CN101121128A - Fluidized bed catalyst for ammoxidating propylene to produce acrylonitrile - Google Patents
Fluidized bed catalyst for ammoxidating propylene to produce acrylonitrile Download PDFInfo
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- CN101121128A CN101121128A CNA2006100299447A CN200610029944A CN101121128A CN 101121128 A CN101121128 A CN 101121128A CN A2006100299447 A CNA2006100299447 A CN A2006100299447A CN 200610029944 A CN200610029944 A CN 200610029944A CN 101121128 A CN101121128 A CN 101121128A
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Abstract
The present invention relates to a fluidized bed catalyst of acrylonitrile, which is produced by a propylene ammoxidation. The present invention mainly solves the problem that an acrylonitrile yield of a prior acrylonitrile catalyst is reduced under a quite high propylene load and a quite high reaction pressure. The present invention solves the problems well by a technical proposal that the catalyst consists of a combination which contains a silicon dioxide carrier, and a combination chemical formula counted at an atomic ratio is as follows: in a formula of AaBbCcDdNieNafFegBihMo12Ox, the A is selected from at least one of Li, K, Rb, Cs or Tl; the B is selected from at least one of W, P, B, Cr or Sb; the C is selected from at least one of Al, Ge or Nb; the D is selected from at least one of Zn or Mg. The present invention can be used for the industrial production of the acrylonitrile.
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 the investigation condition of embodiment is a fixed bed in the above-mentioned patent, 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. 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 cobalt element 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 fluid catalyst of new ammoxidating propylene to produce acrylonitrile is 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 fluid catalyst of ammoxidating propylene to produce acrylonitrile, contain silica supports and with the following composition of atomic ratio measuring chemical formula:
A
aB
bC
cD
dNi
eNa
fFe
gBi
hMo
12O
x
A is selected from least a among Li, K, Rb, Cs or the Tl in the formula;
B is selected from least a among W, P, B, Cr or the Sb;
C is selected from least a among Al, Ge or the Nb;
D is selected from least a among Zn or the Mg;
The span of a is 0.005～1.0;
The span of b is 0～2.5;
The span of c is 0～1.0;
The span of d is 0.1～6.0;
The span of e is 0.1～6.5;
The span of f is 0.005～1.0;
The span of g is 0.5～4.0;
The span of h is 0.05～1.5;
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.
A value preferable range is 0.05～0.7 in the technique scheme, b value preferable range is 0～1.5, c value preferable range is 0～0.7, d value preferable range is 0.5～4.0, e value preferable range is 0.5～4.5, f value preferable range is 0.05～0.7, and g value preferable range is 0.5～3.0, and h value preferable range is 0.1～1.2.The consumption 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 hydroxide of niobium and oxide or its solable matter; 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 catalyst has kept good oxidation and reducing power balance in forming, reduced the further oxidation of product acrylonitrile, under the high propylene conversion situation of maintenance, improved the acrylonitrile selectivity, made catalyst in low air/propylene mol ratio (9.5: 1), (WWH is 0.085 hour than high-response pressure (0.14MPa), higher load
-1) operating condition under, acrylonitrile yield can reach 80.1%, 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 present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
8.3 gram sodium nitrate are mixed with 8.46 gram potassium nitrate, add water 25 grams and the dissolving of heating back, obtain material (A); 21.91 gram chromium trioxides are dissolved in the 20 gram water, add 10.0 gram niobium oxide then and get material (B); 881.6 gram ammonium molybdates are dissolved in 60～90 ℃ of hot water of 500 grams, get material (C); 201.9 gram bismuth nitrates, 427.9 gram nickel nitrates, 309.5 gram zinc nitrates and 339.7 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) 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％K
0.3Cr
0.5Nb
0.1Zn
2.5Ni
3.5Na
0.5Fe
2.0Bi
1.0Mo
12O
x+50％SiO
2。
[embodiment 2～16 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 | 50％K 0.3Cr 0.5Nb 0.3Zn 2.5Ni 3.5Na 0.5Fe 2.0Bi 1.0Mo 12O x+50％SiO 2 | 79.7 |
| Embodiment 2 | 50％Cs 0.3P 0.5W 0.2Ge 0.3Mg 2.5Ni 3.5Na 0.5Fe 2.0Bi 1.0Mo 12O x+50％SiO 2 | 79.5 |
| Embodiment 3 | 50％K 0.3Cr 0.5Zn 2.5Ni 3.5Na 0.5Fe 2.0Bi 1.0Mo 12O x+50％SiO 2 | 79.7 |
| Embodiment 4 | 50％K 0.3Ge 0.3Mg 2.5Ni 3.5Na 0.5Fe 2.0Bi 1.0Mo 12O x+50％SiO 2 | 79.5 |
| Embodiment 5 | 50％K 0.3P 0.5Al 0.1Mg 2.0Zn 1.5Ni 3.5Na 0.5Fe 2.0Bi 1.0Mo 12O x+50％SiO 2 | 79.8 |
| Embodiment 6 | 50％K 0.3Cs 0.1Mg 2.0Zn 1.5Ni 3.5Na 0.5Fe 2.0Bi 1.0Mo 12O x+50％SiO 2 | 79.5 |
