CN103769161B - Acrylic aldehyde catalyst and preparation method thereof - Google Patents
Acrylic aldehyde catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN103769161B CN103769161B CN201210412591.4A CN201210412591A CN103769161B CN 103769161 B CN103769161 B CN 103769161B CN 201210412591 A CN201210412591 A CN 201210412591A CN 103769161 B CN103769161 B CN 103769161B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- grams
- preparation
- span
- precarsor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
Abstract
The present invention relates to acrylic aldehyde catalyst and preparation method thereof, mainly solve the problem that in prior art, catalyst long-term operation performance declines.The present invention is by including with selected from SiO2Or Al2O3In the powder catalyst precursor that at least one is carrier mix with binding agent and molybdenum additives, molding, last roasting obtains described catalyst；Wherein said molybdenum additives with molar percent by 50～100% ammonium heptamolybdate and 0～50% the technical scheme that forms of molybdenum trioxide preferably solve this technical problem, can be used in the commercial production of propylene oxidation acrolein catalyst.
Description
Technical field
The present invention relates to acrylic aldehyde catalyst and preparation method thereof.
Background technology
α, β unsaturated aldehyde is prepared in the selective oxidation of alkene and unsaturated acids is important chemical process, wherein unsaturated aldehyde
A kind of active component of production and application contain the catalyst of Mo, Bi.Improving of catalyst is mainly from the activity of catalyst with steady
Qualitative aspect is carried out, and as in active constituent, addition transition metal is to improve activity, the list increasing product is received；Add rare earth unit
Element improves redox ability；Adding the distillation with suppression Mo of the elements such as Fe, Co, Ni, stabilizing catalyst activity component, raising is urged
The service life etc. of agent.
For alkene selective oxidation a lot of patent reports:
Chinese patent ZL99106659.6 reduces organic acid, height by the strict alkynes controlled in propylene feedstocks gas and diene amount
The generation of boiling compound and tar-like substance extends catalyst service life；The used catalyst of Chinese patent ZL00118705.8
For the selective oxidation of isobutene., 4000 hours conversion ratios and yield about decline 0.5 percentage point；Chinese patent
ZL97191983.6, ZL00122609.6, ZL01111960.8 are by axially joining along reactor from reaction gas inlet to outlet
Put the catalyst layer that multiple reactivity is gradually increased to reach to control reaction focus, extend the purpose of catalyst stability.Its
The modulation of middle reactivity is by changing catalyst activity component with key component in inert carrier ratio, change catalyst such as
Bi, Fe realize with Mo ratio, catalyst calcination temperature and regulation alkali metal kind consumption etc..In prior art, propylene selects oxygen
Change acrolein catalyst exist one clearly, universal technological deficiency, i.e. Mo-Bi Containing Oxide Catalyst makes
During with, owing to molybdenum oxide is in the presence of reaction water steam, the speed of distillation is than very fast, during causing catalyst to use
Activity decrease is than very fast.The composite oxide catalysts of the type is when being used in ammoxidation of propylene reaction acrylonitrile production, the most logical
This is solved to the distillation loss supplementing fluidized bed powder catalyst molybdenum component in reactor after periodically adding molybdate compound
A difficult problem.Although acrylic aldehyde catalyst uses Mo-Bi Containing Oxide Catalyst equally, but generally uses fixed bed reactors,
Catalyst particle size is bigger, and this benefit molybdenum method can not be applicable to this reaction, the best this problem of solution
Technical scheme.The present invention is by adding molybdate compound during shaping of catalyst, it is possible to gradually discharge in course of reaction
Go out molybdenum component, reach to supplement the effect of catalyst molybdenum component distillation loss, improve catalyst and use the cycle.
Summary of the invention
One of the technical problem to be solved is used catalyst long period fortune in existing acrylic aldehyde preparation method
The problem that the propylene conversion of row existence and acrylic aldehyde yield decline, it is provided that the preparation method of a kind of new acrylic aldehyde catalyst,
Catalyst prepared by the method has the advantage and catalyst stability that propylene conversion is high, acrylic aldehyde yield is high, selectivity is good
Good advantage.
The two of the technical problem to be solved in the present invention are to provide a kind of by the preparation method one of above-mentioned technical problem Suo Shu
The catalyst obtained.
The three of the technical problem to be solved in the present invention are the acrylic aldehyde of the catalyst described in two using above-mentioned technical problem
Synthetic method.
