CN1915501A - Catalyst for producing acrylonitrile from ammoxidation of propylene - Google Patents
Catalyst for producing acrylonitrile from ammoxidation of propylene Download PDFInfo
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- CN1915501A CN1915501A CNA2005100287680A CN200510028768A CN1915501A CN 1915501 A CN1915501 A CN 1915501A CN A2005100287680 A CNA2005100287680 A CN A2005100287680A CN 200510028768 A CN200510028768 A CN 200510028768A CN 1915501 A CN1915501 A CN 1915501A
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- catalyst
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- propylene
- acrylonitrile
- produce acrylonitrile
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
A fluidized-bed catalyst for preparing acrylonitrile from acrylamine by oxidizing with high output rate contains SiO2 as carrier and the active component. AaBbSrcMgdFeeBifCe1-fNagMo12Ox, where A is chosen from Li, K, Rb, and Cs, and B is chosen from W, P, B, Cr, Sb, Al, Ge, Nb, Ta and V.
Description
Technical field
The present invention relates to a kind of fluid catalyst of ammoxidating propylene to produce acrylonitrile.
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.Require the catalyst use instead should be able to long-time running under higher propylene load and higher reaction pressure for this reason, and keep higher acrylonitrile yield.
The load 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 magnesium is the basic element during catalyst is formed in the above-mentioned patent.The investigation condition of embodiment is a fixed bed simultaneously, and 430 ℃ of reaction temperatures are not mentioned reaction pressure concrete in the experimental implementation and operational load situation data.This fixed bed investigation condition is difficult to reflect the truth of fluidized bed process.
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, does not mention the situation data under high pressure, high operational load condition.
The place of the fluid catalyst of the present invention's ammoxidating propylene to produce acrylonitrile different from the past is: 1. element such as magnesium or cobalt is basic element or the optional element during catalyst was formed in the past, and catalyst of the present invention does not relate to elements such as magnesium and cobalt in forming, therefore the catalyst among the present invention is formed simple, cheap; 2. the invention provides a kind of fluid catalyst of new production acrylonitrile, be used for overcoming the catalyst that exists in the above-mentioned document and do not relate to problem than high-response pressure and operational load.
Summary of the invention
Technical problem to be solved by this invention is to overcome the catalyst that exists in the above-mentioned document not relate to problem than high-response pressure and operational load, and a kind of element novel propylene ammoxidation catalysts such as bismuth, magnesium or cobalt that do not relate to are provided.This catalyst can adapt under lower air/propylene mol ratio, higher reaction pressure and higher loading condiction to be operated, and can keep higher acrylonitrile yield.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of ammoxidating propylene to produce acrylonitrile fluid bed new catalyst, contain silica supports and with the following composition of atomic ratio measuring chemical formula:
A
aB
bSr
cMg
dFe
eBi
fCe
1-fNa
gMo
12O
x
A is selected from least a among Li, K, Rb, the Cs in the formula;
B is selected from least a among W, P, B, Cr, Sb, Al, Ge, Nb, Ta and the V;
The span of a is 0.01～2.0;
The span of b is 0.01～5.0;
The span of c is 0.1～6.0;
The span of d is 0.1～6.0;
The span of c+d is 1.0～8.0;
The span of e is 0.1～5.0;
The span of f is 0.01～1.0;
The span of g is 0.01～1.5;
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 0.01～1.0 in the technique scheme, the value preferable range of b is 0.01～3.5, the value preferable range of c is 0.1～4.5, the value preferable range of d is 0.1～4.5, the value preferable range of c+d is 3.5～7.0, the value preferable range of e is 0.1～4.0, and the value preferable range of f is 0.05～0.8, and the value preferable range of g is 0.01～1.0.
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; Niobium and the most handy nitrate of tantalum, 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 9.0～9.8.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 410～470 ℃, was preferably 420～440 ℃.Therefore catalyst of the present invention is a kind of catalyst that is applicable to higher reaction pressure and higher load, and reaction pressure can be more than 0.08MPa in process units, for example, and 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.
Though catalyst of the present invention is formed simple, but because it is right not only to have introduced new combined oxidation-reduction in catalyst is formed, and the existence of strontium and magnesium elements, the oxidisability and the reproducibility that have guaranteed catalyst are in good balance, thereby reduce the generation that reduces acrylonitrile because of the too weak pi-allyl dimerization of catalyst oxidation ability and the too strong deep oxidation of oxidability, make that catalyst has low air/propylene mol ratio (9.5: 1), (WWH is 0.085 hour than high-response pressure (0.14MPa), higher load
-1) operational capacity under the condition, and keep acrylonitrile yield preferably.
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]
8.5 gram sodium nitrate are mixed with 8.61 gram potassium nitrate, add water 25 grams and the dissolving of heating back, obtain material (A); 21.6 gram chromium trioxides are dissolved in the 20 gram water, get material (B); 897.6 gram ammonium molybdates are dissolved in 60～90 ℃ of hot water of 500 grams, get material (C); 123.3 gram bismuth nitrates, 73.6 gram cerous nitrates, 4.39 gram germanium oxides, 380.2 gram magnesium nitrates, 269 gram strontium nitrates and 345.8 gram ferric nitrates are mixed, add water 300 grams, after the heating for dissolving as material (D).
With material (A) and 1250 gram weight concentration is that 40% Ludox mixes, under agitation add material (C), (B), (D) and (E) 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
12Na
0.5Bi
0.6Ce
0.4Fe
2.0Mg
3.5Sr
3.0K
0.3Cr
0.5Ge
0.1O
x+50％SiO
2。
[embodiment 2～6 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.
