CN103769161A - Acrolein catalyst and preparation method thereof - Google Patents
Acrolein catalyst and preparation method thereof Download PDFInfo
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- CN103769161A CN103769161A CN201210412591.4A CN201210412591A CN103769161A CN 103769161 A CN103769161 A CN 103769161A CN 201210412591 A CN201210412591 A CN 201210412591A CN 103769161 A CN103769161 A CN 103769161A
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Abstract
The invention relates to an acrolein catalyst and a preparation method thereof, which mainly solve the problem of performance reduction of the catalyst after long-time running in the prior art. With the adoption of the technical scheme that the method comprises the following steps of mixing a powdered catalyst precursor selected from at least one of SiO2 or Al2O3 as a carrier, with an adhesive agent and a molybdenum additive, forming, and finally roasting to obtain the catalyst, wherein the molybdenum additive comprises 50-100 mol% of ammonium heptamolybdate and 0-50 mol% of molybdenum trioxide, the technical problem is better solved, and the method can be used for industrial production of the propylene oxidation to acrolein catalyst.
Description
Technical field
The present invention relates to methacrylaldehyde Catalysts and its preparation method.
Background technology
It is important chemical process that α, β unsaturated aldehyde and unsaturated acids are prepared in the selective oxidation of alkene, the catalyst that wherein a kind of active component of the production and application of unsaturated aldehyde contains Mo, Bi.The improvement of catalyst is mainly to carry out from the activity of catalyst and stability aspect, as added transition metal to improve activity in active constituent, increases the single of product and receives; Add rare earth element to improve redox ability; Add the elements such as Fe, Co, Ni to suppress the distillation of Mo, stabilizing catalyst activity component, improves the service life of catalyst etc.
Have a lot of patent reports for alkene selective oxidation:
Chinese patent ZL99106659.6 reduces the generation extending catalyst service life of organic acid, high boiling compound and burnt oily substance by the alkynes in strict control propylene feedstocks gas and diene amount; Chinese patent catalyst that ZL00118705.8 uses is used for the selective oxidation of isobutene, and 4000 hours conversion ratios and yield approximately decline 0.5 percentage point; Chinese patent ZL97191983.6, ZL00122609.6, ZL01111960.8 are reached and are controlled reaction focus, the object of extending catalyst stability by the catalyst layer axially increasing gradually to the multiple reactivities of outlet configuration from reaction gas inlet along reactor.Wherein the modulation of reactivity is by changing catalyst activity component and inert carrier ratio, changes in catalyst key component and realize as Bi, Fe and Mo ratio, catalyst calcination temperature and adjusting alkali metal kind consumption etc.In prior art there is a technological deficiency clearly, general in Selective Oxidation of Propylene acrolein catalyst, be Mo-Bi Containing Oxide Catalyst in use, because molybdenum oxide is under the existence of reaction water steam, the velocity ratio of distillation is very fast, causes in catalyst use procedure active suppression ratio very fast.The composite oxide catalysts of the type is when being used for ammoxidation of propylene reaction acrylonitrile production, generally by regularly adding molybdate compound to this difficult problem of distillation loss solution of supplementing fluidized bed powder catalyst molybdenum component in reactor.Although methacrylaldehyde catalyst uses Mo-Bi Containing Oxide Catalyst equally, generally use fixed bed reactors, catalyst particle size is larger, and this benefit molybdenum method can not be applicable to this reaction, at present the not good technical scheme addressing this problem still.The present invention, by add molybdate compound in shaping of catalyst process, can discharge gradually molybdenum component in course of reaction, reaches the effect of make-up catalyst molybdenum component distillation loss, improves catalyst life cycle.
Summary of the invention
One of technical problem to be solved by this invention is the propylene conversion of used catalyst long-term operation existence in existing methacrylaldehyde preparation method and the problem that methacrylaldehyde yield declines, a kind of preparation method of new methacrylaldehyde catalyst is provided, and catalyst prepared by the method has that propylene conversion is high, methacrylaldehyde yield is high, selective good advantage and the good advantage of catalyst stability.
Two of the technical problem to be solved in the present invention is to provide a kind of catalyst being obtained by the preparation method one of above-mentioned technical problem Suo Shu.