For solving one of above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of Selective Oxidation of Propylene legal system
The preparation method of acrylic aldehyde catalyst, including by selected from SiO2Or Al2O3In the powder catalyst that at least one is carrier before
Body mixes with binding agent and molybdenum additives, molding, last roasting (wherein roasting condition is not the key of the present invention, but optimum
Roasting condition be: sintering temperature is 460 ~ 530 DEG C, and roasting time is 1.5 ~ 2.5 hours) obtain described catalyst；Wherein institute
The catalyst precarsor stated contains by the active component of following general formula:
Mo12BiaFebNicSbdXeYfZgQhOx
In formula, X is at least one in Mg, Co, Ca, Be, Cu, Zn, Pb or Mn；
Y is to select at least one in Zr, Th or Ti；
Z is at least one in 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 is to meet the oxygen atom sum needed for other element valence；
Described molybdenum additives with molar percent by 50～100% ammonium heptamolybdate and 0～50% molybdenum trioxide form；
Before described powder catalyst, production procedure comprises the following steps:
A) metal nitrate by the desired amount of for catalyst precarsor ammonium molybdate with selected from Z component is dissolved in water to obtain material 1,
It can be appointing in ammonium dimolybdate, ammonium tetramolybdate, ammonium heptamolybdate or ammonium octamolybdate that wherein said ammonium molybdate is not particularly limited it
What is a kind of or by any two or the two or more compositions formed, and then will prepare the carrier needed for catalyst precarsor and add shape
Become material 2；
B) by the desired amount of for catalyst precarsor Bi, Fe, Ni and selected from x, the metal soluble salt of y, z, q class is dissolved in water shape
Become material 3；
D) under agitation, material 3 is added formation catalyst pulp in material 2；
E) by mist projection granulating, (wherein mist projection granulating condition is not the key of the present invention to catalyst pulp, but suitable spray
Mist granulation conditions be intake air temperature 330 ~ 350 DEG C, air outlet temperature 120 ~ 135 DEG C, atomizing disk rotating speed 20000 ~
25000rpm), roasting, obtain described powder shaped catalyst precarsor.
In technique scheme, in described catalyst precarsor the consumption of carrier be preferably catalyst precarsor weight 5～
40%；Described binding agent preferably is selected from least one in Ludox or Alumina gel；Described molybdenum additives is preferred with molar percent
Ammonium heptamolybdate and 20 ~ 50% molybdenum trioxides by 50 ~ 80% form；Described molybdenum additives is preferably catalyst in terms of molybdenum element weight
The 0.27 ~ 2.2% of front body weight；In described step e), sintering temperature is preferably 280 ~ 380 DEG C, that roasting time is preferably 1 ~ 3 is little
Time.
For solving the two of above-mentioned technical problem, the technical solution used in the present invention is as follows: one of above-mentioned technical problem is described
The catalyst that technical scheme obtains.
For solving the three of above-mentioned technical problem, the technical solution used in the present invention is as follows: the synthetic method of acrylic aldehyde, to rub
You consist of acrylic aldehyde than meter reaction raw materials: air: water vapour=10:60 ~ 80:10 ~ 30, in reaction temperature 350 ~ 390 DEG C, anti-
Answer pressure 0 ~ 0.05MPa, raw material volume air speed 800 ~ 1500h-1Under the conditions of, connect with the catalyst described in the two of above-mentioned technical problem
Touch, generate acrylic aldehyde.
In technique scheme, described reaction temperature be preferably 360 ~ 385 DEG C, raw material volume air speed be preferably 900 ~
1350h-1。
Due to the fact that during shaping of catalyst, add described molybdenum additives, owing to molybdenum component can react
Journey is supplemented the sublimation of respective components in catalytic component, delays catalyst hydraulic performance decline during life-time service, with
Time this feed postition will not change catalyst (precursor) chemical composition itself, catalyst activity phase composition and chemical constitution, energy
Achievement that in laboratory research catalytic component optimize enough is better achieved.
Catalyst in the present invention prepares acrylic aldehyde for Selective Oxidation of Propylene, propylene: air: steam molar ratio is
10:60 ~ 80:10 ~ 30, reaction temperature 350 ~ 390 DEG C, reaction pressure 0 ~ 0.05MPa, raw material volume air speed 800 ~ 1500h-1Condition
Under, its propylene conversion is up to 99.1%, product propylene aldehyde yield is up to 79.6%, and is running 3000 hours continuously
After, catalyst propylene conversion and acrylic aldehyde yield are not decreased obviously, and achieve preferable technique effect.
Below by embodiment, the present invention is further elaborated:
Detailed description of the invention
Embodiment 1
By 1000 grams of (NH4)6Mo7O24·4H2O(i.e. ammonium heptamolybdate) join in the warm water of 1000 grams 70 DEG C, stirring makes
It all dissolves, and adds 2.88 grams of KNO3And 5.49 grams of CsNO3Obtain material 1, in material 1,573.9 grams of concentration of addition are 40
Material 2 made by the Ludox of wt%.
By 396.9 grams of Fe (NO3)3·9H2O adds in 70 DEG C of hot water of 150 grams, adds 229.0 grams of Bi after stirring and dissolving
(NO3)3·5H2O, 480.8 grams of Co (NO3)2·6H2O, 452.1 grams of Ni (NO3)2·6H2O, 150.5 grams of concentration are the Mn of 50wt %
(NO3)2Aqueous solution, 19.6 grams of La (NO3)3·3H2O and 41.7 grams of Sb2O3Material 3 is made in stirring.
Material 3 is added in material 2 under fast stirring, forms catalyst pulp, and stir aging 2 little at 65 DEG C
Time, slurry mist projection granulating and in 350 DEG C, obtain powder shaped catalyst precarsor (spray condition: intake air temperature after roasting in 2 hours
345 DEG C, air outlet temperature 125 DEG C, atomizing disk rotating speed 22000rpm), catalyst precarsor chemical composition is listed in table 1.Take powder shaped
Catalyst precarsor 1000 grams adds the Ludox and 25 grams of (NH that 200 grams of concentration are 40wt%4)6Mo7O24·4H2O is in kneader
Mediating 2 hours, extrusion molding obtains the hollow cylindrical thing of φ 5x2x5mm, then 500 DEG C, roasting in 2 hours obtain catalyst
Product.
