CN1136980C - 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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- CN1136980C CN1136980C CNB001117157A CN00111715A CN1136980C CN 1136980 C CN1136980 C CN 1136980C CN B001117157 A CNB001117157 A CN B001117157A CN 00111715 A CN00111715 A CN 00111715A CN 1136980 C CN1136980 C CN 1136980C
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- catalyst
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- acrylonitrile
- propylene
- 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
The present invention relates to a fluid bed catalyst used for producing acrylonitrile by propylene ammoxidation, which comprises a silicon dioxide carrier and a composition with a chemical formula counted by atomic ratio: A<a>B<b>C<c>Ge<d>Mn<e>W<f>Fe<g>Bi<h>Mo<i>O<x>, wherein A is at least two kinds of Li, Na, K, Rb and Cs, B is at least one kind of Co, Ni, Cr, Ca, Mg, La, Ce and V, and C is at least one kind of B, P and As. The catalyst of the present invention is especially suitable for being used under conditions of lower reaction temperature, higher reaction pressure and high propene loading, high single yield of acrylonitrile and high ammonia conversion rate can be maintained, and the present invention can be used for industrial production.
Description
Technical field
The present invention relates to the 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 30 years of development, and the production capacity of factory and the market demand are near balance.The main development trend of acrylonitrile process has been turned to the transformation of original factory, further to cut down the consumption of raw materials and to increase production capacity by the construction new equipment 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.
The reaction pressure of fluidized-bed reactor is to be determined to the resistance drop that absorbs a series of heat exchangers, tower and pipe arrangement the cat head by reactor outlet.Because the increase of production capacity obviously increases the inventory of reactor outlet, above-mentioned resistance drop is increased.In addition, each heat exchanger heat transfer area also need increase heat transmission equipment inadequately, and resistance drop is further increased.Because environmental requirement, the reactor off-gas that absorbs cat head is forbidden directly to be discharged in the atmosphere, deliver to stove and burn.If like this without air-introduced machine, then must improve the absorption tower top pressure.For all the foregoing reasons, the operating pressure of reactor will increase by 0.5～1.0 times than design load at present, promptly reaches more than the 0.08MPa.
Above-mentioned second load that problem is a catalyst, i.e. WWH.Its definition is a catalyst per ton, per hour manageable tonnage.Because the increase of reactor feed amount, if the load of catalyst is constant, then the catalyst useful load is also wanted corresponding increase.But cooling water pipe insufficient height in the intrinsic fluidized-bed reactor, so the fluid height of catalyst reactor might surpass the height of cooling water pipe.In addition, because the increase of reactor feed amount, so operating linear velocity also significantly improves.The combined influence of these two variations might make reactor dilute phase temperature rise, and causes carbon dioxide production to increase, and the acrylonitrile selectivity descends.Therefore the WWH of catalyst is higher can prevent the problems referred to above.If can effectively reduce reaction temperature, can cut down the consumption of energy on the one hand in addition, also can improve reaction condition on the other hand, reach the purpose that improves 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 single-pass yield of acrylonitrile, but the propylene of catalyst load is lower, and single-pass yield of acrylonitrile descends bigger under higher reaction pressure.Studies show that further the B component in the above-mentioned catalyst is relevant with performance under high pressure to the load of catalyst with M.Though some element in the B component has effect to improving single-pass yield of acrylonitrile, and the raising of catalyst loading and the performance of high-response pressure are had negative effect, be unfavorable for that catalyst adapts to elevated pressures, operates under the higher load condition.Once in stipulating in CN1021638C in addition that above-mentioned catalyst was formed, the summation of i and j is 12, promptly is a constant.Cancel this regulation in the present invention,, will influence single-pass yield of acrylonitrile because molybdenum component will reduce when increasing by this regulation M component.
Introduced a kind of germanic ammoxidation catalyst that obtains the high acrylonitrile yield among document US 5688739 and the US5770757.Adopt molybdenum, bismuth, germanium system in the document, alkali metal containing in the optional elements, but the unexposed example that contains sodium among the embodiment, only disclosing reaction pressure in addition in the document is the reaction condition of normal pressure, not the concrete investigation data under high pressure, high-load condition.
