CN1751791A - Fluidized bed catalyst for preparing acetonitrile - Google Patents
Fluidized bed catalyst for preparing acetonitrile Download PDFInfo
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- CN1751791A CN1751791A CN 200410066623 CN200410066623A CN1751791A CN 1751791 A CN1751791 A CN 1751791A CN 200410066623 CN200410066623 CN 200410066623 CN 200410066623 A CN200410066623 A CN 200410066623A CN 1751791 A CN1751791 A CN 1751791A
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- acetonitrile
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- ethanol
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Abstract
A fluidized-bed catalyst for preparing acetonitrile by ammoxidizing ethanol is composed of SiO2 as carrier and the composition AaBbCcDdNieM013Ox, where A is chosen from Li, Na, K, Rb, Cs, In and T1, B is chosen from Fe, Bi, La, Pr, Sm, Eu, Tb and Nd, C is chosen from W, P, B, Ga, Cr, Sb, Al, Ge, Nb and V, and D is chosen from Mg, Co, Mn, Cu, Zn, Ca, Ba, Sr, Pb and Cd. Its advantages are low reaction temp and high output rate.
Description
Technical field
The present invention relates to a kind of fluid catalyst for preparing acetonitrile, particularly prepare the fluid catalyst of acetonitrile about a kind of ethanol ammoxidation.
Background technology
Acetonitrile is a kind of important fine chemistry industry intermediate products and chemical solvent, can be used as the intermediate and the solvent of industries such as pharmacy and agricultural chemicals, also can be used for the extractant of industries such as synthetic rubber.At present the production method of acetonitrile mainly is an acrylonitrile by-product route, owing to be the accessory substance of acrylonitrile process, so product quality is difficult to guarantee, and output is also less.Also useful in addition synthesizing acetonitrile by ethanol ammoniation method, as European patent EP-206632, but this catalyst reaction temperatures height, ammonia be than high, and ethanol conversion is low, the acetonitrile yield is low; Chinese patent 92100589, this catalyst are fixed bde catalyst, and the catalyst preparation process complexity, and it is higher than very to react required ammonia, NH
3: ethanol (mol ratio) reaches 5.
Summary of the invention
To be prior art in the ethanol ammoxidation prepare technical problem to be solved by this invention exists ammonia than high in the acetonitrile process, the reaction temperature height, and the problem that the acetonitrile yield is low provides a kind of fluid catalyst of new preparation acetonitrile.This catalyst is used for the direct ammoxidation of ethanol and prepares the acetonitrile process and have ammonia than low, and reaction temperature is low, ethanol conversion height and the high characteristics of acetonitrile yield.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of fluid catalyst for preparing acetonitrile, contain silica supports and with the following composition of atomic ratio measuring chemical formula:
A
aB
bC
cD
dNi
eMo
13O
x
A is selected from least a among Li, Na, K, Rb, Cs, In or the Tl in the formula;
B is selected from least a among Fe, Ce, Bi, La, Pr, Sm, Eu, Tb or the Nd;
C is selected from least a among W, P, B, Ga, Cr, Sb, Al, Ge, Nb or the V;
D is selected from least a among Mg, Co, Mn, Cu, Zn, Ca, Ba, Sr, Pb or the Cd;
The span of a is 0.01～2.0;
The span of b is 0.1～5.5;
The span of c is 0～2.5;
The span of d is 0.01～8;
The span of e is 0.5～10.0;
X satisfies the required oxygen atom sum of each element valence in the catalyst;
Wherein carrier silica is 30～70% by weight percentage in the catalyst.
The value preferable range of a is 0.1～1.2 in the technique scheme; The value preferable range of b is 1.5～3.5; The value preferable range of c is 0.1～2.0; The value preferable range of d is 1.0～5.0; The value preferable range of e is 2.5～8.0; The consumption preferable range of carrier silica is 40～60% by weight percentage in the catalyst.
Preparation of catalysts method of the present invention there is no specific (special) requirements, can prepare by well-established law.At first the catalyst each component is made solution, be mixed and made into slurry with carrier again, spray-dried moulding is after calcination activation is made catalyst.
The raw material of making catalyst of the present invention is:
The molybdenum component is with molybdenum oxide or ammonium molybdate in the catalyst.
Phosphorus in the catalyst, the most handy corresponding acids of boron or its ammonium salt; Tungsten, the most handy corresponding oxide of antimony or its ammonium salt; Niobium, germanium can be used oxide; The most handy chromium trioxide of chromium, chromic nitrate; The most handy its nitrate of all the other components, hydroxide maybe can be decomposed into the salt of oxide.
Raw material available silicon colloidal sol as carrier silica.
Adopt catalyst of the present invention to make required feed ethanol, ammonia and the molecular oxygen of acetonitrile and do not have special requirement.Ethanol can be used technical grade ethanol, and ammonia can be used fertilizer grade liquefied ammonia, reacts required molecular oxygen from the available pure oxygen of technological standpoint, oxygen-enriched air, but considers from economic resources are convenient, and is more reasonable as source of molecular oxygen with air.