The investigation appreciation condition of catalyst is as follows:
Reactor: fixed bed single tube reactor, internal diameter 25.4 millimeters, reactor length 3000 millimeters
Catalyst: 600 grams
Reaction temperature: 375 DEG C
Reaction pressure: 0.01MPa
Response time: 3000 hours
Material molar ratio: propylene: air: water vapour=10:73:17
Raw material volume air speed: 1200 hours-1
Product use gas chromatographic analysis, and calculate Carbon balance, it is significant figure when Carbon balance is at (95～105) %
According to.
Propylene conversion, product yield and be optionally defined as:
Evaluating catalyst result is listed in table 2.
Embodiment 2
By 1000 grams of (NH4)6Mo7O24·4H2O joins in the warm water of 1000 grams 70 DEG C, and stirring makes it all dissolve, and adds
Enter 2.88 grams of KNO3And 5.49 grams of CsNO3Obtain material 1, in material 1,573.9 grams of concentration of addition are the Ludox of 40 wt%
Make material 2.
By 396.9 grams of Fe (NO3)3·9H2O adds in 70 DEG C of hot water of 150 grams, adds 229.0 grams of Bi after stirring and dissolving
(NO3)3·5H2O, 480.8 grams of Co (NO3)2·6H2O, 452.1 grams of Ni (NO3)2·6H2O, 150.5 grams of concentration are the Mn of 50wt %
(NO3)2Aqueous solution, 19.6 grams of La (NO3)3·3H2O and 41.7 grams of Sb2O3Material 3 is made in stirring.
Material 3 is added in material 2 under fast stirring, forms catalyst pulp, and stir aging 2 little at 65 DEG C
Time, slurry mist projection granulating and in 350 DEG C, obtain powder shaped catalyst precarsor (spray condition: intake air temperature after roasting in 2 hours
345 DEG C, air outlet temperature 125 DEG C, atomizing disk rotating speed 22000rpm), catalyst precarsor chemical composition is listed in table 1.Take powder shaped
Catalyst precarsor 1000 grams adds the Ludox and 20 grams of (NH that 200 grams of concentration are 40wt%4)6Mo7O24·4H2O and 4.1 gram of three oxygen
Changing molybdenum to mediate in kneader 2 hours, extrusion molding obtains the hollow cylindrical thing of φ 5x2x5mm, then 500 DEG C, roasting in 2 hours
Burning obtains finished catalyst.
The evaluation methodology of catalyst, in addition to reaction temperature changes, other conditions are the most same as in Example 1, for ease of than
Relatively, evaluation temperature and evaluation result are listed in table 2.
Embodiment 3
By 1000 grams of (NH4)6Mo7O24·4H2O joins in the warm water of 1000 grams 70 DEG C, and stirring makes it all dissolve, and adds
Enter 2.88 grams of KNO3And 5.49 grams of CsNO3Obtain material 1, in material 1,573.9 grams of concentration of addition are the Ludox of 40 wt%
Make material 2.
By 396.9 grams of Fe (NO3)3·9H2O adds in 70 DEG C of hot water of 150 grams, adds 229.0 grams of Bi after stirring and dissolving
(NO3)3·5H2O, 480.8 grams of Co (NO3)2·6H2O, 452.1 grams of Ni (NO3)2·6H2O, 150.5 grams of concentration are the Mn of 50wt %
(NO3)2Aqueous solution, 19.6 grams of La (NO3)3·3H2O and 41.7 grams of Sb2O3Material 3 is made in stirring.
Material 3 is added in material 2 under fast stirring, forms catalyst pulp, and stir aging 2 little at 65 DEG C
Time, slurry mist projection granulating and in 350 DEG C, obtain powder shaped catalyst precarsor (spray condition: intake air temperature after roasting in 2 hours
345 DEG C, air outlet temperature 125 DEG C, atomizing disk rotating speed 22000rpm), catalyst precarsor chemical composition is listed in table 1.Take powder shaped
Catalyst precarsor 1000 grams adds the Ludox and 12.5 grams of (NH that 200 grams of concentration are 40wt%4)6Mo7O24·4H2O and 10.2 grams
Molybdenum trioxide is mediated 2 hours in kneader, and extrusion molding obtains the hollow cylindrical thing of φ 5x2x5mm, then 500 DEG C, 2 little
Time roasting obtain finished catalyst.
The evaluation methodology of catalyst, in addition to reaction temperature changes, other conditions are the most same as in Example 1, for ease of than
Relatively, evaluation temperature and evaluation result are listed in table 2.
Embodiment 4
By 1000 grams of (NH4)6Mo7O24·4H2O joins in the warm water of 1000 grams 70 DEG C, and stirring makes it all dissolve, and adds
Enter 3.84 grams of KNO3Obtain material 1, in material 1, add Ludox that 860 grams of concentration are 40 wt% and 543.2 grams of concentration are
The Alumina gel of 20 wt % makes material 2.
By 473.9 grams of Fe (NO3)3·9H2O adds in 70 DEG C of hot water of 150 grams, adds 217.5 grams of Bi after stirring and dissolving
(NO3)3·5H2O, 634.7 grams of Co (NO3)2·6H2O, 468.7 grams of Ni (NO3)2·6H2O, 70.2 grams of concentration are the Mn of 50wt%
(NO3)2Aqueous solution, 102.5 grams of Ce (NO3)3·6H2O and 29.2 grams of Sb2O3Material 3 is made in stirring.