Three of the technical problem to be solved in the present invention be adopt above-mentioned technical problem two described in the synthetic method of methacrylaldehyde of catalyst.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of Selective Oxidation of Propylene legal system methacrylaldehyde catalyst, comprises by being selected from SiO
2or Al
2o
3in at least one powder catalyst precursor that is carrier mix with binding agent and molybdenum additives, moulding, (wherein roasting condition is not key of the present invention in last roasting, but optimum roasting condition is: sintering temperature is 460 ~ 530 ℃, and roasting time is 1.5 ~ 2.5 hours) obtain described catalyst; Wherein said catalyst precarsor contains the active component by following general formula:
Mo
12Bi
aFe
bNi
cSb
dX
eY
fZ
gQ
hO
x
In formula, X is at least one being selected from Mg, Co, Ca, Be, Cu, Zn, Pb or Mn;
Y is at least one that select in Zr, Th or Ti;
Z is at least one being selected from K, Rb, Na, Li, Tl or Cs;
Q is at least one in La, Ce, Sm or Th;
The span of a is 0.05～6.0;
The span of b is 0.05～8.5;
The span of c is 0.05～11.0;
The span of d is 0.05 ~ 2.0;
The span of e is 0.2～9.0;
The span of f is 0.3～9.0;
The span of g is >0～0.5;
The span of h is 0.08～5.0;
X meets the required oxygen atom sum of other element valence;
Described molybdenum additives is made up of 50～100% ammonium heptamolybdates and 0～50% molybdenum trioxide in molar percentage;
Described powder catalyst precursor preparation process comprises the following steps:
A) ammonium molybdate of catalyst precarsor aequum and the metal nitrate that is selected from Z component are dissolved in water to obtain to material 1, it can be any in ammonium dimolybdate, ammonium tetramolybdate, ammonium heptamolybdate or ammonium octamolybdate or by any composition that two or more forms that wherein said ammonium molybdate is not particularly limited it, then carrier required Kaolinite Preparation of Catalyst precursor is added and forms material 2;
B) by the Bi of catalyst precarsor aequum, Fe, Ni and be selected from x, y, z, the metal soluble salt of q class is dissolved in and in water, forms material 3;
D) under agitation, material 3 is added in material 2 and forms catalyst pulp;
E) by mist projection granulating, (wherein mist projection granulating condition is not key of the present invention to catalyst pulp, but suitable mist projection granulating condition is 330 ~ 350 ℃ of intake air temperatures, 120 ~ 135 ℃ of air outlet temperature, atomizing disk rotating speed 20000 ~ 25000rpm), roasting, obtains described powder shaped catalyst precarsor.
In technique scheme, in described catalyst precarsor, the consumption of carrier is preferably 5～40% of catalyst precarsor weight; Described binding agent is at least one in Ludox or aluminium colloidal sol preferably; Described molybdenum additives is preferably made up of 50 ~ 80% ammonium heptamolybdate and 20 ~ 50% molybdenum trioxides in molar percentage; Described molybdenum additives is preferably 0.27 ~ 2.2% of catalyst precarsor weight with molybdenum element weighing scale; Described step e) in sintering temperature be preferably 280 ~ 380 ℃, roasting time and be preferably 1 ~ 3 hour.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: the catalyst that the described technical scheme of one of above-mentioned technical problem obtains.
For solve the problems of the technologies described above three, the technical solution used in the present invention is as follows: the synthetic method of methacrylaldehyde, consists of methacrylaldehyde with molar ratio computing reaction raw materials: air: water vapour=10:60 ~ 80:10 ~ 30, at 350 ~ 390 ℃ of reaction temperatures, reaction pressure 0 ~ 0.05MPa, raw material volume space velocity 800 ~ 1500h
-1under condition, with above-mentioned technical problem two described in catalyst contact, generate methacrylaldehyde.
In technique scheme, described reaction temperature is preferably 360 ~ 385 ℃, raw material volume space velocity and is preferably 900 ~ 1350h
-1.
The present invention is owing to adding described molybdenum additives in shaping of catalyst process, due to molybdenum component can be in course of reaction the sublimation of respective components in make-up catalyst component, delaying catalyst declines at long-term use procedure performance, this mode that adds can not change catalyst (precursor) chemical composition itself, catalyst activity phase composition and chemical constitution simultaneously, can realize better the achievement that in laboratory research, catalytic component is optimized.
Catalyst in the present invention is prepared methacrylaldehyde, propylene for Selective Oxidation of Propylene: air: water vapour mol ratio is 10:60 ~ 80:10 ~ 30,350 ~ 390 ℃ of reaction temperatures, reaction pressure 0 ~ 0.05MPa, raw material volume space velocity 800 ~ 1500h
-1under condition, its propylene conversion is up to 99.1%, product methacrylaldehyde yield is up to 79.6%, and operation is after 3000 hours continuously, catalyst propylene conversion and methacrylaldehyde yield obviously do not decline, and have obtained good technique effect.
Below by embodiment, the present invention is further elaborated:
The specific embodiment
embodiment 1
By 1000 grams of (NH
4)
6mo
7o
244H
2o(is ammonium heptamolybdate) join in the warm water of 1000 grams 70 ℃, stir it is all dissolved, add 2.88 grams of KNO
3and 5.49 grams of CsNO
3obtain material 1, in material 1, add the Ludox that 573.9 grams of concentration are 40 wt% to make material 2.
By 396.9 grams of Fe (NO
3)
39H
2o adds in 70 ℃ of hot water of 150 grams, adds 229.0 grams of Bi (NO after stirring and dissolving again
3)
35H
2o, 480.8 grams of Co (NO
3)
26H
2o, 452.1 grams of Ni (NO
3)
26H
2o, 150.5 grams of Mn (NO that concentration is 50wt %
3)
2the aqueous solution, 19.6 grams of La (NO
3)
33H
2o and 41.7 grams of Sb
2o
3material 3 is made in stirring.
Material 3 is added in material 2 under rapid stirring, form catalyst pulp, and at 65 ℃, stir aging 2 hours, slurry mist projection granulating also obtains powder shaped catalyst precarsor (spray condition: 345 ℃ of intake air temperatures, 125 ℃ of air outlet temperature, atomizing disk rotating speed 22000rpm) after roasting in 350 ℃, 2 hours, and catalyst precarsor chemical composition is listed in table 1.Get 1000 grams of powder shaped catalyst precarsors and add Ludox and the 25 grams of (NH that 200 grams of concentration are 40wt%
4)
6mo
7o
244H
2o mediates 2 hours in kneader, and extrusion molding obtains the hollow cylindrical thing of φ 5x2x5mm, and roasting in then 500 ℃, 2 hours obtains catalyst finished product.
