CN1031662A - The rich acrylonitrile catalyst that produces prussic acid - Google Patents
The rich acrylonitrile catalyst that produces prussic acid Download PDFInfo
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- CN1031662A CN1031662A CN 87101099 CN87101099A CN1031662A CN 1031662 A CN1031662 A CN 1031662A CN 87101099 CN87101099 CN 87101099 CN 87101099 A CN87101099 A CN 87101099A CN 1031662 A CN1031662 A CN 1031662A
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- catalyzer
- prussic acid
- vinyl cyanide
- rich
- iii
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Abstract
A kind ofly prepare the catalyzer of vinyl cyanide by propylene ammmoxidation process, it not only generates vinyl cyanide has higher activity and selectivity, and under the situation that acrylonitrile yield does not reduce substantially the rich prussic acid that produces.The composition of catalyzer is by following general formula:
Mo
12Bi
aFe
bCr
cMndM
e' M
f" I
gII
hIII
iO
xM ' in the formula=Li, K, Rb, Cs, Tl; M "=Co, Ni, Zn, Mg, Cd, Al, Ca; I=Ce, La, Pr, Nd; II=Pb, Ge, Cu; III=Sb, Ti, Zr, Hf; A, b ..., h, i be the atomicity of 12 o'clock respective element for the Mo component, x satisfies the required oxygen atomicity of its valency.
Description
The invention belongs to the light alkene ammonia oxidation and prepare the catalyzer of unsaturated nitrile.
The catalyzer that the light alkene oxidation proceses of ammonia prepares unsaturated nitrile has carried out a series of improvement, as EP44875, JK59-98731, EP57918, the catalyzer that patents such as USP4212766 are released, ammoxidation of propylene had acrylonitrile yield preferably, but the ratio of prussic acid is less in byproduct of reaction, we know, generally under the certain prerequisite of propylene conversion and acrylonitrile yield, if in the by product prussic acid at least other as propenal, acetonitrile, full oxide is just many, and in these by products, prussic acid is not only more easily separated, to production have no adverse effects and industrial be a kind of industrial chemicals of having many uses.
Therefore, under the constant substantially situation of acrylonitrile yield rich produce prussic acid for the economic return that improves factory beyond doubt highly significant.
Purpose of the present invention just provides a kind of new catalyzer, and it is used for the ammoxidation of propylene reaction, not only vinyl cyanide is generated to have higher activity and selectivity, and richness is produced prussic acid under the situation that acrylonitrile yield does not reduce substantially.
Essence of the present invention is to add the element of IV, IV B, VII B isofamily on the Mo-Bi-Fe series catalysts, and the composition of catalyzer is by following general formula:
Mo
12Bi
aFe
bCr
cMn
dM′
eM″
fⅠ
gⅡ
hⅢ
iO
x
M ' is Li in the formula, K, Rb, Cs, the mixture of Tl or above-mentioned element, M " be Co, Ni, Zn, Mg; Cd, Al, the mixture of Ca or above-mentioned element, I is Ce; La, Pr, Nd, II is Pb; Ge, Cu, III is Sb, Ti; Zr, Hf, a, b ..., h, i be the atomicity of 12 o'clock respective element for the Mo component, x is that other element is to satisfy the required oxygen atomicity of its valency when existing.A=0.2～3 wherein, b=0.5～4, c=0.1～4, d=0.1～3, e=0.01～1, f=1～10, g=0～1, h=0.1～3, i=0.1～3, b+c+g is between 2～8.
Catalyzer prepares with Slurry mixing, slurry drying, decomposition, pulverizes, sieves or the direct spray-dried moulding of slurry, carries out solid state reaction then under 450 ℃, 540～650 ℃ of following roastings.Catalyzer can add carrier, generally adopts SiO
2, content is 20～80% of catalyzer total amount, is preferably between 40～60% when being applied to fluidized-bed.
Roasting rear catalyst thing is mainly molybdate and heteropoly acid type mixed oxide mutually, and bulk density is 0.98～1.02g/ml, and specific surface is 35～45m
2/ g.
In the used raw material of Preparation of Catalyst, molybdenum compound can be used molybdic oxide, molybdic acid, ammonium molybdate, Ce, La, Nd can use oxide compound, nitrate, carbonate, oxalate, also available mixing salt, antimony compounds can be used antimonous oxide, antimony powder or butter of antimony, Cr can use chromic acid, chromium nitrate, ammonium dichromate, and other element all adopts nitrate or oxide compound.
It is to carry out in the 8mm stainless steel reaction pipe that evaluating catalyst ties up to internal diameter, in insert catalyzer 1～2g, reaction gas raw material ratio of components is a propylene: ammonia: air=1: 1.2: 10, air speed are 600～1200hr, temperature of reaction is 380～440 ℃, and reaction pressure is 0.05～0.2kg/cm
2, reactor product adopts gas-chromatography and chemical analysis to analyze, and calculates the carbon balance before and after the reaction.