Material 3 is added in material 2 under fast stirring, forms catalyst pulp, and stir aging 2 little at 65 DEG C
Time, slurry mist projection granulating and in 350 DEG C, obtain powder shaped catalyst precarsor (spray condition: intake air temperature after roasting in 2 hours
345 DEG C, air outlet temperature 125 DEG C, atomizing disk rotating speed 22000rpm), catalyst precarsor chemical composition is listed in table 1.Take powder shaped
Catalyst precarsor 1000 grams adds the Ludox and 25 grams of (NH that 200 grams of concentration are 40wt%4)6Mo7O24·4H2O is in kneader
Mediating 2 hours, extrusion molding obtains the hollow cylindrical thing of φ 5x2x5mm, then 500 DEG C, roasting in 2 hours obtain catalyst
Product.
The evaluation methodology of catalyst, in addition to reaction temperature changes, other conditions are the most same as in Example 1, for ease of than
Relatively, evaluation temperature and evaluation result are listed in table 2.
Embodiment 5
By 1000 grams of (NH4)6Mo7O24·4H2O joins in the warm water of 1000 grams 70 DEG C, and stirring makes it all dissolve, and adds
Enter 2.11 grams of KNO3And 5.54 grams of RbNO3Obtain material 1, in material 1,800.3 grams of concentration of addition are the Ludox of 40 wt%
Make material 2.
By 568.3 grams of Fe (NO3)3·9H2O adds in 70 DEG C of hot water of 150 grams, adds 213.0 grams of Bi after stirring and dissolving
(NO3)3·5H2O, 502.8 grams of Co (NO3)2·6H2O, 371.7 grams of Ni (NO3)2·6H2O, 24.7 grams of Sm2O3And 43.8 grams of Sb2O3
Material 3 is made in stirring.
Material 3 is added in material 2 under fast stirring, forms catalyst pulp, and stir aging 2 little at 65 DEG C
Time, slurry mist projection granulating and in 350 DEG C, obtain powder shaped catalyst precarsor (spray condition: intake air temperature after roasting in 2 hours
345 DEG C, air outlet temperature 125 DEG C, atomizing disk rotating speed 22000rpm), catalyst precarsor chemical composition is listed in table 1.Take powder shaped
Catalyst precarsor 1000 grams adds the Ludox and 25 grams of (NH that 200 grams of concentration are 40wt%4)6Mo7O24·4H2O is in kneader
Mediating 2 hours, extrusion molding obtains the hollow cylindrical thing of φ 5x2x5mm, then 500 DEG C, roasting in 2 hours obtain catalyst
Product.
The evaluation methodology of catalyst, in addition to reaction temperature changes, other conditions are the most same as in Example 1, for ease of than
Relatively, evaluation temperature and evaluation result are listed in table 2.
Embodiment 6
By 1000 grams of (NH4)6Mo7O24·4H2O joins in the warm water of 1000 grams 70 DEG C, and stirring makes it all dissolve, and adds
Enter 5.96 grams of RbNO3And 5.49 grams of CsNO3Obtain material 1, in material 1,872.6 grams of concentration of addition are the Ludox of 40 wt%
Make material 2.
By 539.4 grams of Fe (NO3)3·9H2O adds in 70 DEG C of hot water of 150 grams, adds 297.7 grams of Bi after stirring and dissolving
(NO3)3·5H2O, 406.7 grams of Co (NO3)2·6H2O, 466.0 grams of Ni (NO3)2·6H2O, 205.8 grams of Mg (NO3)2·6H2O、
99.2 grams of Th (NO3)4·4H2O and 66.0 grams of Sb2O3Material 3 is made in stirring.
Material 3 is added in material 2 under fast stirring, forms catalyst pulp, and stir aging 2 little at 65 DEG C
Time, slurry mist projection granulating and in 350 DEG C, obtain powder shaped catalyst precarsor (spray condition: intake air temperature after roasting in 2 hours
345 DEG C, air outlet temperature 125 DEG C, atomizing disk rotating speed 22000rpm), catalyst precarsor chemical composition is listed in table 1.Take powder shaped
Catalyst precarsor 1000 grams adds the Ludox and 25 grams of (NH that 200 grams of concentration are 40wt%4)6Mo7O24·4H2O is in kneader
Mediating 2 hours, extrusion molding obtains the hollow cylindrical thing of φ 5x2x5mm, then 500 DEG C, roasting in 2 hours obtain catalyst
Product.
The evaluation methodology of catalyst, in addition to reaction temperature changes, other conditions are the most same as in Example 1, for ease of than
Relatively, evaluation temperature and evaluation result are listed in table 2.
Embodiment 7
By 1000 grams of (NH4)6Mo7O24·4H2O joins in the warm water of 1000 grams 70 DEG C, and stirring makes it all dissolve, and adds
Enter 2.88 grams of KNO3And 11.0 grams of RbNO3Obtain material 1, in material 1,645.9 grams of concentration of addition are the Ludox system of 40wt%
Become material 2.
By 404.6 grams of Fe (NO3)3·9H2O adds in 70 DEG C of hot water of 150 grams, adds 274.8 grams of Bi after stirring and dissolving
(NO3)3·5H2O, 416.0 grams of Ni (NO3)2·6H2O, 242.1 grams of Mg (NO3)2·6H2O, 266.5 grams of Ce (NO3)3·6H2O and
76.5 gram Sb2O3Material 3 is made in stirring.