The investigation appreciation condition of catalyst is as follows:
Reactor: fixed bed single tube reactor, 25.4 millimeters of internal diameters, 3000 millimeters of reactor length
Catalyst: 600 grams
Reaction temperature: 375 ℃
Reaction pressure: 0.01MPa
Reaction time: 3000 hours
Material molar ratio: propylene: air: water vapour=10:73:17
Raw material volume space velocity: 1200 hours
-1
Product use gas chromatographic analysis, and calculate Carbon balance, when Carbon balance is valid data during at (95～105) %.
Propylene conversion, product yield and be optionally defined as:
Evaluating catalyst the results are shown in table 2.
embodiment 2
By 1000 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 1000 grams 70 ℃, stirs it is all dissolved, and adds 2.88 grams of KNO
3and 5.49 grams of CsNO
3obtain material 1, in material 1, add the Ludox that 573.9 grams of concentration are 40 wt% to make material 2.
By 396.9 grams of Fe (NO
3)
39H
2o adds in 70 ℃ of hot water of 150 grams, adds 229.0 grams of Bi (NO after stirring and dissolving again
3)
35H
2o, 480.8 grams of Co (NO
3)
26H
2o, 452.1 grams of Ni (NO
3)
26H
2o, 150.5 grams of Mn (NO that concentration is 50wt %
3)
2the aqueous solution, 19.6 grams of La (NO
3)
33H
2o and 41.7 grams of Sb
2o
3material 3 is made in stirring.
Material 3 is added in material 2 under rapid stirring, form catalyst pulp, and at 65 ℃, stir aging 2 hours, slurry mist projection granulating also obtains powder shaped catalyst precarsor (spray condition: 345 ℃ of intake air temperatures, 125 ℃ of air outlet temperature, atomizing disk rotating speed 22000rpm) after roasting in 350 ℃, 2 hours, and catalyst precarsor chemical composition is listed in table 1.Get 1000 grams of powder shaped catalyst precarsors and add Ludox and the 20 grams of (NH that 200 grams of concentration are 40wt%
4)
6mo
7o
244H
2o and 4.1 grams of molybdenum trioxides are mediated 2 hours in kneader, and extrusion molding obtains the hollow cylindrical thing of φ 5x2x5mm, and roasting in then 500 ℃, 2 hours obtains catalyst finished product.
The evaluation method of catalyst, except reaction temperature changes, other conditions are all identical with embodiment 1, for ease of relatively, evaluation temperature and evaluation result listed in to table 2.
embodiment 3
By 1000 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 1000 grams 70 ℃, stirs it is all dissolved, and adds 2.88 grams of KNO
3and 5.49 grams of CsNO
3obtain material 1, in material 1, add the Ludox that 573.9 grams of concentration are 40 wt% to make material 2.
By 396.9 grams of Fe (NO
3)
39H
2o adds in 70 ℃ of hot water of 150 grams, adds 229.0 grams of Bi (NO after stirring and dissolving again
3)
35H
2o, 480.8 grams of Co (NO
3)
26H
2o, 452.1 grams of Ni (NO
3)
26H
2o, 150.5 grams of Mn (NO that concentration is 50wt %
3)
2the aqueous solution, 19.6 grams of La (NO
3)
33H
2o and 41.7 grams of Sb
2o
3material 3 is made in stirring.
Material 3 is added in material 2 under rapid stirring, form catalyst pulp, and at 65 ℃, stir aging 2 hours, slurry mist projection granulating also obtains powder shaped catalyst precarsor (spray condition: 345 ℃ of intake air temperatures, 125 ℃ of air outlet temperature, atomizing disk rotating speed 22000rpm) after roasting in 350 ℃, 2 hours, and catalyst precarsor chemical composition is listed in table 1.Get 1000 grams of powder shaped catalyst precarsors and add Ludox and the 12.5 grams of (NH that 200 grams of concentration are 40wt%
4)
6mo
7o
244H
2o and 10.2 grams of molybdenum trioxides are mediated 2 hours in kneader, and extrusion molding obtains the hollow cylindrical thing of φ 5x2x5mm, and roasting in then 500 ℃, 2 hours obtains catalyst finished product.
The evaluation method of catalyst, except reaction temperature changes, other conditions are all identical with embodiment 1, for ease of relatively, evaluation temperature and evaluation result listed in to table 2.
embodiment 4
By 1000 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 1000 grams 70 ℃, stirs it is all dissolved, and adds 3.84 grams of KNO
3obtain material 1, in material 1, add the aluminium colloidal sol that Ludox that 860 grams of concentration are 40 wt% and 543.2 grams of concentration are 20 wt % to make material 2.
By 473.9 grams of Fe (NO
3)
39H
2o adds in 70 ℃ of hot water of 150 grams, adds 217.5 grams of Bi (NO after stirring and dissolving again
3)
35H
2o, 634.7 grams of Co (NO
3)
26H
2o, 468.7 grams of Ni (NO
3)
26H
2o, 70.2 grams of Mn (NO that concentration is 50wt%
3)
2the aqueous solution, 102.5 grams of Ce (NO
3)
36H
2o and 29.2 grams of Sb
2o
3material 3 is made in stirring.
