CN1107541C - Fluid bed catalyst for acrylonitrile production - Google Patents
Fluid bed catalyst for acrylonitrile production Download PDFInfo
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- CN1107541C CN1107541C CN99119954A CN99119954A CN1107541C CN 1107541 C CN1107541 C CN 1107541C CN 99119954 A CN99119954 A CN 99119954A CN 99119954 A CN99119954 A CN 99119954A CN 1107541 C CN1107541 C CN 1107541C
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- acrylonitrile
- propylene
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Abstract
The present invention relates to a fluid bed catalyst used for producing acrylonitrile, which comprises a silicon dioxide carrier and a composition with a chemical formula (by atomic ratio): A<a>B<b>C<c>Gr<d>La<e>Mg<f>Fe<g>Bi<h>Mo<i>O<x>, wherein A is at least one of Li, Na, K, Rb and Cs; B is at least one of Ni, Mn, Co, Ca, Sr, W, Ce and Zn; C is at least one of B, P and As. The catalyst of the present invention is particularly suitable for being used under conditions of low temperature which is slightly lower than usual reaction temperature, low ratio of air to propylene, higher reaction pressure and high propene load. The present invention can maintain high single yield of acrylonitrile and can be used for industrial production.
Description
The present invention relates to a kind of fluid catalyst of producing acrylonitrile.
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.
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 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.Find out that from embodiment its catalyst system and catalyzing is not contain sodium, though mention thulium cerium and chromium in the optional elements, only use as optional elements.There is not to disclose the collocation operating position of other rare earth element and chromium and magnesium elements among the embodiment.The investigation condition of embodiment is a fixed bed, 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.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.
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 objective of the invention is to overcome the catalyst that exists in the above-mentioned document and do not relate to problem, a kind of fluid catalyst of new production acrylonitrile is provided than high-response pressure and operational load.This catalyst can adapt under usually lower slightly reaction temperature, higher reaction pressure and higher loading condiction to be operated, and keeps high acrylonitrile once through yield.
The objective of the invention is to realize by following technical scheme: a kind of fluid catalyst of producing acrylonitrile, contain silica supports and with the following composition of atomic ratio measuring chemical formula:
A
aB
bC
cCr
dLa
eMg
fFe
gBi
hMo
iO
x
A is selected among Li, Na, K, Rb or the Cs at least a in the formula;
B is selected among Ni, Mn, Co, Ca, Sr, W, Ce or the Zn at least a;
C is selected among B, P or the As at least a;
The span of a is 0.01～1.5;
The span of b is 0.1～10.0;
The span of c is 0～0.6;
The span of d is 0.05～1.0;
The span of e is 0.05～2.0;
The span of f is 0.8～7.5;
The span of g is 0.1～8.0;
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, aluminium oxide or its mixture; Its consumption is 30～70% by weight percentage.
The value preferable range of a is 0.01～0.7 in the technique scheme, the value preferable range of c is 0.01～0.45, the value preferable range of d is 0.1～0.5, the value preferable range of e is 0.3～1.0, the value preferable range of f is 1.0～4.0, the value preferable range of g is 1.0～3.0, and the value preferable range of h is 0.2～2.5.The preferred silica of carrier in the catalyst, its consumption are 40～60% by weight percentage.
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, arsenic and boron or its ammonium salt; Tungsten can be with ammonium tungstate or tungsten 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, 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 ℃.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, 0.08～0.15MPa.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.
Because the magnesium in the component is loaded to improving, the reduction reaction temperature is favourable, lanthanum can improve the performance of catalyst under high-response pressure, therefore remove some have negative effect to high pressure, high load capacity reactivity worth component, increase the use amount of magnesium, and magnesium, lanthanum and chromium uses simultaneously, makes that catalyst has had in 430 ℃ lower slightly usually of reaction temperatures, (WWH is 0.085 hour than high-response pressure (0.14MPa), higher load
-1) operational capacity under the condition, and the acrylonitrile once through yield has been up to 79.6% level, 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 400g, 430 ℃ of reaction temperatures, reaction pressure 0.14MPa, raw material proportioning (mole) is a propylene: ammonia: air=1: 1.2: 9.8, 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.[embodiment 1]
1.8 gram cesium nitrates, 4.05 gram sodium nitrate and 2.36 gram potassium nitrate are mixed, add water 30 grams and the dissolving of heating back, obtain material (A); 10.15 gram chromium trioxides are dissolved in the 10 gram water, get material (B); 457.5 gram ammonium molybdates are dissolved in 60～90 ℃ of hot water of 350 grams, get material (C); 92.2 gram bismuth nitrates, 23.4 gram manganese nitrates, 268 gram nickel nitrates, 62.8 gram lanthanum nitrates, 217 gram magnesium nitrates and 196 gram ferric nitrates are mixed, add water 150 grams, after the heating for dissolving as material (D); Take by weighing phosphoric acid solution 4.01 grams as material (E).
With material (A) and 1296 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 605 ℃ of roastings 1.5 hours, make and consist of
50％K
0.15Na
0.20Cs
0.05P
0.05Ni
5.0Mn
0.15Cr
0.55La
0.45Mg
2.5Fe
2.5Bi
1.0Mo
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, the results are shown in Table 1 with carrying out the reaction that ammoxidation of propylene generates acrylonitrile under the prepared catalyst reaction condition below.
