CN1810360A - Fluid-bed catalyst for propylene ammoxidation to prepare acrylonitrile - Google Patents
Fluid-bed catalyst for propylene ammoxidation to prepare acrylonitrile Download PDFInfo
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- CN1810360A CN1810360A CNA2005100236034A CN200510023603A CN1810360A CN 1810360 A CN1810360 A CN 1810360A CN A2005100236034 A CNA2005100236034 A CN A2005100236034A CN 200510023603 A CN200510023603 A CN 200510023603A CN 1810360 A CN1810360 A CN 1810360A
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Abstract
The fluid bed catalyst for preparing acrylonitrile through ammoxidizing propylene contains silica carrier and the composition AaBbCcDdaNbeFefBigMo12Ox, where A is at least one of Li, Na, K, Rb and Cs; B is at least one of Ni, Co, Mg, Ca, Ba, Zn, Ge, Mn and Pb; C is at least one of B, P, Sb, Cr, W and V; and D is at least two of La, Ce, Pr and Sm. The catalyst has excellent oxidation-reduction stability, capability of obtaining high acrylonitrile yield at high reaction pressure and high propylene load, and acrylonitrile yield unchanged after long term running, can result in greatly raised acrylonitrile producing efficiency and economic performance, and may be used in industrial acrylonitrile production.
Description
Technical field
The present invention relates to the fluid catalyst of preparing acrylonitrile by allylamine oxidation.
Background technology
Acrylonitrile is important Organic Chemicals, and it is produced by the ammoxidation of propylene reaction.For obtaining the fluid catalyst of high activity, high selectivity, people have carried out a series of improvement through constantly exploring.These improve and mostly relate to the catalyst activity composition, pay attention to the collocation between the catalyst activity component, and improve activity of such catalysts and selectivity, thereby reach the raising of acrylonitrile once through yield, and the raising of producing load.
Ammonia oxidation is produced acrylonitrile through 40 years of development, and the production capacity of factory and the market demand are near balance.The main development trend of acrylonitrile process is built the technological transformation that new equipment turns to original factory by emphasis, further to cut down the consumption of raw materials and to increase production capacity at present.By transformation to original factory, change the bottleneck in effective catalyst and the elimination production technology, the production capacity of acrylonitrile might improve 50～80%, and required investment only is 20～30% of a new device, economic benefit is very huge.
Can produce two problems during factory transforms: 1. the reaction pressure of fluidized-bed reactor will rise; 2. the useful load of catalyst can not be too many.The catalyst that for this reason requires to use instead should have higher propylene load and can bear higher reaction pressure, and keeps higher acrylonitrile yield.
The WWH that improves catalyst in theory should increase the adsorption activation ability of catalyst to propylene, but at present still in the catalyst-free certain element can improve report to propylene adsorption activation ability.The catalyst of following composition has been proposed in document CN1021638C:
A
aB
bC
cNi
dCo
eNa
fFe
gBi
hM
iMo
jO
x
Wherein A is potassium, rubidium, caesium, samarium, thallium; B is manganese, magnesium, strontium, calcium, barium, lanthanum, rare earth element; C is phosphorus, arsenic, boron, antimony, chromium; M is tungsten, vanadium.
Above-mentioned catalyst can obtain higher acrylonitrile yield, but the propylene of catalyst load is lower, and acrylonitrile yield descends bigger under higher reaction pressure.
Introduced the catalyst that a kind of catalyst that uses molybdenum, bismuth, iron, nickel, magnesium, potassium and caesium system carries out preparing acrylonitrile by allylamine oxidation among document US 5093299 and the US5212137.Introduce in this patent, its catalyst can be operated under lower slightly usually reaction temperature, and it has advantages of high catalytic activity and advantages of excellent oxidation-reduction stability, thereby compares conditional operation applicable to lower air/propylene.But it should be noted that the investigation condition of above-mentioned patent working example is a fixed bed, 430 ℃ of reaction temperatures are not mentioned reaction pressure concrete in the experimental implementation and operational load situation data.Introduced a kind of manufacture method of acrylonitrile among the flat 8-27089 of document, it adopts the catalyst of molybdenum, bismuth, iron, magnesium and tungsten system to carry out the ammoxidation of propylene reaction, and the investigation condition among the document embodiment is a normal pressure.