| Embodiment 7 | 50％K 0.3Cs 0.2Mg 2.5Ni 3.5Na 0.5Fe 2.0Bi 1.0Mo 12O x+50％SiO 2 | 79.7 |
| Embodiment 8 | 50％K 0.3Cs 0.2Zn 2.5Ni 3.5Na 0.5Fe 2.0Bi 1.0Mo 12O x+50％SiO 2 | 79.7 |
| Embodiment 9 | 50％K 0.3Ge 0.3Zn 2.5Ni 3.5Na 0.5Fe 2.0Bi 1.0Mo 12O x+50％SiO 2 | 79.8 |
| Embodiment 10 | 50％Li 0.3Ge 0.3Mg 2.0Zn 1.5Ni 3.5Na 0.5Fe 2.0Bi 1.0Mo 12O x+50％SiO 2 | 80.1 |
| Embodiment 11 | 50％Li 0.3W 0.3Mg 2.5Ni 3.5Na 0.5Fe 2.0Bi 1.0Mo 12O x+50％SiO 2 | 80.0 |
| Embodiment 12 | 50％Li 0.3Ge 0.3Zn 1.5Ni 3.5Na 0.5Fe 2.0Bi 1.0Mo 12O x+50％SiO 2 | 79.5 |
| Embodiment 13 | 45％Li 0.3W 0.3Mg 2.5Ni 3.5Na 0.5Fe 2.0Bi 1.0Mo 12O x+55％SiO 2 | 79.6 |
| Embodiment 14 | 45％K 0.3Cs 0.1Mg 2.0Zn 1.5Ni 3.5Na 0.5Fe 2.0Bi 1.0Mo 12O x+55％SiO 2 | 79.8 |
| Embodiment 15 | 45％Cs 0.3P 0.5W 0.2Ge 0.3Mg 2.5Ni 3.5Na 0.5Fe 2.0Bi 1.0Mo 12O x+55％SiO 2 | 79.6 |
| Embodiment 16 | 45％K 0.3Cs 0.2Mg 2.5Ni 3.5Na 0.5Fe 2.0Bi 1.0Mo 12O x+55％SiO 2 | 79.8 |
| 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 0.3Ge 0.05O x | 77.5 |
Claims (10)
1. the fluid catalyst of an ammoxidating propylene to produce acrylonitrile, contain silica supports and with the following composition of atomic ratio measuring chemical formula:
A
aB
bC
cD
dNi
eNa
fFe
gBi
hMo
12O
x
A is selected from least a among Li, K, Rb, Cs or the Tl in the formula;
B is selected from least a among W, P, B, Cr or the Sb;
C is selected from least a among Al, Ge or the Nb;
D is selected from least a among Zn or the Mg;
The span of a is 0.005～1.0;
The span of b is 0～2.5;
The span of c is 0～1.0;
The span of d is 0.1～6.0;
The span of e is 0.1～6.5;
The span of f is 0.005～1.0;
The span of g is 0.5～4.0;
The span of h is 0.05～1.5;
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 catalyst of the described ammoxidating propylene to produce acrylonitrile of claim 1, it is characterized in that a span is 0.05～0.7.
3. according to the catalyst of the described ammoxidating propylene to produce acrylonitrile of claim 1, it is characterized in that the b span is 0～1.5.
4. according to the catalyst of the described ammoxidating propylene to produce acrylonitrile of claim 1, it is characterized in that the c span is 0～0.7.
5. according to the catalyst of the described ammoxidating propylene to produce acrylonitrile of claim 1, it is characterized in that the d span is 0.5～4.0.
6. according to the catalyst of the described ammoxidating propylene to produce acrylonitrile of claim 1, it is characterized in that the e span is 0.5～4.5.
7. according to the catalyst of the described ammoxidating propylene to produce acrylonitrile of claim 1, it is characterized in that the f span is 0.05～0.7.
8. according to the catalyst of the described ammoxidating propylene to produce acrylonitrile of claim 1, it is characterized in that the g span is 0.5～3.0.
9. according to the catalyst of the described ammoxidating propylene to produce acrylonitrile of claim 1, it is characterized in that the h span is 0.1～1.2.
10. according to the catalyst of the described ammoxidating propylene to produce acrylonitrile of claim 1, it is characterized in that carrier silica consumption is 40～60% by weight percentage in the catalyst.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103418403A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Low-temperature high-load catalyst for olefin ammoxidation reaction |
| CN103418406A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Low-temperature high-load catalyst for olefin ammoxidation reaction |
| CN103657669A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Fluidized bed catalyst for preparing unsaturation nitrile through ammoxidation and method thereof |
| CN105980051A (en) * | 2013-04-11 | 2016-09-28 | 科莱恩公司 | Method for producing a catalyst for the partial oxidation/ammoxidation of olefins |
| CN113477243A (en) * | 2015-03-31 | 2021-10-08 | 旭化成株式会社 | Method for producing oxide catalyst and method for producing unsaturated nitrile |
-
2006
- 2006-08-11 CN CNB2006100299447A patent/CN100506377C/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103418403A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Low-temperature high-load catalyst for olefin ammoxidation reaction |
| CN103418406A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Low-temperature high-load catalyst for olefin ammoxidation reaction |
| CN103657669A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Fluidized bed catalyst for preparing unsaturation nitrile through ammoxidation and method thereof |
| CN105980051A (en) * | 2013-04-11 | 2016-09-28 | 科莱恩公司 | Method for producing a catalyst for the partial oxidation/ammoxidation of olefins |
| CN113477243A (en) * | 2015-03-31 | 2021-10-08 | 旭化成株式会社 | Method for producing oxide catalyst and method for producing unsaturated nitrile |
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|---|---|
| CN100506377C (en) | 2009-07-01 |
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