Summary of the invention
The objective of the invention is to overcome the catalyst that exists in the above-mentioned document and do not relate to adaptation, a kind of fluid catalyst of new ammoxidating propylene to produce acrylonitrile is provided than high-response pressure, high operational load and in the reaction temperature problem of reactivity worth under the low condition slightly.This catalyst can adapt at higher reaction pressure, higher load and the lower slightly and lower air/propylene of reaction temperature to be operated than under the condition, and keeps high acrylonitrile once through yield and high ammonia conversion ratio.
The objective of the invention is to realize by following technical scheme: a kind of fluidized bed catalyst for ammoxidation of propylene, form by silica supports with the following composition of atomic ratio measuring chemical formula:
A
aB
bC
cGe
dMn
eW
fFe
gBi
hMo
iO
x
A is selected among Li, Na, K, Rb or the Cs at least two kinds in the formula;
B is selected from least a among Co, Ni, Cr, Ca, Mg, La, Ce or the V;
C is selected from least a among B, P or the As;
The span of a is 0.01～1.5;
The span of b is 0.1～12.0;
The span of c is 0.1～0.6;
The span of d is 0.01～2.0;
The span of e is 0.01～2.5;
The span of f is 0.05～1.5;
The span of g is 0.1～4.0;
The span of h is 0.2～2.5;
The span of i is 12.0～14.5;
X satisfies the required oxygen atom sum of each element valence in the catalyst;
Wherein catalyst carrier is selected from silica, and its consumption is 30～70% by weight percentage.
The value preferable range of a is 0.01～0.7 in the technique scheme, and the value preferable range of c is 0.1～0.45, and the value preferable range of d is 0.01～1.0, and the value preferable range of e is 0.2～1.5, and the value preferable range of f is 0.1～1.0.
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:
The molybdenum component is with molybdenum oxide or ammonium molybdate in the catalyst.
The most handy corresponding acids of phosphorus, arsenic and boron or its ammonium salt in the catalyst; Tungsten can be with ammonium tungstate or its oxide; Vanadium can be used ammonium metavanadate; Its oxide of germanium; The most handy chromium trioxide of chromium, chromic nitrate or the mixture of the two; Other component can maybe can be decomposed into the salt of oxide with its nitrate, oxide, but preferably uses water miscible nitrate.
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, prevent that catalyst is by over reduction.
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 420～470 ℃, was preferably 425～450 ℃.Therefore catalyst of the present invention is a kind of low reaction temperatures, high pressure, high load capacity catalyst of being applicable to, reaction pressure can be more than 0.08MPa in process units, for example, and 0.08～0.15MPa.Also do not have any adverse effect if reaction pressure is lower than 0.08MPa, single-pass yield of acrylonitrile can further improve.
The propylene load (WWH) of catalyst of the present invention is 0.06～0.15 hour
-1, be preferably 0.07～0.10 hour
-1Loading to hang down not only wastes catalyst, and carbon dioxide production is increased, and selectivity descends, and is disadvantageous.Loading does not too highly have practical significance, because the catalyst addition is very few, the heat transfer area that can make cooling water pipe in the catalyst layer causes reaction temperature uncontrollable less than removing the required area of reaction heat.
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.
The present invention is by adding component germanium and tungsten in molybdenum, bismuth, iron catalyst system and catalyzing, find that this catalyst system and catalyzing has than high-response pressure (0.14MPa), and (WWH is 0.085 hour to higher load
-1) operational capacity under the condition, in catalyst system, add component manganese again, find that this catalyst system and catalyzing under 430 ℃ of conditions of reaction temperature, has advantages of high catalytic activity and selectivity; Suitably add other effective active components and nonmetalloid B, P in addition or/and As, make this catalyst 430 ℃ of reaction temperatures, elevated pressures 0.14MPa, higher load 0.085 hour
-1With low air/propylene ratio is (mole) condition under to operate at 9.5: 1, and its acrylonitrile once through yield reaches as high as 80.3%, and the ammonia conversion ratio can reach 98%, has obtained effect 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]
2.16 gram cesium nitrates, 1.64 gram potassium nitrate are mixed, add water 30 gram and heating for dissolving, obtain material (A); 7.02 gram germanium dioxides, 11.48 gram ammonium tungstates and 421.8 gram ammonium molybdates are dissolved in 60～90 ℃ of hot water of 350 grams, get material (B); 10.8 gram chromium trioxides are dissolved in the 15 gram water, get material (C); 67.2 gram bismuth nitrates, 17.47 gram manganese nitrates, 282 gram nickel nitrates, 48.4 gram cerous nitrates, 102 gram magnesium nitrates and 168 gram ferric nitrates are mixed, add water 190 grams, after the heating for dissolving as material (D); Take by weighing phosphoric acid solution 4.12 grams as material (E).