With regard to the acrylonitrile yield of initial reaction stage, disclosed catalyst has had bigger improvement in the above-mentioned patent document.But all do not relate to catalyst acrylonitrile yield data under higher propylene load and higher reaction pressure in above-mentioned all patents, more do not relate to catalyst under higher propylene load and higher reaction pressure, acrylonitrile yield data after the long-time running.
A kind of catalyst that contains preparing acrylonitrile by allylamine oxidation at least a at least a in molybdenum, bismuth, cerium, iron, nickel, magnesium or the zinc, potassium or caesium or the rubidium is disclosed among document JP 9401312 and the CN1121321A.Introduce in this patent, its catalyst can prevent effectively under the situation in reaction time that acrylonitrile yield from reducing prolonging, but its evaluating catalyst is to carry out under quite low reaction pressure and low operational load condition.
The place of the fluid catalyst of the present invention's ammoxidating propylene to produce acrylonitrile different from the past is: the fluid catalyst that the invention provides a kind of new production acrylonitrile, this catalyst not only has higher acrylonitrile yield under higher propylene load and higher reaction pressure, and long-time running under these conditions, acrylonitrile yield remains unchanged.
Summary of the invention
Technical problem to be solved by this invention is the problem that does not relate in the conventional art that catalyst is loaded at high propylene, reacts under the high-response pressure condition, and a kind of fluid catalyst of new preparing acrylonitrile by allylamine oxidation is provided.This catalyst not only has higher acrylonitrile yield under higher propylene load and higher reaction pressure, and long-time running under these conditions, and acrylonitrile yield remains unchanged.
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 preparing acrylonitrile by allylamine oxidation, contain silica supports and with the following composition of atomic ratio measuring chemical formula:
A
aB
bC
cD
dNb
eFe
fBi
gMo
12O
x
A is selected from least a among Li, Na, K, Rb or the Cs in the formula;
B is selected from least a among Ni, Co, Mg, Ca, Ba, Zn, Ge, Mn or the Pb;
C is selected from least a among B, P, Sb, Cr, W or the V;
D is selected from least two kinds among La, Ce, Pr or the Sm;
The span of a is 0.01～1.5;
The span of b is 0.1～12.0;
The span of c is 0.01～5.0;
The span of d is 0.01～3.5;
The span of e is 0.001～1.0;
The span of f is 0.1～7.0;
The span of g is 0.01～3.0;
X satisfies the required oxygen atom sum of each element valence in the catalyst;
Wherein the consumption of carrier silica is 30～70% by weight percentage in the catalyst.
The value preferable range of a is 0.1～0.7 in the technique scheme, the value preferable range of b is 0.1～8.0, the value preferable range of c is 0.1～1.5, the value preferable range of d is 0.1～1.2, the value preferable range of e is 0.01～0.5, the value preferable range of f is 0.1～4.0, and the value preferable range of g is 0.1～2.0, and the consumption preferable range of carrier silica is 40～60% by weight percentage in the catalyst.
The manufacture method of catalyst of the present invention there is no specific (special) requirements, can be undertaken by well-established law.At first the catalyst each component is made solution, be mixed and made into slurry with carrier again, the spray-dried microspheroidal that is shaped to, catalyst is made in last roasting.The preparation of slurry is preferably undertaken by the CN1005248C method.
The raw material of making catalyst of the present invention is:
Molybdenum component in the catalyst is with molybdenum oxide or ammonium molybdate.
The most handy corresponding acids of phosphorus in the catalyst and boron or its ammonium salt; Germanium can be used germanium oxide; The most handy corresponding oxide of tungsten and antimony or its ammonium salt; The most handy nitrate of niobium, hydroxide and oxide; The most handy chromium trioxide of chromium, chromic nitrate or the mixture of the two; 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, silicon gel or both mixtures as carrier silica.If use Ludox, its quality will meet the requirement of CN1005248C.