The fixed bed reaction data are in 1 1/2 inch fluidized-bed reactor authentications, catalyst levels is 550g, the unstripped gas partition ratio is a propylene: ammonia: air=1: (1.1～1.2): (9.5～10.5), WWH=0.045～0.06, the reactor product liquid freezing absorbs, analyze with gas-chromatography and chemical analysis, HCH content is with the free total cyanometer of reactor product, and carbon balance is controlled at 100 ± 5%.
Enumerate some examples and comparative example below, to further specify technical characterictic of the present invention.Wherein the yield of each product, transformation efficiency, optionally be defined as follows:
Acrylonitrile yield (%)=(vinyl cyanide mole number in the product)/(propylene mole number in the raw material) * 100
Propylene conversion (%)=(remaining propylene mole number in the product)/(propylene mole number in the raw material) * 100
Vinyl cyanide selectivity (%)=(vinyl cyanide amount (gram) in the product)/(catalytic amount (gram) * reaction times (hour)) * 100
Prussic acid yield (%)=(prussic acid mole number in the product)/(propylene mole number in the raw material) * 100
Example one: in 50ml water, add 0.12g 40% KOH, 40g Ammonium Heptamolybdate and 40% silicon sol 126g, PH is adjusted to 6.4, in this solution, add the solution that contains 5.6g chromium nitrate and 2.1g manganous nitrate, also drip goes into to contain 14.8g iron nitrate, 24.1g Xiao Suangu, 13.4g nickel nitrate solution again, contain the 8.9g Bismuth trinitrate, 0.32g cesium nitrate solution and contain the 1.05g lead nitrate solution and make yellow slurry, splash into the solution that contains the 1.2g tin tetrachloride after PH＜3, wore out 0.5～4 hour in 80～100 ℃ of following slurries.In 110～120 ℃ down evaporation do solid (or spray drying formings), under 200～240 ℃, decompose, pulverize, sieve 40～80 order particles.In 400～460 ℃ of following preroastings 0.5～2 hour, roasting promptly got the catalyzer finished product in 3 hours in 580 ℃ of following oxygen deprivation atmosphere or nitrogen gas stream then.
This catalyzer consists of:
Cs
0.1K
0.1Co
4.5Ni
2.5Bi
1.0Fe
2.0Cr
1.0Mn
0.5Sn
0.2Pb
0.2Mo
12.3O
x
SiO
2Content is 50% of total catalyst weight.
Get above-mentioned catalyzer 0.9g and insert in the 8mm stainless steel reaction pipe, feed unstripped gas, propylene: ammonia: air=1: 1.2: 10, air speed=600hr.
Reaction result sees Table 1.
Example two:, replace tin tetrachloride with the 0.76g butter of antimony with example one preparation method.
Catalyzer consists of:
Cs
0.1K
0.1Co
4.5Ni
2.5Bi
1.0Fe
2.0Cr
1.0Mn
0.5Pb
0.2Sb
0.2Mo
12.3O
x
SiO
2Be 50%.
Get catalyzer and estimate, the results are shown in Table 1 with example one method.
Example three: with the preparation method of example two, add lead nitrate 2.1g, catalyzer consists of:
Cs
0.1K
0.1Co
4.5Ni
2.5Bi
1.0Fe
2.0Cr
1.0Mn
0.5Pb
0.4Sb
0.2Mo
12.3O
x
SiO
2Be 50%.
Get catalyzer and estimate, the results are shown in Table 1 with example one method.
Example four: with the preparation method of example two, add lead nitrate 0.4g, catalyzer consists of:
Cs
0.1K
0.1Co
4.5Ni
2.5Bi
1.0Fe
2.0Cr
1.0Mn
0.5Pb
0.07Sb
0.2Mo
12.3O
x
SiO
2Be 50%.
Get catalyzer and estimate, the results are shown in Table 1 with example one method.
Example five: with the preparation method of example two, catalyzer consists of:
Cs
0.1K
0.1Co
4.5Mg
2.5Bi
1.0Fe
2.0Cr
1.0Mn
0.5Pb
0.2Sb
0.2Mo
12.3O
x
SiO
2Be 50%.
Get catalyzer and estimate, the results are shown in Table 1 with example one method.
Example six: with the preparation method of example two, catalyzer consists of:
Cs
0.1Co
4.5Ni
2.5Bi
1.0Fe
2.0Cr
1.0Mn
0.5Pb
0.2Sb
0.2Mo
12.3O
x
SiO
2Be 50%.
Get catalyzer and estimate, the results are shown in Table 1 with example one method.
