CN1329369C - Fluidized catalyst for acetonitrile production by ammoxidation - Google Patents
Fluidized catalyst for acetonitrile production by ammoxidation Download PDFInfo
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- CN1329369C CN1329369C CNB2004100676129A CN200410067612A CN1329369C CN 1329369 C CN1329369 C CN 1329369C CN B2004100676129 A CNB2004100676129 A CN B2004100676129A CN 200410067612 A CN200410067612 A CN 200410067612A CN 1329369 C CN1329369 C CN 1329369C
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Abstract
The present invention relates to a fluidized bed catalyst for preparing acetonitrile through ethyl alcohol ammonia oxidation, which mainly solves the problems of high ammonia ratio, high reaction temperature and low acetonitrile yield in the prior art. The fluidized bed catalyst adopts compositions which contain a silica carrier and have the chemical formula of A<a>B<b>C<c>D<d>Ce<e>Ni<f>Mo<13>O<x> according to the atomic ratio, wherein A in the chemical formula is selected from at least one of Li, Na, K, Rb, Cs, In or Tl and B is selected from at least one of Fe, Bi, La, Pr, Sm, Eu, Tb or Nd; C is selected from at least one of W, P, B, Ga, Cr, Sb, Al, Ge, Nb or V and D is selected from at least one of Mg, Co, Mn, Cu, Zn, Ca, Ba, Sr, Pb or Cd; with the technical scheme, the fluidized bed catalyst better solves the problems of the prior art and can be used in acetonitrile industrial production.
Description
Technical field
The present invention relates to the fluid catalyst of acetonitrile production by ammoxidation, particularly prepare the fluid catalyst of acetonitrile about a kind of ethanol ammonia oxidation.
Background technology
Acetonitrile is a kind of important fine chemistry industry intermediates and chemical solvents, 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 a vinyl cyanide by-product route, owing to be the by product of acrylonitrile process, so quality product 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 catalyzer are fixed bed 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 ammonia oxidation prepare technical problem to be solved by this invention exists ammonia than high in the acetonitrile process, the temperature of reaction height, and the problem that the acetonitrile yield is low provides a kind of fluid catalyst of new acetonitrile production by ammoxidation.This catalyzer is used for the direct ammonia oxidation manufacturing of ethanol acetonitrile process and has ammonia than low, and temperature of reaction 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 of acetonitrile production by ammoxidation, contain silica supports and with the following composition of atomic ratio measuring chemical formula:
A
aB
bC
cD
dCe
eNi
fMo
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, 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 0.1～3.0;
The span of f is 0.5～10.0;
X satisfies the required Sauerstoffatom sum of each element valence in the catalyzer;
Wherein the consumption of carrier silicon-dioxide is 30～70% by weight percentage in the catalyzer.
The value preferable range of a is 0.2～1.2 in the technique scheme; The value preferable range of b is 1.5～4.5; The value preferable range of c is 0.1～1.5; The value preferable range of d is 2.5～4; The value preferable range of e is 0.1～2.0; The value preferable range of f is 5～8.0; The consumption preferable range of carrier silicon-dioxide is 40～60% by weight percentage in the catalyzer.
Preparation of catalysts method of the present invention there is no particular requirement, can prepare by well-established law.At first the catalyzer each component is made solution, be mixed and made into slurry with carrier again, spray-dried moulding is after calcination activation is made catalyzer.
The raw material of making catalyzer of the present invention is:
The molybdenum component is with molybdenum oxide or ammonium molybdate in the catalyzer.
Phosphorus in the catalyzer, the most handy corresponding acids of boron or its ammonium salt; Tungsten, the most handy corresponding oxide compound of antimony or its ammonium salt; Niobium, germanium can be used oxide compound; The most handy chromium trioxide of chromium, chromium nitrate; The most handy its nitrate of all the other components, oxyhydroxide maybe can be decomposed into the salt of oxide compound.
Raw material available silicon colloidal sol as carrier silicon-dioxide.
Adopt catalyzer 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-rich air, but considers from economic resources are convenient, and is more reasonable as source of molecular oxygen with air.
The ammonia and the alcoholic acid mol ratio that enter fluidized-bed reactor 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 alcoholic acid is preferably between 6.5: 1 to 8.5: 1.
When adopting catalyzer of the present invention to carry out the ethanol ammonia oxidation in fluidized-bed reactor, temperature of reaction is 370～450 ℃, and the best is 390～430 ℃, and reaction pressure is a normal pressure.
Catalyst loading (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 catalyzer 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.
Embodiment
[embodiment 1]
3.28 gram SODIUMNITRATE are mixed with 1.79 gram saltpetre, 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 trinitrates, 143.9 gram iron nitrates, 93.7 gram cerous nitrates, 310.8 gram nickelous nitrates, 113 gram magnesium nitrates and 31.2 gram manganous 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% silicon sol mixes, under agitation add material B and material C, after fully stirring in 90 ℃ of following thermal 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 stoving oven in 350 ℃ of following roastings 2 hours, again 650 ℃ of following calcination activations 1 hour, make active catalyzer composed as follows:
Mo
13Ni
6Na
0.3K
0.15Fe
2Bi
1Mg
2.5Ce
1Mn
0.5Ge
0.1
It is 38 millimeters fluidized-bed reactor that the catalyzer of making places internal diameter, and be that 375 ℃, reaction pressure are normal pressure, ethanol in temperature of reaction: ammonia: air=1: 1: 6.5 (mole), WWH are 0.22 hour
-1Condition under carry out activity rating, the result is as follows:
Ethanol conversion 100%
Acetonitrile yield 81.6%
Prussic acid yield 5.0%
[embodiment 2～7]
Adopt method substantially the same manner as Example 1 to make to have the catalyzer that different activities is formed in the table 1, and adopt the reaction conditions identical, carry out the reaction of ethanol ammonia oxidation generation acetonitrile, the results are shown in Table 1 with embodiment 1 with prepared catalyzer.