Material 3 is added in material 2 under rapid stirring, form catalyst pulp, and at 65 ℃, stir aging 2 hours, slurry mist projection granulating also obtains powder shaped catalyst precarsor (spray condition: 345 ℃ of intake air temperatures, 125 ℃ of air outlet temperature, atomizing disk rotating speed 22000rpm) after roasting in 350 ℃, 2 hours, and catalyst precarsor chemical composition is listed in table 1.Get 1000 grams of powder shaped catalyst precarsors and add Ludox and the 25 grams of (NH that 200 grams of concentration are 40wt%
4)
6mo
7o
244H
2o mediates 2 hours in kneader, and extrusion molding obtains the hollow cylindrical thing of φ 5x2x5mm, and roasting in then 500 ℃, 2 hours obtains catalyst finished product.
The evaluation method of catalyst, except reaction temperature changes, other conditions are all identical with embodiment 1, for ease of relatively, evaluation temperature and evaluation result listed in to table 2.
embodiment 5
By 1000 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 1000 grams 70 ℃, stirs it is all dissolved, and adds 2.11 grams of KNO
3and 5.54 grams of RbNO
3obtain material 1, in material 1, add the Ludox that 800.3 grams of concentration are 40 wt% to make material 2.
By 568.3 grams of Fe (NO
3)
39H
2o adds in 70 ℃ of hot water of 150 grams, adds 213.0 grams of Bi (NO after stirring and dissolving again
3)
35H
2o, 502.8 grams of Co (NO
3)
26H
2o, 371.7 grams of Ni (NO
3)
26H
2o, 24.7 grams of Sm
2o
3and 43.8 grams of Sb
2o
3material 3 is made in stirring.
Material 3 is added in material 2 under rapid stirring, form catalyst pulp, and at 65 ℃, stir aging 2 hours, slurry mist projection granulating also obtains powder shaped catalyst precarsor (spray condition: 345 ℃ of intake air temperatures, 125 ℃ of air outlet temperature, atomizing disk rotating speed 22000rpm) after roasting in 350 ℃, 2 hours, and catalyst precarsor chemical composition is listed in table 1.Get 1000 grams of powder shaped catalyst precarsors and add Ludox and the 25 grams of (NH that 200 grams of concentration are 40wt%
4)
6mo
7o
244H
2o mediates 2 hours in kneader, and extrusion molding obtains the hollow cylindrical thing of φ 5x2x5mm, and roasting in then 500 ℃, 2 hours obtains catalyst finished product.
The evaluation method of catalyst, except reaction temperature changes, other conditions are all identical with embodiment 1, for ease of relatively, evaluation temperature and evaluation result listed in to table 2.
embodiment 6
By 1000 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 1000 grams 70 ℃, stirs it is all dissolved, and adds 5.96 grams of RbNO
3and 5.49 grams of CsNO
3obtain material 1, in material 1, add the Ludox that 872.6 grams of concentration are 40 wt% to make material 2.
By 539.4 grams of Fe (NO
3)
39H
2o adds in 70 ℃ of hot water of 150 grams, adds 297.7 grams of Bi (NO after stirring and dissolving again
3)
35H
2o, 406.7 grams of Co (NO
3)
26H
2o, 466.0 grams of Ni (NO
3)
26H
2o, 205.8 grams of Mg (NO
3)
26H
2o, 99.2 grams of Th (NO
3)
44H
2o and 66.0 grams of Sb
2o
3material 3 is made in stirring.
Material 3 is added in material 2 under rapid stirring, form catalyst pulp, and at 65 ℃, stir aging 2 hours, slurry mist projection granulating also obtains powder shaped catalyst precarsor (spray condition: 345 ℃ of intake air temperatures, 125 ℃ of air outlet temperature, atomizing disk rotating speed 22000rpm) after roasting in 350 ℃, 2 hours, and catalyst precarsor chemical composition is listed in table 1.Get 1000 grams of powder shaped catalyst precarsors and add Ludox and the 25 grams of (NH that 200 grams of concentration are 40wt%
4)
6mo
7o
244H
2o mediates 2 hours in kneader, and extrusion molding obtains the hollow cylindrical thing of φ 5x2x5mm, and roasting in then 500 ℃, 2 hours obtains catalyst finished product.
The evaluation method of catalyst, except reaction temperature changes, other conditions are all identical with embodiment 1, for ease of relatively, evaluation temperature and evaluation result listed in to table 2.
embodiment 7
By 1000 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 1000 grams 70 ℃, stirs it is all dissolved, and adds 2.88 grams of KNO
3and 11.0 grams of RbNO
3obtain material 1, in material 1, add the Ludox that 645.9 grams of concentration are 40wt% to make material 2.
By 404.6 grams of Fe (NO
3)
39H
2o adds in 70 ℃ of hot water of 150 grams, adds 274.8 grams of Bi (NO after stirring and dissolving again
3)
35H
2o, 416.0 grams of Ni (NO
3)
26H
2o, 242.1 grams of Mg (NO
3)
26H
2o, 266.5 grams of Ce (NO
3)
36H
2o and 76.5 grams of Sb
2o
3material 3 is made in stirring.