Table 1
| Embodiment | Catalyst is formed | Acrylonitrile yield % |
| Embodiment 1 | Mo 12Na 0.5Bi 0.6Ce 0.4Fe 2.0Mg 3.5Sr 3.0K 0.3Cr 0.5Ge 0.1O x | 80.1 |
| Embodiment 2 | Mo 12Na 0.5Bi 0.6Ce 0.4Fe 2.0Mg 3.5Sr 3.0K 0.3Cs 0.05W 0.5Nb 0.1O x | 79.8 |
| Embodiment 3 | Mo 12Na 0.5Bi 0.6Ce 0.4Fe 2.0Mg 3.5Sr 3.0K 0.3B 0.5Sb 0.1O x | 79.9 |
| Embodiment 4 | Mo 12Na 0.5Bi 0.6Ce 0.4Fe 2.0Mg 3.5Sr 3.0K 0.2Cs 0.05V 0.3Nb 0.05O x | 80.3 |
| Embodiment 5 | Mo 12Na 0.5Bi 0.4Ce 0.6Fe 2.0Mg 3.5Sr 3.0K 0.2Cr 0.5V 0.5P 0.5O x | 80.3 |
| Embodiment 6 | Mo 12Na 0.5Bi 0.4Ce 0.6Fe 2.0Mg 3.5Sr 3.0K 0.5W 0.3P 0.3Sb 0.5O x | 80.0 |
| Embodiment 7 | Mo 12Na 0.5Bi 0.4Ce 0.6Fe 2.0Mg 3.5Sr 3.0K 0.5Cs 0.05W 1.0P 0.25O x | 80.2 |
| Comparative example 1 | Mo 12Bi 0.75Fe 2.0Ni 5.5K 0.17W 0.45O x | 78.1 |
| Comparative example 2 | Mo 12Bi 0.75Fe 2.0Ni 5.5Na 0.15K 0.21O x | 77.3 |
| Comparative example 3 | Mo 12Fe 2.0Ni 4.0Na 0.15K 0.15P 0.3Sb 0.5O x | 77.6 |
| Comparative example 4 | Mo 12Fe 2.0Ni 5.5Na 0.15Cs 0.09P 0.3V 0.3Ge 0.05O x | 77.5 |
Claims (10)
1, a kind of ammoxidating propylene to produce acrylonitrile fluid bed new catalyst, contain silica supports and with the following composition of atomic ratio measuring chemical formula:
A
aB
bSr
cMg
dFe
eBi
fCe
1-fNa
gMo
12O
x
A is selected from least a among Li, K, Rb, the Cs in the formula;
B is selected from least a among W, P, B, Cr, Sb, Al, Ge, Nb, Ta and the V;
The span of a is 0.01～2.0;
The span of b is 0.01～5.0;
The span of c is 0.1～6.0;
The span of d is 0.1～6.0;
The span of c+d is 1.0～8.0;
The span of e is 0.1～5.0;
The span of f is 0.01～1.0;
The span of g is 0.01～1.5;
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 ammoxidating propylene to produce acrylonitrile of claim 1, the span that it is characterized in that a is 0.01～1.0.
3, according to the fluid catalyst of the described ammoxidating propylene to produce acrylonitrile of claim 1, the span that it is characterized in that b is 0.01～3.5.
4, according to the fluid catalyst of the described ammoxidating propylene to produce acrylonitrile of claim 1, the span that it is characterized in that c is 0.1～4.5.
5, according to the fluid catalyst of the described ammoxidating propylene to produce acrylonitrile of claim 1, the span that it is characterized in that d is 0.1～4.5.
6, according to the fluid catalyst of the described ammoxidating propylene to produce acrylonitrile of claim 1, the span that it is characterized in that c+d is 3.5～7.0.
7, according to the fluid catalyst of the described ammoxidating propylene to produce acrylonitrile of claim 1, the span that it is characterized in that e is 0.1～4.0.
8, according to the fluid catalyst of the described ammoxidating propylene to produce acrylonitrile of claim 1, the span that it is characterized in that f is 0.05～0.8.
9, according to the fluid catalyst of the described ammoxidating propylene to produce acrylonitrile of claim 1, the span that it is characterized in that g is 0.01～1.0.
10, according to the fluid catalyst of the described ammoxidating propylene to produce acrylonitrile 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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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101306373B (en) * | 2007-05-16 | 2012-01-25 | 中国石油化工股份有限公司 | High load fluid bed catalyst for acrylonitrile production |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1086154C (en) * | 1998-03-30 | 2002-06-12 | 中国石油化工总公司 | Propylene ammonoxidating catalyst |
| CN1092540C (en) * | 1999-06-24 | 2002-10-16 | 中国石油化工集团公司 | Fluidized bed catalyst for ammoxidation of propylene |
| CN1100612C (en) * | 1999-08-19 | 2003-02-05 | 中国石油化工集团公司 | Fluidized bed catalyst for oxidation of propene ammonia |
| RO121181B1 (en) * | 1999-10-18 | 2007-01-30 | Mitsubishi Rayon Co., Ltd. | Process for producing acrylonitrile, catalyst to be used therefor and process for preparing the same |
| CN1104282C (en) * | 1999-10-28 | 2003-04-02 | 中国石化上海石油化工股份有限公司 | Fluidized-bed catalyst for ammoxidation of propylene or isobutylene |
| 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 |
| JP2002123291A (en) * | 2000-10-18 | 2002-04-26 | Olympus Optical Co Ltd | System controller |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101306373B (en) * | 2007-05-16 | 2012-01-25 | 中国石油化工股份有限公司 | High load fluid bed catalyst for acrylonitrile production |
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