It is 47～55% back spray-dryings that the prepared slurry heating is concentrated to solid content.Spray dryer available pressure formula, two streamings or centrifugal turntable formula, but, can guarantee that the catalyst of making has good size distribution with centrifugal better.
The roasting of catalyst can be divided into two stages and carry out: each element decomposition of salts and high-temperature roasting in the catalyst.The catabolic phase temperature is preferably 200～300 ℃, and the time is 0.5～2 hour.Sintering temperature is 500～800 ℃, is preferably 550～700 ℃; Roasting time is 20 minutes to 2 hours.Above-mentioned decomposition and roasting are carried out respectively in two roasters, also can be divided into two zones in a stove, also can finish simultaneously in the continous way rotary roasting furnace and decompose and roasting.In catalyst decomposes and roasting process, to feed an amount of air,, and prevent that catalyst is by over reduction with generation catalytic activity phase.
Adopt the specification of catalyst manufacturing acrylonitrile of the present invention required propylene, ammonia and molecular oxygen identical with other ammoxidation catalyst of use.Though the low molecule saturated hydrocarbon content in the raw material propylene to the reaction did not influence, considers that from economic point of view density of propylene is more preferably greater than 85% (mole).Ammonia can be used fertilizer grade liquefied ammonia.Reaction desired molecule oxygen can be used pure oxygen from technical standpoint, oxygen enrichment and air, but from economy and the most handy air of security consideration.
Entering the ammonia of fluidized-bed reactor and the mol ratio of propylene is between 0.8～1.5, is preferably 1.0～1.3.The mol ratio of air and propylene is 8～10.5, is preferably 8.8～9.8.If owing to some operational reason must with higher air than the time, can increase to 11, reaction is not had significant impact.But from security consideration, the excess of oxygen in the reacting gas can not preferably be not more than 4% greater than 7% (volume).
When catalyst of the present invention was used for fluidized-bed reactor, reaction temperature was 410～460 ℃, was preferably 420～440 ℃.Catalyst of the present invention is a kind of usually lower slightly reaction temperature that is applicable to, high pressure, high load capacity catalyst, and therefore reaction pressure can be more than 0.08MPa in process units, for example, 0.08～0.18MPa.Also do not have any adverse effect if reaction pressure is lower than 0.08MPa, acrylonitrile yield can further improve.
The propylene load (WWH) of catalyst of the present invention is 0.06～0.15 hour
-1, be preferably 0.08～0.12 hour
-1Loading to hang down not only wastes catalyst, and carbon dioxide production is increased, and selectivity descends, and is disadvantageous.
The product of making acrylonitrile with catalyst of the present invention reclaims process for refining, and available existing production technology need not done any transformation.The eluting gas that is fluidized-bed reactor is removed unreacted ammonia through neutralizing tower, with water at low temperature whole organic products is absorbed again.Absorption liquid gets high-purity propylene nitrile product through extractive distillation after dehydrogenation cyanic acid and the processed.
Brought into play good synergism between each component of catalyst of the present invention, it is right to have introduced combined oxidation-reduction in the catalyst simultaneously, quicken gas phase oxygen and entered caltalyst phase and the body diffusion of oxygen mutually, make the oxidation rapidly of reacted catalyst, again recover active, thereby help improving activity of such catalysts and stability.Use the catalyst among the present invention to carry out the ammoxidation of propylene reaction, not only can under higher propylene load and higher reaction pressure, obtain higher acrylonitrile yield, even prolong the reaction time, acrylonitrile yield almost remains unchanged, and has obtained better technical effect.
Activity of such catalysts of the present invention examination is to carry out in internal diameter is 38 millimeters fluidized-bed reactor.Loaded catalyst 400 grams, 430 ℃ of reaction temperatures, reaction pressure 0.14MPa, raw material proportioning (mole) is a propylene: ammonia: air=1: 1.2: 9.5, the propylene load (WWH) of catalyst is 0.085 hour
-1
Propylene conversion, acrylonitrile selectivity and once through yield are defined as follows in the present invention:
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
1.84 gram cesium nitrates, 3.19 gram sodium nitrate are mixed with 2.25 gram potassium nitrate, add water 30 grams and the dissolving of heating back, obtain material (A); 9.60 gram chromium trioxides are dissolved in the 15 gram water, get material (B); 402.8 gram ammonium molybdates are dissolved in 60～90 ℃ of hot water of 350 grams, get material (C); 18.4 gram bismuth nitrates, 307.2 gram nickel nitrates, 110.7 gram cobalt nitrates, 16.5 gram cerous nitrates, 19.4 gram lanthanum nitrates, 5.05 gram nitric acid niobiums and 151.2 gram ferric nitrates are mixed, add water 250 grams, after the heating for dissolving as material (D).