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 gram catalyst propylene loads (WWH) 0.085 hour
-1Raw material proportioning (mole) C
3 =/ NH
3/ air=1/1.2/9.8
Table 1
| Embodiment | Catalyst is formed | Acrylonitrile yield % | Acrylonitrile selectivity % | Propylene conversion % |
| Embodiment 1 | K 0.15Na 0.20Cs 0.05P 0.05Ni 5.0Mn 0.15Cr 0.55La 0.45Mg 2.5Fe 2.5Bi 1.0Mo 13.0O x | 79.6 | 81.0 | 98.3 |
| Embodiment 2 | K 0.15Na 0.20Cs 0.05P 0.05Co 1.5Ni 2.5Mn 0.15Cr 0.55La 0.45Mg 2.5Fe 2.5Bi 1.0Mo 13.0O x | 79.3 | 80.9 | 98.0 |
| Embodiment 3 | K 0.10Rb 0.1Cs 0.1P 0.025Ni 5.6Mn 0.15Cr 0.55La 0.45Mg 2.0Fe 2.5Bi 0.75Mo 13.0O x | 79.5 | 81.3 | 97.8 |
| Embodiment 4 | K 0.1Na 0.20Rb 0.025Cs 0.07As 0.05Ni 5.6Cr 0.45La 0.50Mg 2.0Fe 2.5Bi 1.0Mo 13.0O x | 78.9 | 80.8 | 97.6 |
| Embodiment 5 | K 0.1Na 0.28Cs 0.07B 0.025P 0.035Ni 5.0W 0.2Cr 0.50La 0.35Mg 2.0Bi 0.75Mo 13.0O x | 79.2 | 80.6 | 98.2 |
| Embodiment 6 | K 0.1Na 0.28Cs 0.07As 0.05Ni 5.0W 0.2Cr 0.50La 0.25Mg 2.0Fe 2.5Bi 0.75Mo 13.0O x | 79.0 | 80.1 | 98.6 |
| Embodiment 7 | K 0.15Na 0.20Rb 0.05Cs 0.1P 0.025Ni 5.6Mn 0.15W 0.15Cr 0.55La 0.45Mg 2.0Fe 2.5Bi 0.75Mo 13.0O x | 78.8 | 80.1 | 98.4 |
| Embodiment 8 | K 0.1Rb 0.1Cs 0.05P 0.045Ni 5.6Mn 0.10W 0.15Cr 0.35La 0.40Mg 2.5Fe 2.5Bi 1.0Mo 13.0O x | 79.2 | 80.8 | 98.0 |
| 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 0.5W 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 (8)
1, a kind of fluid catalyst of producing acrylonitrile, contain silica supports and with the following composition of atomic ratio measuring chemical formula:
A
aB
bC
cCr
dLa
eMg
fFe
gBi
hMo
iO
x
A is selected among Li, Na, K, Rb or the Cs at least a in the formula;
B is selected among Ni, Mn, Co, Ca, Sr, W, Ce or the Zn at least a;
C is selected among B, P or the As at least a;
The span of a is 0.01～1.5;
The span of b is 0.1～10.0;
The span of c is 0～0.6;
The span of d is 0.05～1.0;
The span of e is 0.05～2.0;
The span of f is 0.8～7.5;
The span of g is 0.1～8.0;
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, aluminium oxide or its mixture; Its consumption is 30～70% by weight percentage.
2, according to the fluid catalyst of the described production 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 production acrylonitrile of claim 1, the span that it is characterized in that c is 0.01～0.45.
4, according to the fluid catalyst of the described production acrylonitrile of claim 1, the span that it is characterized in that d is 0.1～0.5.
5, according to the fluid catalyst of the described production acrylonitrile of claim 1, the span that it is characterized in that e is 0.3～1.0.
6, according to the fluid catalyst of the described production acrylonitrile of claim 1, the span that it is characterized in that f is 1.0～4.0.
7, according to the fluid catalyst of the described production acrylonitrile of claim 1, the span that it is characterized in that g is 1.0～3.0.
8, according to the fluid catalyst of the described production acrylonitrile of claim 1, it is characterized in that carrier is selected from silica, its consumption is 40～60% by weight percentage.
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|---|---|---|---|
| CN99119954A CN1107541C (en) | 1999-11-03 | 1999-11-03 | Fluid bed catalyst for acrylonitrile production |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99119954A CN1107541C (en) | 1999-11-03 | 1999-11-03 | Fluid bed catalyst for acrylonitrile production |
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| CN1107541C true CN1107541C (en) | 2003-05-07 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103894203B (en) * | 2012-12-27 | 2017-02-08 | 中国石油化工股份有限公司 | High-load catalyst for olefin ammoxidation reactions |
| CN104275193B (en) * | 2013-07-09 | 2017-06-20 | 中国石油化工股份有限公司 | metathesis catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5212137A (en) * | 1990-01-09 | 1993-05-18 | Standard Oil Company | Catalyst for the manufacture of acrylonitrile and methacrylonitrile |
| CN1021638C (en) * | 1990-11-05 | 1993-07-21 | 中国石油化工总公司 | Fluidized catalyst for acrylonitrile |
-
1999
- 1999-11-03 CN CN99119954A patent/CN1107541C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5212137A (en) * | 1990-01-09 | 1993-05-18 | Standard Oil Company | Catalyst for the manufacture of acrylonitrile and methacrylonitrile |
| CN1021638C (en) * | 1990-11-05 | 1993-07-21 | 中国石油化工总公司 | Fluidized catalyst for acrylonitrile |
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