Material 3 is added in material 2 under fast stirring, forms catalyst pulp, and stir aging 2 little at 65 DEG C
Time, slurry mist projection granulating and in 350 DEG C, obtain powder shaped catalyst precarsor (spray condition: intake air temperature after roasting in 2 hours
345 DEG C, air outlet temperature 125 DEG C, atomizing disk rotating speed 22000rpm), catalyst precarsor chemical composition is listed in table 1.Take powder shaped
Catalyst precarsor 1000 grams adds the Ludox and 25 grams of (NH that 200 grams of concentration are 40wt%4)6Mo7O24·4H2O is in kneader
Mediating 2 hours, extrusion molding obtains the hollow cylindrical thing of φ 5x2x5mm, then 500 DEG C, roasting in 2 hours obtain catalyst
Product.
The evaluation methodology of catalyst, in addition to reaction temperature changes, other conditions are the most same as in Example 1, for ease of than
Relatively, evaluation temperature and evaluation result are listed in table 2.
Embodiment 8
By 1000 grams of (NH4)6Mo7O24·4H2O joins in the warm water of 1000 grams 70 DEG C, and stirring makes it all dissolve, and adds
Enter 1.79 grams of KNO3And 5.49 grams of CsNO3Obtain material 1, add in material 1 Ludox that 602.3 grams of concentration are 40wt% and
401.5 grams of concentration is that the Alumina gel of 20wt% makes material 2.
By 344.9 grams of Fe (NO3)3·9H2O adds in 70 DEG C of hot water of 150 grams, adds 201.5 grams of Bi after stirring and dissolving
(NO3)3·5H2O, 467.1 grams of Co (NO3)2·6H2O, 502.0 grams of Ni (NO3)2·6H2O, 100.3 grams of concentration are the Mn of 50wt%
(NO3)2Aqueous solution, 58.8 grams of La (NO3)3·3H2O and 38.9 grams of Sb2O3Material 3 is made in stirring.
Material 3 is added in material 2 under fast stirring, forms catalyst pulp, and stir aging 2 little at 65 DEG C
Time, slurry mist projection granulating and in 350 DEG C, obtain powder shaped catalyst precarsor (spray condition: intake air temperature after roasting in 2 hours
345 DEG C, air outlet temperature 125 DEG C, atomizing disk rotating speed 22000rpm), catalyst precarsor chemical composition is listed in table 1.Take powder shaped
Catalyst precarsor 1000 grams adds the Ludox and 25 grams of (NH that 200 grams of concentration are 40wt%4)6Mo7O24·4H2O is in kneader
Mediating 2 hours, extrusion molding obtains the hollow cylindrical thing of φ 5x2x5mm, then 500 DEG C, roasting in 2 hours obtain catalyst
Product.
The evaluation methodology of catalyst, in addition to reaction temperature changes, other conditions are the most same as in Example 1, for ease of than
Relatively, evaluation temperature and evaluation result are listed in table 2.
Embodiment 9
By 1000 grams of (NH4)6Mo7O24·4H2O joins in the warm water of 1000 grams 70 DEG C, and stirring makes it all dissolve, and adds
Enter 1.79 grams of KNO3And 15.1 grams of TlNO3Obtain material 1, in material 1,781.7 grams of concentration of addition are the Ludox of 40 wt%
Make material 2.
By 366.0 grams of Fe (NO3)3·9H2O adds in 70 DEG C of hot water of 150 grams, adds 263.3 grams of Bi after stirring and dissolving
(NO3)3·5H2O, 423.1 grams of Co (NO3)2·6H2O, 441.0 grams of Ni (NO3)2·6H2O, 133.8 grams of concentration are 50 wt %
Mn(NO3)2Aqueous solution, 108.9 grams of Mg (NO3)2·6H2O and 24.3 grams of Sb2O3Material 3 is made in stirring.
Material 3 is added in material 2 under fast stirring, forms catalyst pulp, and stir aging 2 little at 65 DEG C
Time, slurry mist projection granulating and in 350 DEG C, obtain powder shaped catalyst precarsor (spray condition: intake air temperature after roasting in 2 hours
345 DEG C, air outlet temperature 125 DEG C, atomizing disk rotating speed 22000rpm), catalyst precarsor chemical composition is listed in table 1.Take powder shaped
Catalyst precarsor 1000 grams adds the Ludox and 25 grams of (NH that 200 grams of concentration are 40wt%4)6Mo7O24·4H2O is in kneader
Mediating 2 hours, extrusion molding obtains the hollow cylindrical thing of φ 5x2x5mm, then 500 DEG C, roasting in 2 hours obtain catalyst
Product.
The evaluation methodology of catalyst, in addition to reaction temperature changes, other conditions are the most same as in Example 1, for ease of than
Relatively, evaluation temperature and evaluation result are listed in table 2.
Embodiment 10
By 1000 grams of (NH4)6Mo7O24·4H2O joins in the warm water of 1000 grams 70 DEG C, and stirring makes it all dissolve, and adds
Enter 1.79 grams of KNO3And 5.49 grams of CsNO3Obtain material 1, in material 1,858.9 grams of concentration of addition are the Ludox of 40 wt%
Make material 2.
By 635.8 grams of Fe (NO3)3·9H2O adds in 70 DEG C of hot water of 150 grams, adds 183.2 grams of Bi after stirring and dissolving
(NO3)3·5H2O, 424.3 grams of Ni (NO3)2·6H2O, 96.8 grams of Mg (NO3)2·6H2O, 250.9 grams of concentration are the Mn of 50 wt %
(NO3)2Aqueous solution, 117.5 grams of La (NO3)3·3H2O, 49.4 grams of Sm2O3And 38.2 grams of Sb2O3Material 3 is made in stirring.
