CN103769160A - Propylene selective oxidation catalyst and application thereof - Google Patents
Propylene selective oxidation catalyst and application thereof Download PDFInfo
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- CN103769160A CN103769160A CN201210412590.XA CN201210412590A CN103769160A CN 103769160 A CN103769160 A CN 103769160A CN 201210412590 A CN201210412590 A CN 201210412590A CN 103769160 A CN103769160 A CN 103769160A
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Abstract
The invention relates to a propylene selective oxidation catalyst and an application thereof, which mainly solve the problem of low mechanical strength of the catalyst in the prior art. The problem is better solved by adopting the technical scheme that the catalyst takes at least one of SiO2 or Al2O3 as a carrier and comprises an active component expressed by the following general formula: Mo12BiaFebNicSbdXeYfZgQqOx, wherein X is at least one of Mg, Co, Ca, Be, Cu, Zn, Pb or Mn, Y is at least one of Zr, Th or Ti, Z is at least one of K, Rb, Na, Li, Tl or Cs, and Q is at least one of La, Ce, Sm or Th, and the catalyst can be used for industrial production of acrolein through propylene oxidation.
Description
Technical field
The present invention relates to a kind of Selective Oxidation of Propylene catalyst and uses thereof.
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.Stability aspect is except the impact of catalyst composition itself, and as catalyst mechanical strength etc., on Catalyst, operation also has great impact to catalyst physical property.
Have a lot of patent reports for alkene selective oxidation:
ZL96190146.2 has introduced a kind of catalyst for oxidation of acrolein preparation method, wherein the catalyst granules of precalcining passes through rotary drum granulating, and in forming process, adds glycol or triol, as glycerine and reinforcement material, as ceramic fibre, catalyst wearability 0.1～0.6%; The aqueous solution that ZL200310114300.4 adopts a kind of PH7.0～10.0 and contains ammonium free radical is as binding agent, and catalyst breakage rate is 0.9～3.7%; Catalyst strength is still not high enough.
Summary of the invention
Technical problem to be solved by this invention one of is to be that existing catalyst exists the problem that mechanical strength is low, breakage rate is high, and a kind of new Selective Oxidation of Propylene catalyst is provided.This catalyst has advantages of that mechanical strength is high.Two of technical problem to be solved by this invention is to provide a kind of purposes of described Selective Oxidation of Propylene 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 oxidation of propylene acrolein catalyst, and to be selected from SiO
2or Al
2o
3in at least one be carrier, contain the active component by following general formula:
Mo
12Bi
aFe
bNi
cSb
dX
eY
fZ
gQ
qO
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 d is 0.20～1.50
The span of c is 0.05～11.0;
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 q is 0.08～5.0;
X meets the required oxygen atom sum of other element valence;
In catalyst, the consumption of carrier is catalyst weight 5～40%; In shaping of catalyst process, add be selected from Ludox or aluminium colloidal sol at least one as binding agent; Catalyst strength >=30N/cm.
In technique scheme, X preferred version is at least one being selected from Mg, Co or Mn; Y preferred version is selected from least one in Zr or Ti; Z preferred version is selected from least one in K, Rb, Tl or Cs; Q is selected from least one in La, Ce or Sm.The value preferable range of a is 0.1～5.0; The value preferable range of b is 1.5～5.5; The value preferable range of c is 0.1～8.0; The value preferable range of d is 0.50～1.0; The value preferable range of e is 1.5～6.0; The value preferable range of f is 2.0～6.0; The value preferable range of g is 0.01～0.3; The value preferable range of q is 1.5～3.0.In catalyst, the consumption preferable range of carrier is catalyst weight 10～30%.The mechanical strength preferable range of described catalyst is 30 ~ 80N/cm.
In technique scheme, the preparation method of described Selective Oxidation of Propylene catalyst, comprises the following steps:
A) ammonium molybdate of aequum and alkali metal salt are dissolved in water to obtain to solution 1, then at least one carrier in Ludox or aluminium colloidal sol of being selected from of aequum are added and in solution 1, forms solution 2;
B) by the Bi of aequum, Fe, Ni and be selected from x, y, z, the metal soluble salt of q class is dissolved in and in water, forms solution 3;
C) solution 3 is joined in solution 2 to the aging slurry that obtains at 50～70 ℃;
D) slurry obtains catalyst precarsor 1 by spray shaping, and catalyst precarsor 1 obtains catalyst precarsor 2 by preroast;
E) catalyst precarsor 2 adds at least one binding agent being selected from Ludox or aluminium colloidal sol, obtains catalyst precarsor 3 through kneading, extrusion molding;
F) catalyst precarsor 3 roastings obtain catalyst finished product.
For solve the problems of the technologies described above two, scheme of the present invention is as follows: described Selective Oxidation of Propylene catalyst is prepared the catalyst of methacrylaldehyde as Selective Oxidation of Propylene.