Material 3 is added in material 2 under rapid stirring, form catalyst pulp, and at 65 ℃, stir aging 2 hours, slurry mist projection granulating also obtains powder shaped catalyst precarsor (spray condition: 345 ℃ of intake air temperatures, 125 ℃ of air outlet temperature, atomizing disk rotating speed 22000rpm) after roasting in 350 ℃, 2 hours, and catalyst precarsor chemical composition is listed in table 1.Get 1000 grams of powder shaped catalyst precarsors and add Ludox and the 25 grams of (NH that 200 grams of concentration are 40wt%
4)
6mo
7o
244H
2o mediates 2 hours in kneader, and extrusion molding obtains the hollow cylindrical thing of φ 5x2x5mm, and roasting in then 500 ℃, 2 hours obtains catalyst finished product.
The evaluation method of catalyst, except reaction temperature changes, other conditions are all identical with embodiment 1, for ease of relatively, evaluation temperature and evaluation result listed in to table 2.
embodiment 8
By 1000 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 1000 grams 70 ℃, stirs it is all dissolved, and adds 1.79 grams of KNO
3and 5.49 grams of CsNO
3obtain material 1, in material 1, add the aluminium colloidal sol that Ludox that 602.3 grams of concentration are 40wt% and 401.5 grams of concentration are 20wt% to make material 2.
By 344.9 grams of Fe (NO
3)
39H
2o adds in 70 ℃ of hot water of 150 grams, adds 201.5 grams of Bi (NO after stirring and dissolving again
3)
35H
2o, 467.1 grams of Co (NO
3)
26H
2o, 502.0 grams of Ni (NO
3)
26H
2o, 100.3 grams of Mn (NO that concentration is 50wt%
3)
2the aqueous solution, 58.8 grams of La (NO
3)
33H
2o and 38.9 grams of Sb
2o
3material 3 is made in stirring.
Material 3 is added in material 2 under rapid stirring, form catalyst pulp, and at 65 ℃, stir aging 2 hours, slurry mist projection granulating also obtains powder shaped catalyst precarsor (spray condition: 345 ℃ of intake air temperatures, 125 ℃ of air outlet temperature, atomizing disk rotating speed 22000rpm) after roasting in 350 ℃, 2 hours, and catalyst precarsor chemical composition is listed in table 1.Get 1000 grams of powder shaped catalyst precarsors and add Ludox and the 25 grams of (NH that 200 grams of concentration are 40wt%
4)
6mo
7o
244H
2o mediates 2 hours in kneader, and extrusion molding obtains the hollow cylindrical thing of φ 5x2x5mm, and roasting in then 500 ℃, 2 hours obtains catalyst finished product.
The evaluation method of catalyst, except reaction temperature changes, other conditions are all identical with embodiment 1, for ease of relatively, evaluation temperature and evaluation result listed in to table 2.
embodiment 9
By 1000 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 1000 grams 70 ℃, stirs it is all dissolved, and adds 1.79 grams of KNO
3and 15.1 grams of TlNO
3obtain material 1, in material 1, add the Ludox that 781.7 grams of concentration are 40 wt% to make material 2.
By 366.0 grams of Fe (NO
3)
39H
2o adds in 70 ℃ of hot water of 150 grams, adds 263.3 grams of Bi (NO after stirring and dissolving again
3)
35H
2o, 423.1 grams of Co (NO
3)
26H
2o, 441.0 grams of Ni (NO
3)
26H
2o, 133.8 grams of concentration are the Mn (NO of 50 wt %
3)
2the aqueous solution, 108.9 grams of Mg (NO
3)
26H
2o and 24.3 grams of Sb
2o
3material 3 is made in stirring.
Material 3 is added in material 2 under rapid stirring, form catalyst pulp, and at 65 ℃, stir aging 2 hours, slurry mist projection granulating also obtains powder shaped catalyst precarsor (spray condition: 345 ℃ of intake air temperatures, 125 ℃ of air outlet temperature, atomizing disk rotating speed 22000rpm) after roasting in 350 ℃, 2 hours, and catalyst precarsor chemical composition is listed in table 1.Get 1000 grams of powder shaped catalyst precarsors and add Ludox and the 25 grams of (NH that 200 grams of concentration are 40wt%
4)
6mo
7o
244H
2o mediates 2 hours in kneader, and extrusion molding obtains the hollow cylindrical thing of φ 5x2x5mm, and roasting in then 500 ℃, 2 hours obtains catalyst finished product.
The evaluation method of catalyst, except reaction temperature changes, other conditions are all identical with embodiment 1, for ease of relatively, evaluation temperature and evaluation result listed in to table 2.
embodiment 10
By 1000 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 1000 grams 70 ℃, stirs it is all dissolved, and adds 1.79 grams of KNO
3and 5.49 grams of CsNO
3obtain material 1, in material 1, add the Ludox that 858.9 grams of concentration are 40 wt% to make material 2.
By 635.8 grams of Fe (NO
3)
39H
2o adds in 70 ℃ of hot water of 150 grams, adds 183.2 grams of Bi (NO after stirring and dissolving again
3)
35H
2o, 424.3 grams of Ni (NO
3)
26H
2o, 96.8 grams of Mg (NO
3)
26H
2o, 250.9 grams of concentration are the Mn (NO of 50 wt %
3)
2the aqueous solution, 117.5 grams of La (NO
3)
33H
2o, 49.4 grams of Sm
2o
3and 38.2 grams of Sb
2o
3material 3 is made in stirring.