Comparative example one: in 40ml water, add 40% KOH 0.12g, Ammonium Heptamolybdate 39.2g, 40% silicon sol 126g, 85% H
3PO
40.72ml, PH=6.2, splash into the solution that contains 21g iron nitrate, 24.1g Xiao Suangu, 13.4g nickelous nitrate, 8.9g Bismuth trinitrate, slurry wore out viscosity 150cp two hours in 100 ℃, solid content 51.2%, in 110～120 ℃ down evaporation do admittedly, 200～220 ℃ are decomposed (or spraying drying shaping) down, 400～420 ℃ of following preroasting 0.5 hour, 640 ℃ of following roastings 2 hours, the gained catalyzer consists of:
K
0.1Co
4.5Ni
2.5Fe
3.0Bi
1.0P
0.5Mo
12O
x
SiO
2Be 50%.
Get catalyzer and estimate, the results are shown in Table 1 with example one method.
Comparative example two: with the preparation method of example two, catalyzer consists of:
Cs
0.1K
0.1Co
4.5Ni
2.5Bi
1.0Fe
2.0Cr
1.0Mn
0.5Sn
0.2Sb
0.2Mo
12.3O
x
SiO
2Be 50%.
Get catalyzer and estimate, the results are shown in Table 1 with example one method
Table 1:
Propylene conversion vinyl cyanide selectivity acrylonitrile yield prussic acid yield
（%）????（%）????（%）????（%）
Example 1
Example 2 96.8 94.6 81.9 4.6
Example 3 99.2 82.0 81.4 6.2
Example 4 96.4 84.4 81.4 5.2
Example 5 98.2 83.0 81.6 6.1
Example 6 98.4 82.5 81.2 6.2
Comparative example 1
Comparative example 2 98.0 84.8 83.1 2.1
From the evaluation result of above-mentioned catalyzer as seen, catalyzer provided by the invention not only propylene conversion, vinyl cyanide selectivity is all very desirable, and the prussic acid yield is obviously increased under the situation of not losing acrylonitrile yield substantially.
Claims (4)
1, a kind ofly prepare the catalyzer of vinyl cyanide by propylene ammmoxidation process, the composition that it is characterized in that it is by following general formula:
M ' is Li in the formula, K, Rb, Cs, the mixture of T1 or above-mentioned element, M " be Co, Ni, Zn, Mg; Cd, Al, the mixture of Ca or above-mentioned element, I is Ce; La, Pr, Nd, II is Pb; Ge, Cu, III is Sb, Ti; Zr, Hf, a, b ..., h, i be the atomicity of 12 o'clock respective element for the Mo component, x is that other element is to satisfy the required oxygen atomicity of its valency when existing.A=0.2～3 wherein, b=0.5～4, c=0.1～4, d=0.1～3, e=0.01～1, f=1～10, g=0～1, h=0.1～3, i=0.1～3, b+c+g is between 2～8.Catalyzer prepares with Slurry mixing, and bulk density is 0.98～1.02g/ml, and specific surface is 35～45m
2/ g.
2, according to the described catalyzer of claim 1, it is characterized in that described catalyzer has carrier, carrier is SiO
2, content is 20～80% of total catalyst weight, the best is 40～60%.
3, according to the described catalyzer of claim 1, " be Co and Ni, II is Pb, and III is Sb to it is characterized in that described M ' is Cs and K, M.
4, a kind ofly prepare the method for vinyl cyanide, it is characterized in that using catalyzer as claimed in claim 1 by propylene ammmoxidation process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87101099 CN1031662A (en) | 1987-08-29 | 1987-08-29 | The rich acrylonitrile catalyst that produces prussic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87101099 CN1031662A (en) | 1987-08-29 | 1987-08-29 | The rich acrylonitrile catalyst that produces prussic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1031662A true CN1031662A (en) | 1989-03-15 |
Family
ID=4813182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87101099 Pending CN1031662A (en) | 1987-08-29 | 1987-08-29 | The rich acrylonitrile catalyst that produces prussic acid |
Country Status (1)
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|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5840648A (en) * | 1997-09-02 | 1998-11-24 | The Standard Oil Company | Catalyst for the manufacture of acrylonitrile and hydrogen cyanide |
| CN102451710A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Acrylaldehyde catalyst prepared by propylene oxidation method and its preparation method |
| US8585870B2 (en) | 2008-03-05 | 2013-11-19 | E I Du Pont De Nemours And Company | Process to C-manufacture acrylonitrile and hydrogen cyanide |
-
1987
- 1987-08-29 CN CN 87101099 patent/CN1031662A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5840648A (en) * | 1997-09-02 | 1998-11-24 | The Standard Oil Company | Catalyst for the manufacture of acrylonitrile and hydrogen cyanide |
| US8585870B2 (en) | 2008-03-05 | 2013-11-19 | E I Du Pont De Nemours And Company | Process to C-manufacture acrylonitrile and hydrogen cyanide |
| CN102451710A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Acrylaldehyde catalyst prepared by propylene oxidation method and its preparation method |
| CN102451710B (en) * | 2010-10-21 | 2013-08-14 | 中国石油化工股份有限公司 | Acrylaldehyde catalyst prepared by propylene oxidation method and its preparation method |
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| PB01 | Publication | ||
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