In technique scheme, take propylene and air as raw material, the mol ratio of propylene and air is 10:(60 ~ 80), preferable range is 10:(66 ~ 75).Reaction condition is: 350 ~ 390 ℃ of reaction temperatures, and preferable range is 360 ~ 385 ℃; Reaction gauge pressure 0 ~ 0.05MPa, preferable range is 0.01 ~ 0.04MPa; Air speed 800 ~ 1500 hours
-1, preferable range is 900 ~ 1350 hours
-1.
The present invention, owing to using binding agent kind and the consumption optimized can guarantee the mechanical strength of catalyst final products in shaping of catalyst process, extends the industrial catalyst cycle of operation steady.Catalyst of the present invention is prepared methacrylaldehyde for Selective Oxidation of Propylene, is 10:60～80,350～390 ℃ of reaction temperatures, reaction pressure 0～0.05MPa, air speed 800～1500h in propylene, air mol ratio
-1under condition, its propylene conversion can reach 98.9%, product methacrylaldehyde and acrylic acid yield can reach 93.2%, and catalyst strength>=30N/cm, through 2000h stability test rear catalyst breakage rate <0.5%.
The present invention, by controlling kind and the consumption of having optimized binding agent in catalyst preparation process, has obtained high catalyst strength, has 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 joins in the warm water of 1000 grams 70 ℃, stirs it is all dissolved, and adds the Ludox of 948 gram 40% (wt.) and 379 gram of 20% aluminium colloidal sol to make material A.
By 397 grams of Fe (NO
3)
39H
2o adds in 70 ℃ of hot water of 150 grams, adds 275 grams of Bi (NO after stirring and dissolving again
3)
35H
2o, 495 grams of Co (NO
3)
26H
2o, 452 grams of Ni (NO
3)
26H
2o, 84 grams of Mn (NO
3)
2solution (50%), 20 grams of La (NO
3)
33H
2after O stirring and dissolving, make material B.
250 gram of 20% ammoniacal liquor is joined in 150 grams of tartaric acid, after dissolving, add 55.6 grams of Sb
2o
3, stir until Sb
2o
3dissolve completely, obtain material C.
In 20 grams of water, add 2.9 grams of KNO
3and 5.5 grams of CsNO
3after dissolving, added and in material B, formed material D.
Material C and material D are dripped successively in material A under rapid stirring, form catalyst pulp, and at 65 ℃, stir aging 2 hours, slurry is dried by spraying, then obtains catalyst precarsor 250 ℃ of preroasts.Get 1000 grams of catalyst precarsors and add 150 grams of Ludox and 100 grams of kneadings of water, extrusion molding, obtain the cylinder of φ 3.5x3.5mm, then obtain catalyst finished product roasting in 490 ℃, 1 hour.This catalyst propylene conversion 98.4%, methacrylaldehyde acrylic acid total recovery 92.8%, catalyst strength 58.8N/cm.
The investigation appreciation condition of catalyst is:
Reactor: fixed bed single tube reactor, 25.4 millimeters of internal diameters, 3000 millimeters of reactor length
Catalyst: 600 grams
Reaction temperature: 370 ℃
Raw material ratio: propylene/air/water steam=10/73/17
Reaction velocity: 1200 hours
～1
Product absorbs with 0 ℃ of diluted acid, uses gas chromatographic analysis product.And calculate Carbon balance, when Carbon balance is valid data during at (95～105) %.
Propylene conversion, product yield and be optionally defined as:
[embodiment 2～10]
[embodiment 2～10] catalyst, with [embodiment 1], just adds different binding agents in shaping of catalyst, and shaping of catalyst condition and intensity etc. the results are shown in table 1.
[comparative example]
Comparative example catalyst same [embodiment 1], but in shaping of catalyst, only add water as binding agent
Table 1 shaping of catalyst condition and intensity results
Claims (10)
1. a Selective Oxidation of Propylene catalyst, to be selected from SiO
2or Al
2o
3in at least one be carrier, contain the active component by following general formula:
Mo
12Bi
aFe
bNi
cSb
dX
eY
fZ
gQ
qO
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 d is 0.20～1.50
The span of c is 0.05～11.0;
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 q is 0.08～5.0;
X meets the required oxygen atom sum of other element valence;
In catalyst, the consumption of carrier is catalyst weight 5～40%; In shaping of catalyst process, add be selected from Ludox or aluminium colloidal sol at least one as binding agent; Catalyst strength >=30N/cm.
2. Selective Oxidation of Propylene catalyst according to claim 1, is characterized in that X is at least one being selected from Mg, Co or Mn; Y is selected from least one in Zr or Ti; Z is selected from least one in K, Rb, Tl or Cs; Q is selected from least one in La, Ce or Sm.
3. Selective Oxidation of Propylene catalyst according to claim 1, the span that it is characterized in that a is 0.1～5.0; The span of b is 1.5～5.5; The span of c is 0.1～8.0; The span of d is 0.50～1.0; The span of e is 1.5～6.0; The span of f is 2.0～6.0; The span of g is 0.01～0.3; The span of q is 1.5～3.0.
4. Selective Oxidation of Propylene catalyst according to claim 1, the consumption that it is characterized in that carrier in catalyst is catalyst weight 10～30%.