Material 3 is added in material 2 under rapid stirring, form catalyst pulp, and at 65 ℃, stir aging 2 hours, slurry mist projection granulating also obtains powder shaped catalyst precarsor (spray condition: 345 ℃ of intake air temperatures, 125 ℃ of air outlet temperature, atomizing disk rotating speed 22000rpm) after roasting in 350 ℃, 2 hours, and catalyst precarsor chemical composition is listed in table 1.Get 1000 grams of powder shaped catalyst precarsors and add Ludox and the 25 grams of (NH that 200 grams of concentration are 40wt%
4)
6mo
7o
244H
2o mediates 2 hours in kneader, and extrusion molding obtains the hollow cylindrical thing of φ 5x2x5mm, and roasting in then 500 ℃, 2 hours obtains catalyst finished product.
The evaluation method of catalyst, except reaction temperature changes, other conditions are all identical with embodiment 1, for ease of relatively, evaluation temperature and evaluation result listed in to table 2.
embodiment 11
By 1000 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 1000 grams 70 ℃, stirs it is all dissolved, and adds 1.79 grams of KNO
3and 5.49 grams of CsNO
3obtain material 1, in material 1, add the Ludox that 781.3 grams of concentration are 40 wt% to make material 2.
By 462.4 grams of Fe (NO
3)
39H
2o adds in 70 ℃ of hot water of 150 grams, adds 302.3 grams of Bi (NO after stirring and dissolving again
3)
35H
2o, 463.0 grams of Co (NO
3)
26H
2o, 588.0 grams of Ni (NO
3)
26H
2o, 117.1 grams of concentration are the Mn (NO of 50 wt %
3)
2the aqueous solution, 410.0 grams of Ce (NO3) 36H2O and 57.7 grams of Sb
2o
3material 3 is made in stirring.
Material 3 is added in material 2 under rapid stirring, form catalyst pulp, and at 65 ℃, stir aging 2 hours, slurry mist projection granulating also obtains powder shaped catalyst precarsor (spray condition: 345 ℃ of intake air temperatures, 125 ℃ of air outlet temperature, atomizing disk rotating speed 22000rpm) after roasting in 350 ℃, 2 hours, and catalyst precarsor chemical composition is listed in table 1.Get 1000 grams of powder shaped catalyst precarsors and add Ludox and the 25 grams of (NH that 200 grams of concentration are 40wt%
4)
6mo
7o
244H
2o mediates 2 hours in kneader, and extrusion molding obtains the hollow cylindrical thing of φ 5x2x5mm, and roasting in then 500 ℃, 2 hours obtains catalyst finished product.
The evaluation method of catalyst, except reaction temperature changes, other conditions are all identical with embodiment 1, for ease of relatively, evaluation temperature and evaluation result listed in to table 2.
embodiment 12
By 1000 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 1000 grams 70 ℃, stirs it is all dissolved, and adds 3.84 grams of KNO
3and 2.64 grams of KNO
3obtain material 1, in material 1, add the aluminium colloidal sol that Ludox that 586.1 grams of concentration are 40 wt% and 439.6 grams of concentration are 20wt% to make material 2.
By 402.6 grams of Fe (NO
3)
39H
2o adds in 70 ℃ of hot water of 150 grams, adds 153.4 grams of Bi (NO after stirring and dissolving again
3)
35H
2o, 493.7 grams of Ni (NO
3)
26H
2o, 96.8 grams of Mg (NO
3)
26H
2o, 19.6 grams of La (NO
3)
33H
2o, 16.5 grams of Sm
2o
3and 55.6 grams of Sb
2o
3material 3 is made in stirring.
Material 3 is added in material 2 under rapid stirring, form catalyst pulp, and at 65 ℃, stir aging 2 hours, slurry mist projection granulating also obtains powder shaped catalyst precarsor (spray condition: 345 ℃ of intake air temperatures, 125 ℃ of air outlet temperature, atomizing disk rotating speed 22000rpm) after roasting in 350 ℃, 2 hours, and catalyst precarsor chemical composition is listed in table 1.Get 1000 grams of powder shaped catalyst precarsors and add Ludox and the 25 grams of (NH that 200 grams of concentration are 40wt%
4)
6mo
7o
244H
2o mediates 2 hours in kneader, and extrusion molding obtains the hollow cylindrical thing of φ 5x2x5mm, and roasting in then 500 ℃, 2 hours obtains catalyst finished product.
The evaluation method of catalyst, except reaction temperature changes, other conditions are all identical with embodiment 1, for ease of relatively, evaluation temperature and evaluation result listed in to table 2.
comparative example 1
Catalyst precarsor, with embodiment 1, does not add molybdenum additives in shaping of catalyst, all the other operating conditions are with embodiment 1.For ease of relatively, evaluation temperature and evaluation result are listed in to table 2.
comparative example 2
Catalyst precarsor preparation adds (NH
4)
6mo
7o
244H
2o amount is 1038.3 grams, does not add molybdenum additives in shaping of catalyst, and all the other operating conditions are with embodiment 1.For ease of relatively, evaluation temperature and evaluation result are listed in to table 2.
comparative example 3
Catalyst precarsor preparation adds (NH
4)
6mo
7o
244H
2o amount is 1019.1 grams, and the molybdenum additives adding in shaping of catalyst is (NH
4)
6mo
7o
244H
212.5 grams of O, all the other operating conditions are with embodiment 1.For ease of relatively, evaluation temperature and evaluation result are listed in to table 2.
comparative example 4
Catalyst precarsor, with embodiment 1, does not add (NH in shaping of catalyst
4)
6mo
7o
244H
2o and add 20.4 grams of molybdenum trioxides, all the other operating conditions are with embodiment 1.For ease of relatively, evaluation temperature and evaluation result are listed in to table 2.