Material 3 is added in material 2 under fast stirring, forms catalyst pulp, and stir aging 2 little at 65 DEG C
Time, slurry mist projection granulating and in 350 DEG C, obtain powder shaped catalyst precarsor (spray condition: intake air temperature after roasting in 2 hours
345 DEG C, air outlet temperature 125 DEG C, atomizing disk rotating speed 22000rpm), catalyst precarsor chemical composition is listed in table 1.Take powder shaped
Catalyst precarsor 1000 grams adds the Ludox and 25 grams of (NH that 200 grams of concentration are 40wt%4)6Mo7O24·4H2O is in kneader
Mediating 2 hours, extrusion molding obtains the hollow cylindrical thing of φ 5x2x5mm, then 500 DEG C, roasting in 2 hours obtain catalyst
Product.
The evaluation methodology of catalyst, in addition to reaction temperature changes, other conditions are the most same as in Example 1, for ease of than
Relatively, evaluation temperature and evaluation result are listed in table 2.
Embodiment 11
By 1000 grams of (NH4)6Mo7O24·4H2O joins in the warm water of 1000 grams 70 DEG C, and stirring makes it all dissolve, and adds
Enter 1.79 grams of KNO3And 5.49 grams of CsNO3Obtain material 1, in material 1,781.3 grams of concentration of addition are the Ludox of 40 wt%
Make material 2.
By 462.4 grams of Fe (NO3)3·9H2O adds in 70 DEG C of hot water of 150 grams, adds 302.3 grams of Bi after stirring and dissolving
(NO3)3·5H2O, 463.0 grams of Co (NO3)2·6H2O, 588.0 grams of Ni (NO3)2·6H2O, 117.1 grams of concentration are 50 wt %
Mn(NO3)2Aqueous solution, 410.0 grams of Ce (NO3) 3 6H2O and 57.7 grams of Sb2O3Material 3 is made in stirring.
Material 3 is added in material 2 under fast stirring, forms catalyst pulp, and stir aging 2 little at 65 DEG C
Time, slurry mist projection granulating and in 350 DEG C, obtain powder shaped catalyst precarsor (spray condition: intake air temperature after roasting in 2 hours
345 DEG C, air outlet temperature 125 DEG C, atomizing disk rotating speed 22000rpm), catalyst precarsor chemical composition is listed in table 1.Take powder shaped
Catalyst precarsor 1000 grams adds the Ludox and 25 grams of (NH that 200 grams of concentration are 40wt%4)6Mo7O24·4H2O is in kneader
Mediating 2 hours, extrusion molding obtains the hollow cylindrical thing of φ 5x2x5mm, then 500 DEG C, roasting in 2 hours obtain catalyst
Product.
The evaluation methodology of catalyst, in addition to reaction temperature changes, other conditions are the most same as in Example 1, for ease of than
Relatively, evaluation temperature and evaluation result are listed in table 2.
Embodiment 12
By 1000 grams of (NH4)6Mo7O24·4H2O joins in the warm water of 1000 grams 70 DEG C, and stirring makes it all dissolve, and adds
Enter 3.84 grams of KNO3And 2.64 grams of KNO3Obtain material 1, add in material 1 Ludox that 586.1 grams of concentration are 40 wt% and
439.6 grams of concentration is that the Alumina gel of 20wt% makes material 2.
By 402.6 grams of Fe (NO3)3·9H2O adds in 70 DEG C of hot water of 150 grams, adds 153.4 grams of Bi after stirring and dissolving
(NO3)3·5H2O, 493.7 grams of Ni (NO3)2·6H2O, 96.8 grams of Mg (NO3)2·6H2O, 19.6 grams of La (NO3)3·3H2O、16.5
Gram Sm2O3And 55.6 grams of Sb2O3Material 3 is made in stirring.
Material 3 is added in material 2 under fast stirring, forms catalyst pulp, and stir aging 2 little at 65 DEG C
Time, slurry mist projection granulating and in 350 DEG C, obtain powder shaped catalyst precarsor (spray condition: intake air temperature after roasting in 2 hours
345 DEG C, air outlet temperature 125 DEG C, atomizing disk rotating speed 22000rpm), catalyst precarsor chemical composition is listed in table 1.Take powder shaped
Catalyst precarsor 1000 grams adds the Ludox and 25 grams of (NH that 200 grams of concentration are 40wt%4)6Mo7O24·4H2O is in kneader
Mediating 2 hours, extrusion molding obtains the hollow cylindrical thing of φ 5x2x5mm, then 500 DEG C, roasting in 2 hours obtain catalyst
Product.
The evaluation methodology of catalyst, in addition to reaction temperature changes, other conditions are the most same as in Example 1, for ease of than
Relatively, evaluation temperature and evaluation result are listed in table 2.
Comparative example 1
Catalyst precarsor, with embodiment 1, is added without molybdenum additives in shaping of catalyst, remaining operating condition is with embodiment 1.
For ease of comparing, evaluation temperature and evaluation result are listed in table 2.
Comparative example 2
Catalyst precarsor preparation adds (NH4)6Mo7O24·4H2O amount is 1038.3 grams, is added without molybdenum and adds in shaping of catalyst
Adding agent, remaining operating condition is with embodiment 1.For ease of comparing, evaluation temperature and evaluation result are listed in table 2.