With material (A) and 1280 gram weight concentration is that 40% Ludox mixes, under agitation add material (B), (C), (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 590 ℃ of roastings 1.5 hours, make and consist of 50%K
0.1Cs
0.07P
0.020Ni
5.6Cr
0.35Ce
0.35Mg
1.2Ge
0.05Mn
0.2W
0.15Fe
2.0Bi
0.75Mo
13.0O
x+ 50%SiO
2[embodiment 2～8 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
Unstripped gas proportioning (mole) C
3 =/ NH
3/ air=1/1.2/9.5
Table 1
| Embodiment | Catalyst is formed | Acrylonitrile yield % | Acrylonitrile selectivity % | Ammonia conversion ratio % | Propylene conversion % |
| Embodiment 1 | K 0.1Cs 0.07P 0.020Ni 5.6Cr 0.35Ce 0.35Mg 1.2Ge 0.05Mn 0.2W 0.15Fe 2.0Bi 0.75Mo 13.0O x | 80.3 | 81.9 | 98.0 | 98.0 |
| Embodiment 2 | K 0.1Cs 0.07P 0.020Ni 5.6Cr 0.35Ce 0.35Mg 1.2Ge 0.05Mn 0.25W 0.2Fe 2.0Bi 0.75Mo 13.0O x | 79.9 | 81.7 | 97.2 | 97.8 |
| Embodiment 3 | K 0.08Na 0.2Cs 0.05P 0.020Ni 5.6Cr 0.35La 0.30Mg 1.2Ge 0.05Mn 0.2W 0.15Fe 2.0Bi 0.75Mo 13.0O x | 79.2 | 81.1 | 98.1 | 97.6 |
| Embodiment 4 | K 0.08Na 0.25Cs 0.05P 0.020Ni 3.0Cr 2.5Ce 0.35Mg 1.2Ge 0.05Mn 0.2W 0.15Fe 2.0Bi 0.75Mo 13.0O x | 79.3 | 81.4 | 96.9 | 97.4 |
| Embodiment 5 | K 0.08Na 0.2Cs 0.05P 0.020Cr 0.35Co 4.5Ce 0.35Ge 0.1Mn 0.25W 0.2Fe 2.0Bi 0.75Mo 13.0O x | 79.6 | 81.0 | 96.8 | 98.2 |
| Embodiment 6 | K 0.15Cs 0.07P 0.020Ni 3.0Co 2.5Cr 0.35Ce 0.35Mg 1.2Ge 0.05Mn 0.25W 0.15Fe 2.0Bi 0.75Mo 13.0O x | 80.0 | 81.8 | 97.4 | 97.8 |
| Embodiment 7 | Li 0.05Na 0.2Rb 0.065P 0.025Ni 6.0Cr 0.35La 0.35Ge 0.05Mn 0.20W 0.15Fe 2.0Bi 0.75Mo 13.0O x | 79.0 | 80.1 | 98.2 | 98.6 |
| Embodiment 8 | K 0.15Rb 0.05Cs 0.05Ni 3.0Co 2.5Cr 0.35Ce 0.35Mg 1.2Ge 0.05Mn 0.25W 0.10Fe 2.0Bi 0.75Mo 13.0O x | 78.6 | 80.7 | 98.8 | 97.4 |
| Comparative example 1 | Mo 12Bi 0.9Fe 1.8Ni 2.0Co 5.0Na 0.15Mn 0.45Cr 0.45K 0.17Cs 0.05O x | 76.8 | |||
| Comparative example 2 | Mo 12Bi 0.9Fe 1.8Ni 2.4Co 4.3Na 0.15W 0.45Cr 0.45K 0.15Cs 0.07O x | 77.1 | |||
| Comparative example 3 | Mo 12Bi 0.9Fe 1.8Ni 2.0Co 5.0Na 0.15Mn 0.45Cr 0.45K 0.21O x | 76.2 | |||
| Comparative example 4 | Mo 12Bi 0.9Fe 1.8Ni 5.0Mg 2.0Na 0.15W 0.45Cr 0.45Cs 0.09O x | 77.4 |
Claims (6)
1, a kind of fluid catalyst of ammoxidating propylene to produce acrylonitrile, form by silica supports with the following composition of atomic ratio measuring chemical formula:
A
aB
bC
cGe
dMn
eW
fFe
gBi
hMo
iO
x
A is selected among Li, Na, K, Rb or the Cs at least two kinds in the formula;
B is selected from least a among Co, Ni, Cr, Ca, Mg, La, Ce or the V;
C is selected from least a among B, P or the As;
The span of a is 0.01～1.5;
The span of b is 0.1～12.0;
The span of c is 0.1～0.6;