5. Selective Oxidation of Propylene catalyst according to claim 1, the mechanical strength that it is characterized in that described catalyst is 30 ~ 80N/cm.
6. Selective Oxidation of Propylene catalyst according to claim 1, the preparation method of the Selective Oxidation of Propylene catalyst described in it is characterized in that, comprises the following steps:
A) ammonium molybdate of aequum and alkali metal salt are dissolved in water to obtain to solution 1, then at least one carrier in Ludox or aluminium colloidal sol of being selected from of aequum are added and in solution 1, forms solution 2;
B) by the Bi of aequum, Fe, Ni and be selected from x, y, z, the metal soluble salt of q class is dissolved in and in water, forms solution 3;
C) solution 3 is joined in solution 2 to the aging slurry that obtains at 50～70 ℃;
D) slurry obtains catalyst precarsor 1 by spray shaping, and catalyst precarsor 1 obtains catalyst precarsor 2 by preroast;
E) catalyst precarsor 2 adds at least one binding agent being selected from Ludox or aluminium colloidal sol, obtains catalyst precarsor 3 through kneading, extrusion molding;
F) catalyst precarsor 3 roastings obtain catalyst finished product.
7. Selective Oxidation of Propylene catalyst claimed in claim 1 is prepared the catalyst of methacrylaldehyde as Selective Oxidation of Propylene.
8. the purposes of Selective Oxidation of Propylene catalyst according to claim 7, it is characterized in that take propylene and air as raw material, the mol ratio of propylene and air is 10:(60 ~ 80), reaction condition is: 350 ~ 390 ℃ of reaction temperatures, reaction gauge pressure 0 ~ 0.05MPa, air speed 800 ~ 1500 hours
-1.
9. the purposes of propylene oxidation catalyst according to claim 8, is characterized in that reaction temperature is 360 ~ 385 ℃, and reaction gauge pressure is 0.01 ~ 0.04MPa, and air speed is 900 ~ 1350 hours
-1.
10. the purposes of propylene oxidation catalyst according to claim 8, the mol ratio that it is characterized in that propylene and air is 10:(66 ~ 75).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210412590.XA CN103769160A (en) | 2012-10-25 | 2012-10-25 | Propylene selective oxidation catalyst and application thereof |
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|---|---|---|---|
| CN201210412590.XA CN103769160A (en) | 2012-10-25 | 2012-10-25 | Propylene selective oxidation catalyst and application thereof |
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|---|---|---|---|
| CN201210412590.XA Pending CN103769160A (en) | 2012-10-25 | 2012-10-25 | Propylene selective oxidation catalyst and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105597773A (en) * | 2014-11-20 | 2016-05-25 | 中国石油化工股份有限公司 | Catalyst for preparing unsaturated aldehyde and unsaturated acid through olefin oxidation |
| CN105618076A (en) * | 2014-11-20 | 2016-06-01 | 中国石油化工股份有限公司 | Alpha, beta-nonsaturated aldehyde catalyst |
Citations (4)
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|---|---|---|---|---|
| CN1287882A (en) * | 1999-06-24 | 2001-03-21 | 中国石油化工集团公司 | Fluidized bed catalyst for ammoxidation of propylene |
| CN1583261A (en) * | 2004-06-11 | 2005-02-23 | 谷育英 | Composite metal oxide for unsaturated aldehyde selective oxidation and preparing method thereof |
| CN102451710A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Catalyst for preparing acrolein by propylene oxidation method and preparation method thereof |
| CN103736498A (en) * | 2012-10-17 | 2014-04-23 | 中国石油化工股份有限公司 | Propylene oxidation catalyst, preparation method thereof and applications thereof |
-
2012
- 2012-10-25 CN CN201210412590.XA patent/CN103769160A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1287882A (en) * | 1999-06-24 | 2001-03-21 | 中国石油化工集团公司 | Fluidized bed catalyst for ammoxidation of propylene |
| CN1583261A (en) * | 2004-06-11 | 2005-02-23 | 谷育英 | Composite metal oxide for unsaturated aldehyde selective oxidation and preparing method thereof |
| CN102451710A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Catalyst for preparing acrolein by propylene oxidation method and preparation method thereof |
| CN103736498A (en) * | 2012-10-17 | 2014-04-23 | 中国石油化工股份有限公司 | Propylene oxidation catalyst, preparation method thereof and applications thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李大东主编: "《加氢处理工艺与工程》", 31 December 2004, 中国石化出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105597773A (en) * | 2014-11-20 | 2016-05-25 | 中国石油化工股份有限公司 | Catalyst for preparing unsaturated aldehyde and unsaturated acid through olefin oxidation |
| CN105618076A (en) * | 2014-11-20 | 2016-06-01 | 中国石油化工股份有限公司 | Alpha, beta-nonsaturated aldehyde catalyst |
| CN105597773B (en) * | 2014-11-20 | 2018-05-11 | 中国石油化工股份有限公司 | The catalyst of olefin oxidation unsaturated aldehyde and unsaturated acids |
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Application publication date: 20140507 |
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