Table 1 ethanol oxidative ammonolysis result
| Embodiment | Catalyzer is formed | Acetonitrile yield % | Prussic acid yield % | Ethanol conversion % |
| Embodiment 2 | Mo 13Ni 6Ce 1Na 0.3K 0.1Fe 2Bi 1Mg 2.5 Mn 0.5Ge 0.1Cr 0.5 | 80.7 | 5.6 | 100 |
| Embodiment 3 | Mo 13Ni 6Ce 0.8Na 0.3K 0.1Cs 0.1Fe 2Bi 1 Mg 3Ga 0.5 | 82.2 | 4.8 | 100 |
| Embodiment 4 | Mo 13Ni 6Na 0.3Cs 0.1K 0.1Fe 2.5Bi 0.5Co 3 Mn 1Ce 0.5Cr 0.3W 0.1 | 83.1 | 4.2 | 100 |
| Embodiment 5 | Mo 13Ni 8Ce 0.5Na 0.3TL 0.1K 0.1Fe 2.5Bi 1 Mn 1P 0.5Cr 0.5W 0.2Co 2 | 81.9 | 4.5 | 100 |
| Embodiment 6 | Mo 13Ni 6.5Ce 0.3Na 0.3K 0.1Rb 0.05Fe 2Bi 1 Mg 2Nb 0.2Sb 0.5 | 82.7 | 4.3 | 100 |
| Embodiment 7 | Mo 13Ni 7Na 0.3K 0.1Cs 0.1Fe 2Bi 1Nb 0.1 Mg 3Ce 1.5Ge 0.5Mn 0.5 | 82.6 | 4.1 | 100 |
Claims (8)
1, a kind of fluid catalyst of acetonitrile production by ammoxidation, contain silica supports and with the following composition of atomic ratio measuring chemical formula:
A
aB
bC
cD
dCe
eNi
fMo
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, 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 0.1～3.0;
The span of f is 0.5～10.0;
X satisfies the required Sauerstoffatom sum of each element valence in the catalyzer;
Wherein the consumption of carrier silicon-dioxide is 30～70% by weight percentage in the catalyzer.
2, according to the fluid catalyst of the described acetonitrile production by ammoxidation of claim 1, the span that it is characterized in that a is 0.2～1.2.
3, according to the fluid catalyst of the described acetonitrile production by ammoxidation of claim 1, the span that it is characterized in that b is 1.5～4.5.
4, according to the fluid catalyst of the described acetonitrile production by ammoxidation of claim 1, the span that it is characterized in that c is 0.1～1.5.
5, according to the fluid catalyst of the described acetonitrile production by ammoxidation of claim 1, the span that it is characterized in that d is 2.5～4.
6, according to the fluid catalyst of the described acetonitrile production by ammoxidation of claim 1, the span that it is characterized in that e is 0.1～2.0.
7, according to the fluid catalyst of the described acetonitrile production by ammoxidation of claim 1, the span that it is characterized in that f is 5～8.0.
8, according to the fluid catalyst of the described acetonitrile production by ammoxidation of claim 1, the consumption that it is characterized in that carrier silicon-dioxide in the catalyzer is 40～60% by weight percentage.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100676129A CN1329369C (en) | 2004-10-29 | 2004-10-29 | Fluidized catalyst for acetonitrile production by ammoxidation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100676129A CN1329369C (en) | 2004-10-29 | 2004-10-29 | Fluidized catalyst for acetonitrile production by ammoxidation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1765879A CN1765879A (en) | 2006-05-03 |
| CN1329369C true CN1329369C (en) | 2007-08-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100676129A Active CN1329369C (en) | 2004-10-29 | 2004-10-29 | Fluidized catalyst for acetonitrile production by ammoxidation |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774944B (en) * | 2010-02-09 | 2013-05-08 | 南京工业大学 | Acetonitrile production process |
| CN114426503A (en) * | 2020-10-13 | 2022-05-03 | 中国石油化工股份有限公司 | Process for the preparation of dinitrile compounds |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0206632A1 (en) * | 1985-06-10 | 1986-12-30 | IEL Limited | Process for the production of acetonitrile |
| CN1062303A (en) * | 1992-01-31 | 1992-07-01 | 清华大学 | Be used for catalyzer by ethanol and ammonia synthesis acetonitrile |
-
2004
- 2004-10-29 CN CNB2004100676129A patent/CN1329369C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0206632A1 (en) * | 1985-06-10 | 1986-12-30 | IEL Limited | Process for the production of acetonitrile |
| CN1062303A (en) * | 1992-01-31 | 1992-07-01 | 清华大学 | Be used for catalyzer by ethanol and ammonia synthesis acetonitrile |
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| Publication number | Publication date |
|---|---|
| CN1765879A (en) | 2006-05-03 |
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