comparative example 5
Catalyst precarsor, with embodiment 1, does not add (NH in shaping of catalyst
4)
6mo
7o
244H
2o and add 23.5 grams of ammonium tetramolybdates (molecular formula is: (NH
4)
2mo
4o
132H
2o), all the other operating conditions are with embodiment 1.For ease of relatively, evaluation temperature and evaluation result are listed in to table 2.
comparative example 6
Catalyst precarsor, with embodiment 1, does not add (NH in shaping of catalyst
4)
6mo
7o
244H
2o and add ammonium dimolybdate (molecular formula is: (NH
4)
2mo
2o
7) 24.1 grams, all the other operating conditions are with embodiment 1.For ease of relatively, evaluation temperature and evaluation result are listed in to table 2.
comparative example 7
Catalyst precarsor, with embodiment 1, does not add any molybdenum additives in shaping of catalyst, all the other operate with embodiment 1.1080 grams of the catalyst obtaining (are contained to 25 grams of (NH with 75 grams of ammonium heptamolybdate aqueous solution
4)
6mo
7o
244H
2o) mix, dry at 80 ℃.Gained catalyst strength is low, chipping in filling and course of reaction, causes reacting system pressure to raise, and cannot carry out performance evaluation.After being described, shaping of catalyst adds again (NH
4)
6mo
7o
244H
2o has any problem.
table 1, catalyst precarsor composition
| ? | Catalyst precarsor composition |
| Comparative example 1 | Mo 12Bi 1.00Fe 2.06Ni 3.26Sb 0.60Co 3.50Mn 0.90La 0.10K 0.09Cs 0.06+15%SiO 2 |
| Comparative example 2 | Mo 12.46Bi 1.00Fe 2.06Ni 3.26Sb 0.60Co 3.50Mn 0.90La 0.10K 0.09Cs 0.06+15%SiO 2 |
| Comparative example 3 | Mo 12.23Bi 1.00Fe 2.06Ni 3.26Sb 0.60Co 3.50Mn 0.90La 0.10K 0.09Cs 0.06+15%SiO 2 |
| Comparative example 4 | With comparative example 1 |
| Comparative example 5 | With comparative example 1 |
| Comparative example 6 | With comparative example 1 |
| Comparative example 7 | With comparative example 1 |
| Embodiment 1 | With comparative example 1 |
| Embodiment 2 | With comparative example 1 |
| Embodiment 3 | With comparative example 1 |
| Embodiment 4 | Mo 12Bi 0.95Fe 2.46Ni 3.38Sb 0.42Co 4.62Mn 0.42Ce 0.50K 0.12+19%SiO 2+6%Al 2O 3 |
| Embodiment 5 | Mo 12Bi 0.93Fe 2.95Ni 2.68Sb 0.63Co 3.66Sm 0.15K 0.066Rb 0.08+20%SiO 2 |
| Embodiment 6 | Mo 12Bi 1.30Fe 2.80Ni 3.36Sb 0.95 Co 2.96Mg 1.70Th 0.80Cs 0.06Rb 0.086+17%SiO 2 |
| Embodiment 7 | Mo 12Bi 1.20Fe 2.10Ni 3.00Sb 1.10Mg 2.00Ce 1.30K 0.09Cs 0.12+16%SiO 2 |
| Embodiment 8 | Mo 12Bi 0.88Fe 1.79Ni 3.62Sb 0.56Co 3.40Mn 0.60La 0.30K 0.056Cs 0.06+15%SiO 2+5%Al 2O 3 |
| Embodiment 9 | Mo 12Bi 1.15Fe 1.90Ni 3.18Sb 0.35Co 3.08Mg 0.90Mn 0.80Ce 1.30K 0.056Tl 0.12+17%SiO 2 |
| Embodiment 10 | Mo 12Bi 0.80Fe 3.30Ni 3.06Sb 0.55Mg 0.80Mn 1.50La 0.60Sm 0.30K 0.056Cs 0.06+21%SiO 2 |
| Embodiment 11 | Mo 12Bi 1.32Fe 2.40Ni 4.24Sb 0.83Co 3.37Mn 0.70Ce 2.00K 0.056Cs 0.06+17%SiO 2 |
| Embodiment 12 | Mo 12Bi 0.67Fe 2.09Ni 3.56Sb 0.80Mg 0.80La 0.10Sm 0.10Rb 0.066Cs 0.06+16%SiO 2+6%Al 2O 3 |
table 2, evaluating catalyst result
* note: catalyst breakage, fail to carry out performance evaluation.