With material (A) and 1280 gram weight concentration is that 40% Ludox mixes, under agitation add material (C), (B) and (D) successively, after fully stirring, get slurry, according to well-established law the slurry of making is carried out the framboid moulding in spray dryer, it is 89 millimeters at internal diameter at last, length be in the rotary roasting furnace of 1700 millimeters (89 * 1700 millimeters of φ) in 600 ℃ of roastings 2.0 hours, make and consist of:
50％Mo
12Bi
0.2Ce
0.2La
0.35Co
2.0Fe
2.0Ni
5.5Nb
0.1Na
0.29K
0.1Cs
0.05Cr
0.5O
x+50％SiO
2。
[embodiment 2～7 and comparative example 1～4]
Adopt method preparation substantially the same manner as Example 1 to have the different catalyst of forming in the following table, and under following reaction condition, carry out the reaction that ammoxidation of propylene generates acrylonitrile, the results are shown in Table 1 with prepared catalyst.
The reaction condition of the foregoing description and comparative example is:
38 millimeters fluidized-bed reactors of φ
430 ℃ of reaction temperatures
Reaction pressure 0.14MPa
Loaded catalyst 400 grams
Catalyst propylene load (WWH) 0.085 hour
-1
Raw material proportioning (mole) C
3 =/ NH
3/ air=1/1.2/9.5
Reaction result was calculated in the reaction beginning in back 4 hours, 200 hours, 500 hours and 800 hours respectively
Table 1
| Embodiment | Catalyst is formed | Acrylonitrile yield % | |||
| 4 hours | 200 hours | 500 hours | 800 hours | ||
| Embodiment 1 | Mo 12Bi 0.2Ce 0.2La 0.35Co 2.0Fe 2.0Ni 5.5Nb 0.1Na 0.29K 0.1Cs 0.05Cr 0.5O x | 80.1 | 80.2 | 80.3 | 80.1 |
| Embodiment 2 | Mo 12Bi 0.2Ce 0.2Sm 0.2Fe 2.0Ni 7.5Na 0.29K 0.1Nb 0.05Cr 0.5W 0.5Zn 0.5O x | 80.0 | 79.9 | 79.9 | 79.8 |
| Embodiment 3 | Mo 12Bi 0.7Ce 0.2Pr 0.1Mg 2.0Fe 2.0Ni 5.5Na 0.29K 0.1Nb 0.2B 0.3W 1.0O x | 80.4 | 80.3 | 80.4 | 80.3 |
| Embodiment 4 | Mo 12Bi 0.7Ce 0.2La 0.15Mg 2.0Fe 2.0Ni 5.5Na 0.29K 0.1Cs 0.05Nb 0.1Cr 0.5V 0.3Zn 0.5O x | 80.1 | 80.1 | 80.2 | 80.1 |
| Embodiment 5 | Mo 12Bi 0.7Ce 0.2La 0.05Co 2.0Fe 2.0Ni 5.5Na 0.29K 0.1Cs 0.05Cr 0.5Nb 0.5P 0.5O x | 79.8 | 80.2 | 80.0 | 80.0 |
| Embodiment 6 | Mo 12Bi 0.4Ce 0.2Pr 0.2Fe 2.0Ni 7.5Na 0.29K 0.05Nb 0.2Ge 0.3P 0.3Sb 0.5O x | 80.0 | 79.8 | 79.7 | 79.7 |
| Embodiment 7 | Mo 12Bi 0.75Ce 0.2La 0.4Fe 2.0Co 2.0Ni 7.5Na 0.29K 0.1Nb 0.05V 0.3Sb 0.5O x | 80.2 | 79.9 | 80.0 | 79.9 |
| Comparative example 1 | Mo 12Bi 0.25Fe 3.0Ni 7.5Na 0.15K 0.17Ce 0.45O x | 80.1 | 79.6 | 79.1 | 78.0 |
| Comparative example 2 | Mo 12Bi 0.25Fe 3.0Ni 7.5Na 0.15K 0.21O x | 80.4 | 79.0 | 78.4 | 78.3 |
| Comparative example 3 | Mo 12Ce 0.45Fe 3.0Ni 7.5Na 0.15K 0.15Cs 0.07O x | 80.2 | 78.8 | 78.5 | 77.7 |
| Comparative example 4 | Mo 12Ce 0.45Fe 3.0Ni 7.5Na 0.15Cs 0.09O x | 79.7 | 79.4 | 78.4 | 78.3 |
Claims (9)
1, a kind of fluid catalyst of preparing acrylonitrile by allylamine oxidation, contain silica supports and with the following composition of atomic ratio measuring chemical formula:
A
aB
bC
cD
dNb
eFe