Comparative example 3
Catalyst precarsor preparation adds (NH4)6Mo7O24·4H2O amount is 1019.1 grams, and the molybdenum added in shaping of catalyst adds
Add agent for (NH4)6Mo7O24·4H2O 12.5 grams, remaining operating condition is with embodiment 1.For ease of comparing, by evaluation temperature and commenting
Valency result is listed in table 2.
Comparative example 4
Catalyst precarsor, with embodiment 1, is added without (NH in shaping of catalyst4)6Mo7O24·4H2O and add molybdenum trioxide
20.4 grams, remaining operating condition is with embodiment 1.For ease of comparing, evaluation temperature and evaluation result are listed in table 2.
Comparative example 5
Catalyst precarsor, with embodiment 1, is added without (NH in shaping of catalyst4)6Mo7O24·4H2O and add 23.5 gram four
(molecular formula is ammonium molybdate: (NH4)2Mo4O13·2H2O), remaining operating condition is with embodiment 1.For ease of comparing, by evaluation temperature
It is listed in table 2 with evaluation result.
Comparative example 6
Catalyst precarsor, with embodiment 1, is added without (NH in shaping of catalyst4)6Mo7O24·4H2O and add ammonium dimolybdate
(molecular formula is: (NH4)2·Mo2O7) 24.1 grams, remaining operating condition is with embodiment 1.For ease of comparing, by evaluation temperature and commenting
Valency result is listed in table 2.
Comparative example 7
Catalyst precarsor, with embodiment 1, is not added with any molybdenum additives in shaping of catalyst, remaining operation is with embodiment 1.Will
The catalyst obtained 1080 grams and 75 grams of ammonium heptamolybdate aqueous solutions are (containing 25 grams of (NH4)6Mo7O24·4H2O) mixing, does at 80 DEG C
Dry.Gained catalyst strength is low, chipping in filling and course of reaction, causes reacting system pressure to raise, it is impossible to Progressive symmetric erythrokeratodermia
Can evaluate.(NH is added after shaping of catalyst is described4)6Mo7O24·4H2O has any problem.
Table 1, catalyst precarsor form
| Catalyst precarsor forms | |
| Comparative example 1 | Mo12Bi1.00Fe2.06Ni3.26Sb0.60Co3.50Mn0.90La0.10K0.09Cs0.06+15%SiO2 |
| Comparative example 2 | Mo12.46Bi1.00Fe2.06Ni3.26Sb0.60Co3.50Mn0.90La0.10K0.09Cs0.06+15%SiO2 |
| Comparative example 3 | Mo12.23Bi1.00Fe2.06Ni3.26Sb0.60Co3.50Mn0.90La0.10K0.09Cs0.06+15%SiO2 |
| 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 | Mo12Bi0.95Fe2.46Ni3.38Sb0.42Co4.62Mn0.42Ce0.50K0.12+19%SiO2+6%Al2O3 |
| Embodiment 5 | Mo12Bi0.93Fe2.95Ni2.68Sb0.63Co3.66Sm0.15K0.066Rb0.08+20%SiO2 |
| Embodiment 6 | Mo12Bi1.30Fe2.80Ni3.36Sb0.95Co2.96Mg1.70Th0.80Cs0.06Rb0.086+17%SiO2 |
| Embodiment 7 | Mo12Bi1.20Fe2.10Ni3.00Sb1.10Mg2.00Ce1.30K0.09Cs0.12+16%SiO2 |
| Embodiment 8 | Mo12Bi0.88Fe1.79Ni3.62Sb0.56Co3.40Mn0.60La0.30K0.056Cs0.06+15%SiO2+5%Al2O3 |
| Embodiment 9 | Mo12Bi1.15Fe1.90Ni3.18Sb0.35Co3.08Mg0.90Mn0.80Ce1.30K0.056Tl0.12+17%SiO2 |
| Embodiment 10 | Mo12Bi0.80Fe3.30Ni3.06Sb0.55Mg0.80Mn1.50La0.60Sm0.30K0.056Cs0.06+21%SiO2 |
| Embodiment 11 | Mo12Bi1.32Fe2.40Ni4.24Sb0.83Co3.37Mn0.70Ce2.00K0.056Cs0.06+17%SiO2 |
| Embodiment 12 | Mo12Bi0.67Fe2.09Ni3.56Sb0.80Mg0.80La0.10Sm0.10Rb0.066Cs0.06+16%SiO2+6%Al2O3 |
Table 2, evaluating catalyst result
* note: catalyst breakage, fails to carry out performance evaluation.
Claims (10)
1. a preparation method for Selective Oxidation of Propylene legal system acrylic aldehyde catalyst, including with selected from SiO2Or Al2O3In at least
A kind of powder catalyst precursor for carrier mixes with binding agent and molybdenum additives, molding, and last roasting obtains described catalysis
Agent；Wherein said catalyst precarsor contains by the active component of following general formula:
Mo12BiaFebNicSbdXeYfZgQhOx
In formula, X is at least one in Mg, Co, Ca, Be, Cu, Zn, Pb or Mn；
Y is to select at least one in Zr, Th or Ti；
Z is at least one in 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 is to meet the oxygen atom sum needed for other element valence；
Described molybdenum additives with molar percent by more than or equal to 50% to the ammonium heptamolybdate less than 100% and more than 0% to
Molybdenum trioxide composition less than or equal to 50%；
Before described powder catalyst, production procedure comprises the following steps:
A) metal nitrate by the desired amount of for catalyst precarsor ammonium molybdate with selected from Z component is dissolved in water to obtain material 1, then
Formation material 2 is added by preparing the carrier needed for catalyst precarsor；
B) by the desired amount of for catalyst precarsor Bi, Fe, Ni, Sb2O3And the metal soluble salt being selected from X, Y, Z, Q class is dissolved in water
Form material 3；
D) under agitation, material 3 is added formation catalyst pulp in material 2；
E) catalyst pulp passes through mist projection granulating, roasting, obtains described powder catalyst precursor.
