst according to claim 1, it is characterized in that by weight, in catalyst active component content be 10~ 60w%.
3. catalyst according to claim 1, it is characterized in that by weight, vector contg is 40~90w% in catalyst.
4. catalyst according to claim 1, it is characterized in that the carrier is selected from aluminium oxide, lithia, magnesia, dioxy At least one of SiClx and titanium dioxide.
5. the preparation method of catalyst described in claim 1, comprising:
The preparation of active component element mixed liquor；
Active component element mixed liquor is mixed with carrier；
Roasting.
6. preparation method according to claim 5, it is characterized in that the dispersion liquid is solution, suspension or solution and hangs The mixture of supernatant liquid.
7. preparation method according to claim 5, it is characterized in that maturing temperature is 300~550 DEG C.
8. preparation method according to claim 5, it is characterized in that calcining time is 1~12 hour.
9. preparation method according to claim 5, it is characterized in that calcination atmosphere is inert atmosphere or contains O2Atmosphere.
10. application of the catalyst described in claim 1 in prepared by acrolein oxidation acrylic acid.
CN201710628198.1A 2017-07-28 2017-07-28 The catalyst of prepared by acrolein oxidation acrylic acid Pending CN109304157A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5177260A (en) * 1989-11-06 1993-01-05 Nippon Shokubai Kagaku Kogyo Co., Ltd. Method for production of acrylic acid
CN1266106C (en) * 2001-09-19 2006-07-26 株式会社日本触媒 process for producing propenoic acid
CN101107212A (en) * 2005-02-01 2008-01-16 Lg化学株式会社 Method of producing unsaturated fatty acid
CN101328116B (en) * 1999-05-27 2012-03-28 株式会社日本触媒 A process for producing acrylic acid
CN103418402A (en) * 2012-05-16 2013-12-04 中国石油化工股份有限公司 Catalyst for preparing acrylic acid by acrolein oxidation and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5177260A (en) * 1989-11-06 1993-01-05 Nippon Shokubai Kagaku Kogyo Co., Ltd. Method for production of acrylic acid
CN1031050C (en) * 1989-11-06 1996-02-21 日本触媒化学工业株式会社 Method for production of acrylic acid
CN101328116B (en) * 1999-05-27 2012-03-28 株式会社日本触媒 A process for producing acrylic acid
CN1266106C (en) * 2001-09-19 2006-07-26 株式会社日本触媒 process for producing propenoic acid
CN101107212A (en) * 2005-02-01 2008-01-16 Lg化学株式会社 Method of producing unsaturated fatty acid
CN103418402A (en) * 2012-05-16 2013-12-04 中国石油化工股份有限公司 Catalyst for preparing acrylic acid by acrolein oxidation and preparation method thereof

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Title
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Application publication date: 20190205