fBi
gMo
12O
x
A is selected from least a among Li, Na, K, Rb or the Cs in the formula;
B is selected from least a among Ni, Co, Mg, Ca, Ba, Zn, Ge, Mn or the Pb;
C is selected from least a among B, P, Sb, Cr, W or the V;
D is selected from least two kinds among La, Ce, Pr or the Sm;
The span of a is 0.01～1.5;
The span of b is 0.1～12.0;
The span of c is 0.01～5.0;
The span of d is 0.01～3.5;
The span of e is 0.001～1.0;
The span of f is 0.1～7.0;
The span of g is 0.01～3.0;
X satisfies the required oxygen atom sum of each element valence in the catalyst;
Wherein the consumption of carrier silica is 30～70% by weight percentage in the catalyst.
2, according to the fluid catalyst of the described preparing acrylonitrile by allylamine oxidation of claim 1, the span that it is characterized in that a is 0.1～0.7.
3, according to the fluid catalyst of the described preparing acrylonitrile by allylamine oxidation of claim 1, the span that it is characterized in that b is 0.1～8.0.
4, according to the fluid catalyst of the described preparing acrylonitrile by allylamine oxidation 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 preparing acrylonitrile by allylamine oxidation of claim 1, the span that it is characterized in that d is 0.1～1.2.
6, according to the fluid catalyst of the described preparing acrylonitrile by allylamine oxidation of claim 1, the span that it is characterized in that e is 0.01～0.5.
7, according to the fluid catalyst of the described preparing acrylonitrile by allylamine oxidation of claim 1, the span that it is characterized in that f is 0.1～4.0.
8, according to the fluid catalyst of the described preparing acrylonitrile by allylamine oxidation of claim 1, the span that it is characterized in that g is 0.1～2.0.
9, according to the fluid catalyst of the described preparing acrylonitrile by allylamine oxidation of claim 1, the consumption that it is characterized in that carrier silica in the catalyst is 40～60% by weight percentage.
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105435793A (en) * | 2014-09-17 | 2016-03-30 | 中国石油化工股份有限公司 | Catalyst used for synthesizing ethylidene diacetate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1094073C (en) * | 1999-08-19 | 2002-11-13 | 中国石油化工集团公司 | Fluidized bed catalyst for production of acrylonitrile |
| WO2001028985A1 (en) * | 1999-10-18 | 2001-04-26 | Mitsubishi Rayon Co., Ltd. | Method for producing acrylonitrile, catalyst for use therein and the method for preparing the same |
| CN1152008C (en) * | 2001-11-14 | 2004-06-02 | 中国石油化工股份有限公司 | Fluidized bed catalyst for preparing acrylonitrile by propene ammoxidation |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105435793A (en) * | 2014-09-17 | 2016-03-30 | 中国石油化工股份有限公司 | Catalyst used for synthesizing ethylidene diacetate |
| CN105435793B (en) * | 2014-09-17 | 2018-01-09 | 中国石油化工股份有限公司 | Catalyst for ethylidene diacetate synthesis |
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