Entering the ammonia of fluidized-bed reactor and the mol ratio of ethanol can change between 0.8: 1 to 1.3: 1, but best variation between 0.9: 1 to 1.1: 1.The actual mol ratio of air and ethanol is preferably between 6.5: 1 to 8.5: 1.
When adopting catalyst of the present invention to carry out the ethanol ammoxidation in fluidized-bed reactor, reaction temperature is 370～450 ℃, and the best is 390～430 ℃, and reaction pressure is a normal pressure.
Catalyst weight load (WWH) is 0.10～0.30 hour
-1, the best is 0.15～0.25 hour
-1
WWH is defined as:
WWH=ethanol feed weight/(catalyst weight * hour)
Below be the embodiment of catalyst of the present invention, wherein the once through yield of ethanol conversion, acetonitrile is defined as follows:
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
3.28 gram sodium nitrate are mixed with 1.79 gram potassium nitrate, add water 30 gram and heating for dissolving, obtain material (A); 404.6 gram ammonium molybdates are dissolved in the hot water of 360 grams 60～90, obtain material (B); 85.5 gram bismuth nitrates, 143.9 gram ferric nitrates, 310.8 gram nickel nitrates, 113 gram magnesium nitrates and 31.2 gram manganese nitrates are mixed, add water 300 grams, obtain material (C) after the heating for dissolving.
With material A and 1250 gram weight concentration is that 40% Ludox mixes, under agitation add material B and material C, after fully stirring in 90 ℃ of following heat treatments one hour, obtain uniform slurry, be microspheroidal by well-established law with slurry drying and moulding in spray dryer of making then, then in rotary roaster in 350 ℃ of following roastings 2 hours, again 650 ℃ of following calcination activations 1 hour, make active catalyst composed as follows:
Mo
13Ni
6Na
0.3K
0.15Fe
2Bi
1Mg
2.5Mn
0.5Ge
0.1
It is 38 millimeters fluidized-bed reactor that the catalyst of making places internal diameter, and be that 390 ℃, reaction pressure are normal pressure, ethanol in reaction temperature: ammonia: air=1: 1: 7 (mole), WWH are 0.22 hour
-1Condition under carry out activity rating, the result is as follows:
Ethanol conversion 100%
Acetonitrile yield 77.0%
Hydrogen cyanide yield 8.0%
[embodiment 2～7]
Adopt method substantially the same manner as Example 1 to make to have the catalyst that different activities is formed in the table 1, and adopt the reaction condition identical, carry out the reaction of ethanol ammoxidation generation acetonitrile, the results are shown in Table 1 with embodiment 1 with prepared catalyst.
Table 1 ethanol ammoxidation reaction result
| Embodiment | Catalyst is formed | Acetonitrile yield % | Hydrogen cyanide yield % | Ethanol conversion % |
| Embodiment 2 | Mo 13Ni 6Na 0.3K 0.15Fe 2Bi 1Mg 2.5 Mn 0.5Ge 0.1Cr 0.5 | 78.3 | 7.6 | 100 |
| Embodiment 3 | Mo 13Ni 6Na 0.3K 0.15Cs 0.05Fe 2Bi 0.65 Mg 3La 0.4Ga 0.5 | 77.2 | 8.0 | 100 |
| Embodiment 4 | Mo 13Ni 6Na 0.3Cs 0.1Fe 2.5Bi 0.5Co 3 Mn 1La 0.5Cr 0.3W 0.1 | 76.3 | 9.2 | 100 |
| Embodiment 5 | Mo 13Ni 8Na 0.3TL 0.1Fe 2.5Bi 1Co 2 Mn 1P 0.5Cr 0.5W 0.2 | 76.9 | 8.1 | 100 |
| Embodiment 6 | Mo 13Ni 8Na 0.3K 0.1Rb 0.05Fe 2Bi 1 Mg 2Nb 0.2Sb 0.5 | 78.0 | 7.8 | 100 |
| Embodiment 7 | Mo 13Ni 7Na 0.3K 0.1Cs 0.1Fe 2Bi 1 Mg 3La 0.5Ge 0.5Sb 0.1Mn 0.5 | 77.8 | 7.8 | 100 |
Claims (7)
1, a kind of fluid catalyst for preparing acetonitrile, contain silica supports and with the following composition of atomic ratio measuring chemical formula:
A
aB
bC
cD
dNi
eMo
13O
x
A is selected from least a among Li, Na, K, Rb, Cs, In or the Tl in the formula;
B is selected from least a among Fe, Ce, Bi, La, Pr, Sm, Eu, Tb or the Nd;
C is selected from least a among W, P, B, Ga, Cr, Sb, Al, Ge, Nb or the V;
D is selected from least a among Mg, Co, Mn, Cu, Zn, Ca, Ba, Sr, Pb or the Cd;
The span of a is 0.01～2.0;
The span of b is 0.1～5.5;
The span of c is 0～2.5;
The span of d is 0.01～8;
The span of e is 0.5～10.0;
X satisfies the required oxygen atom sum of each element valence in the catalyst;
Wherein carrier silica is 30～70% by weight percentage in the catalyst.
2, according to the fluid catalyst of the described preparation acetonitrile of claim 1, the span that it is characterized in that a is 0.1～1.2.