The span of d is 0.01～2.0;
The span of e is 0.01～2.5;
The span of f is 0.05～1.5;
The span of g is 0.1～4.0;
The span of h is 0.2～2.5;
The span of i is 12.0～14.5;
X satisfies the required oxygen atom sum of each element valence in the catalyst;
Wherein catalyst carrier is selected from silica, and its consumption is 30～70% by weight percentage.
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 0.01～0.7.
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 c is 0.1～0.45.
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 d is 0.01～1.0.
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 e is 0.2～1.5.
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 f is 0.1～1.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001117157A CN1136980C (en) | 2000-02-24 | 2000-02-24 | Fluidized bed catalyst for ammoxidating propylene to produce acrylonitrile |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001117157A CN1136980C (en) | 2000-02-24 | 2000-02-24 | Fluidized bed catalyst for ammoxidating propylene to produce acrylonitrile |
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|---|---|
| CN1310046A CN1310046A (en) | 2001-08-29 |
| CN1136980C true CN1136980C (en) | 2004-02-04 |
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|---|---|---|---|
| CNB001117157A Expired - Fee Related CN1136980C (en) | 2000-02-24 | 2000-02-24 | Fluidized bed catalyst for ammoxidating propylene to produce acrylonitrile |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004050240A1 (en) | 2002-12-02 | 2004-06-17 | The Standard Oil Company | Mixed oxide catalyst of k, cs, ce, cr, co, ni, fe, bi and mo for the manufacture of acrylonitrile |
| US7071140B2 (en) | 2002-12-02 | 2006-07-04 | The Standard Oil Company | Catalyst for the manufacture of acrylonitrile |
| CN100358629C (en) * | 2004-09-24 | 2008-01-02 | 中国石油化工股份有限公司 | Fluidized bed catalyst for preparing acetonitrile |
| US8455388B2 (en) | 2010-03-23 | 2013-06-04 | Ineos Usa Llc | Attrition resistant mixed metal oxide ammoxidation catalysts |
| US8258073B2 (en) | 2010-03-23 | 2012-09-04 | Ineos Usa Llc | Process for preparing improved mixed metal oxide ammoxidation catalysts |
| US8420566B2 (en) | 2010-03-23 | 2013-04-16 | Ineos Usa Llc | High efficiency ammoxidation process and mixed metal oxide catalysts |
| US8153546B2 (en) | 2010-03-23 | 2012-04-10 | Ineos Usa Llc | Mixed metal oxide ammoxidation catalysts |
| JPWO2014129496A1 (en) * | 2013-02-21 | 2017-02-02 | 三菱レイヨン株式会社 | Catalyst for producing acrylonitrile and method for producing acrylonitrile |
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2000
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