Claims (10)
1. a preparation method for Selective Oxidation of Propylene legal system methacrylaldehyde catalyst, comprises being selected from SiO
2or Al
2o
3in at least one powder catalyst precursor that is carrier mix with binding agent and molybdenum additives, moulding, last roasting obtains described catalyst; Wherein said catalyst precarsor contains the active component by following general formula:
Mo
12Bi
aFe
bNi
cSb
dX
eY
fZ
gQ
hO
x
In formula, X is at least one being selected from Mg, Co, Ca, Be, Cu, Zn, Pb or Mn;
Y is at least one that select in Zr, Th or Ti;
Z is at least one being selected from K, Rb, Na, Li, Tl or Cs;
Q is at least one in La, Ce, Sm or Th;
The span of a is 0.05～6.0;
The span of b is 0.05～8.5;
The span of c is 0.05～11.0;
The span of d is 0.05 ~ 2.0;
The span of e is 0.2～9.0;
The span of f is 0.3～9.0;
The span of g is >0～0.5;
The span of h is 0.08～5.0;
X meets the required oxygen atom sum of other element valence;
Described molybdenum additives is made up of 50～100% ammonium heptamolybdates and 0～50% molybdenum trioxide in molar percentage;
Described powder catalyst precursor preparation process comprises the following steps:
A) ammonium molybdate of catalyst precarsor aequum and the metal nitrate that is selected from Z component are dissolved in water and obtain material 1, then carrier required Kaolinite Preparation of Catalyst precursor is added and form material 2;
B) by the Bi of catalyst precarsor aequum, Fe, Ni and be selected from x, y, z, the metal soluble salt of q class is dissolved in and in water, forms material 3;
D) under agitation, material 3 is added in material 2 and forms catalyst pulp;
E) catalyst pulp is by mist projection granulating, and roasting, obtains described powder shaped catalyst precarsor.
2. the preparation method of catalyst according to claim 1, is characterized in that the consumption of carrier in described catalyst precarsor is 5～40% of catalyst precarsor weight.
3. the preparation method of catalyst according to claim 1, is characterized in that described binding agent is selected from least one in Ludox or aluminium colloidal sol.
4. the preparation method of catalyst according to claim 1, is characterized in that described molybdenum additives is made up of 50～80% ammonium heptamolybdate and 20～50% molybdenum trioxides in molar percentage.
5. the preparation method of catalyst according to claim 1, is characterized in that described molybdenum additives counts 0.27 ~ 2.2% of catalyst precarsor weight with molybdenum element weight.
6. the preparation method of catalyst according to claim 1, is characterized in that in described step e) that sintering temperature is that 280 ~ 380 ℃, roasting time are 1 ~ 3 hour.
7. the preparation method of catalyst according to claim 1, is characterized in that catalyst final calcination temperature is that 460 ~ 530 ℃, roasting time are 1.5 ~ 2.5 hours.
8. the catalyst that in claim 1 to 7, described in any one, the preparation method of catalyst obtains.
9. the synthetic method of methacrylaldehyde, consists of methacrylaldehyde with molar ratio computing reaction raw materials: air: water vapour=10:60 ~ 80:10 ~ 30, at 350 ~ 390 ℃ of reaction temperatures, reaction pressure 0 ~ 0.05MPa, raw material volume space velocity 800 ~ 1500h
-1under condition, contact with catalyst claimed in claim 8, generate methacrylaldehyde.
10. the synthetic method of methacrylaldehyde according to claim 9, is characterized in that described reaction temperature is that 360 ~ 385 ℃, raw material volume space velocity are 900 ~ 1350h
-1.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103934000A (en) * | 2013-01-23 | 2014-07-23 | 中国石油化工股份有限公司 | Acrolein catalyst and preparation method thereof |
| CN105080558A (en) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | Catalyst for acrylic acid synthesis and preparation method thereof |
| CN105498794A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Methacrylaldehyde catalyst |
| CN106423190A (en) * | 2015-08-12 | 2017-02-22 | 中国石油化工股份有限公司 | Propylene ammoxidation catalyst for rich production of acetonitrile and hydrocyanic acid |
| CN106582696A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | High selectivity catalyst for production of acrylonitrile by propylene ammoxidation |
| CN106582695A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst used in preparation of acrylonitrile through propylene ammoxidation and capable of realizing high hydrocyanic acid yield |
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| CN101850260A (en) * | 2010-06-01 | 2010-10-06 | 上海华谊丙烯酸有限公司 | Catalyst used in preparation of (methyl) acrylic aldehyde and (methyl) acrylic acid |
| CN101992093A (en) * | 2010-09-28 | 2011-03-30 | 上海华谊丙烯酸有限公司 | Preparation method of catalyst for preparing unsaturated aldehyde and unsaturated acid in high selectivity |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101850260A (en) * | 2010-06-01 | 2010-10-06 | 上海华谊丙烯酸有限公司 | Catalyst used in preparation of (methyl) acrylic aldehyde and (methyl) acrylic acid |
| CN101992093A (en) * | 2010-09-28 | 2011-03-30 | 上海华谊丙烯酸有限公司 | Preparation method of catalyst for preparing unsaturated aldehyde and unsaturated acid in high selectivity |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103934000A (en) * | 2013-01-23 | 2014-07-23 | 中国石油化工股份有限公司 | Acrolein catalyst and preparation method thereof |
| CN105080558A (en) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | Catalyst for acrylic acid synthesis and preparation method thereof |
| CN105080558B (en) * | 2014-05-14 | 2017-10-27 | 中国石油化工股份有限公司 | Acrylic acid catalyst and preparation method thereof |
| CN105498794A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Methacrylaldehyde catalyst |
| CN106423190A (en) * | 2015-08-12 | 2017-02-22 | 中国石油化工股份有限公司 | Propylene ammoxidation catalyst for rich production of acetonitrile and hydrocyanic acid |
| CN106582696A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | High selectivity catalyst for production of acrylonitrile by propylene ammoxidation |
| CN106582695A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst used in preparation of acrylonitrile through propylene ammoxidation and capable of realizing high hydrocyanic acid yield |
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