3, according to the fluid catalyst of the described preparation acetonitrile of claim 1, the span that it is characterized in that b is 1.5～3.5.
4, according to the fluid catalyst of the described preparation acetonitrile of claim 1, the span that it is characterized in that c is 0.1～2.0.
5, according to the fluid catalyst of the described preparation acetonitrile of claim 1, the span that it is characterized in that d is 1.0～5.0.
6, according to the fluid catalyst of the described preparation acetonitrile of claim 1, the span that it is characterized in that e is 2.5～8.0.
7, according to the fluid catalyst of the described preparation acetonitrile of claim 1, the consumption that it is characterized in that carrier silica in the catalyst is 40～60% by weight percentage.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100666235A CN100358629C (en) | 2004-09-24 | 2004-09-24 | Fluidized bed catalyst for preparing acetonitrile |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100666235A CN100358629C (en) | 2004-09-24 | 2004-09-24 | Fluidized bed catalyst for preparing acetonitrile |
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| CN100358629C CN100358629C (en) | 2008-01-02 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279265B (en) * | 2007-04-04 | 2010-12-22 | 中国石油化工股份有限公司 | Fluidized bed catalyst for preparing acrylonitrile |
| CN101279264B (en) * | 2007-04-04 | 2010-12-22 | 中国石油化工股份有限公司 | High load fluidized bed catalyst for preparing acrylonitrile |
| JP2012061394A (en) * | 2010-09-14 | 2012-03-29 | Tokyo Metropolitan Univ | Catalyst composition for synthesizing nitrile and method for producing nitrile using the same |
| CN101602693B (en) * | 2009-04-29 | 2012-06-20 | 南通醋酸化工股份有限公司 | Method for synthesizing acetonitrile by ethanol ammoniation method |
| CN101767014B (en) * | 2009-01-07 | 2012-06-27 | 中国石油化工股份有限公司 | Fluidized bed catalyst for producing acrylonitrile by propylene ammoxidation |
| CN107876085A (en) * | 2017-11-15 | 2018-04-06 | 昌邑市瑞海生物科技有限公司 | A kind of preparation method of the special-purpose catalyst of synthesizing acetonitrile |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1025551C (en) * | 1990-11-05 | 1994-08-03 | 中国石油化工总公司 | Long-term stabilizing method for catalyst activity of acrylonitrile fluidized bed |
| CN1024395C (en) * | 1992-01-31 | 1994-05-04 | 清华大学 | Catalyst for synthesizing acetonitrile from alcohol and ammonia |
| CN1059607C (en) * | 1996-08-06 | 2000-12-20 | 中国石油化工总公司 | Acrylonitrile fluidized bed containing rare earth metal catalyst |
| US6204407B1 (en) * | 1998-12-09 | 2001-03-20 | The Standard Oil Company | Ammoxidation of a mixture of alcohols to a mixture of nitriles to acetonitrile and HCN |
| CN1107541C (en) * | 1999-11-03 | 2003-05-07 | 中国石油化工集团公司 | Fluid bed catalyst for acrylonitrile production |
| CN1099316C (en) * | 1999-11-03 | 2003-01-22 | 中国石油化工集团公司 | Catalyst for acrylonitrile fluid bed |
| CN1102576C (en) * | 2000-02-24 | 2003-03-05 | 中国石油化工集团公司 | Fluidized bed catalyst for ammoxidating propylene to prepare acrylonitrile |
| CN1136980C (en) * | 2000-02-24 | 2004-02-04 | 中国石油化工集团公司 | Fluidized bed catalyst for ammoxidating propylene to produce acrylonitrile |
| JP4854149B2 (en) * | 2001-08-29 | 2012-01-18 | 旭化成ケミカルズ株式会社 | A method to stably increase the production of acetonitrile |
-
2004
- 2004-09-24 CN CNB2004100666235A patent/CN100358629C/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279265B (en) * | 2007-04-04 | 2010-12-22 | 中国石油化工股份有限公司 | Fluidized bed catalyst for preparing acrylonitrile |
| CN101279264B (en) * | 2007-04-04 | 2010-12-22 | 中国石油化工股份有限公司 | High load fluidized bed catalyst for preparing acrylonitrile |
| CN101767014B (en) * | 2009-01-07 | 2012-06-27 | 中国石油化工股份有限公司 | Fluidized bed catalyst for producing acrylonitrile by propylene ammoxidation |
| CN101602693B (en) * | 2009-04-29 | 2012-06-20 | 南通醋酸化工股份有限公司 | Method for synthesizing acetonitrile by ethanol ammoniation method |
| JP2012061394A (en) * | 2010-09-14 | 2012-03-29 | Tokyo Metropolitan Univ | Catalyst composition for synthesizing nitrile and method for producing nitrile using the same |
| CN107876085A (en) * | 2017-11-15 | 2018-04-06 | 昌邑市瑞海生物科技有限公司 | A kind of preparation method of the special-purpose catalyst of synthesizing acetonitrile |
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| Publication number | Publication date |
|---|---|
| CN100358629C (en) | 2008-01-02 |
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