The preparation method of catalyst the most according to claim 1, is characterized in that the use of carrier in described catalyst precarsor
Amount is the 5～40% of catalyst precarsor weight.
The preparation method of catalyst the most according to claim 1, is characterized in that described binding agent is molten selected from Ludox or aluminum
At least one in glue.
The preparation method of catalyst the most according to claim 1, is characterized in that described molybdenum additives is with molar percent
By 50～the ammonium heptamolybdate of 80% and 20～50% molybdenum trioxide form.
The preparation method of catalyst the most according to claim 1, is characterized in that described molybdenum additives is in terms of molybdenum element weight
For catalyst precarsor weight 0.27～2.2%.
The preparation method of catalyst the most according to claim 1, it is characterized in that in described step e) sintering temperature be 280～
380 DEG C, roasting time be 1～3 hour.
The preparation method of catalyst the most according to claim 1, it is characterized in that the last sintering temperature of catalyst be 460～
530 DEG C, roasting time be 1.5～2.5 hours.
8. the catalyst that the preparation method of catalyst according to any one of claim 1 to 7 obtains.
9. the synthetic method of acrylic aldehyde, consists of acrylic aldehyde with molar ratio computing reaction raw materials: air: water vapour=10:60～80:
10～30, in reaction temperature 350～390 DEG C, reaction pressure 0～0.05MPa, raw material volume air speed 800～1500h-1Under the conditions of,
Contact with the catalyst described in claim 8, generate acrylic aldehyde.
The synthetic method of acrylic aldehyde the most according to claim 9, it is characterized in that described reaction temperature be 360～385 DEG C,
Raw material volume air speed is 900～1350h-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210412591.4A CN103769161B (en) | 2012-10-25 | 2012-10-25 | Acrylic aldehyde catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210412591.4A CN103769161B (en) | 2012-10-25 | 2012-10-25 | Acrylic aldehyde catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103769161A CN103769161A (en) | 2014-05-07 |
| CN103769161B true CN103769161B (en) | 2016-08-24 |
Family
ID=50562195
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210412591.4A Active CN103769161B (en) | 2012-10-25 | 2012-10-25 | Acrylic aldehyde catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103769161B (en) |
Families Citing this family (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 |
| 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 |
| 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 |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2012
- 2012-10-25 CN CN201210412591.4A patent/CN103769161B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103769161A (en) | 2014-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103769161B (en) | Acrylic aldehyde catalyst and preparation method thereof | |
| CN103934000A (en) | Acrolein catalyst and preparation method thereof | |
| JP5919870B2 (en) | Method for producing acrylonitrile production catalyst and method for producing acrylonitrile using the acrylonitrile production catalyst | |
| CN100364665C (en) | Process for producing composite oxide catalyst | |
| CN103736498B (en) | Propylene oxidation catalyst, preparation method and its usage | |
| CN104302391A (en) | Catalyst for use in production of methacrylic acid, method for producing said catalyst, and method for producing methacrylic acid using said catalyst | |
| CN103418402A (en) | Catalyst for preparing acrylic acid by acrolein oxidation and preparation method thereof | |
| CN105392761A (en) | Method For Manufacturing Unsaturated Aldehyde And/Or Unsaturated Carboxylic Acid | |
| CN101147869A (en) | Catalyst for preparing acrylonitrile by ammonia oxidizing method | |
| JP6049156B2 (en) | Oxidation catalyst for production of butadiene and method for producing the same | |
| CN104646016B (en) | Unsaturated aldehyde oxidation catalyst and preparation method thereof | |
| CN103739467B (en) | Propylene oxidation prepares propenal method | |
| CN109569638A (en) | Low-temperature alkyl arene dehydrogenating catalyst and preparation method thereof | |
| CN104649892B (en) | Method for selectively oxidizing unsaturated aldehyde | |
| CN104437526B (en) | Catalyst for preparing acrylic acid through acrolein oxidation and preparation method of catalyst | |
| CN106582697B (en) | The low rare earth catalyst of alkyl aromatics dehydrogenation | |
| CN104649876B (en) | Preparation method of acrolein | |
| CN104923245B (en) | Acrylic acid catalyst and acrylic acid synthetic method | |
| CN103521235A (en) | Catalyst for preparing acrylic acid through acrolein oxidation and preparation method thereof | |
| CN104649885B (en) | Method for preparing unsaturated acid from unsaturated aldehyde | |
| CN104107696B (en) | The preparation method of prepared by acrolein oxidation acrylic acid catalyst | |
| CN104646056B (en) | Molybdenum-phosphor series polyoxometalates catalyst, preparation method and application thereof | |
| CN107793282A (en) | The method for preparing divinylbenzene | |
| CN103894205B (en) | Acrylic acid catalyst and preparation method thereof | |
| CN107790149A (en) | Diethylbenzene dehydrogenation and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |