CN103418403A - Low-temperature high-load catalyst for olefin ammoxidation reaction - Google Patents
Low-temperature high-load catalyst for olefin ammoxidation reaction Download PDFInfo
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- CN103418403A CN103418403A CN2012101504923A CN201210150492A CN103418403A CN 103418403 A CN103418403 A CN 103418403A CN 2012101504923 A CN2012101504923 A CN 2012101504923A CN 201210150492 A CN201210150492 A CN 201210150492A CN 103418403 A CN103418403 A CN 103418403A
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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
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Abstract
The invention relates to a low-temperature high-load catalyst for an olefin ammoxidation reaction, and mainly solves the problem of the low yield of acrylonitrile under conditions of low temperature and high load in the prior art. Through use of a technical scheme, the problem is well solved, and the technical scheme can be used in industrial production of acrylonitrile production. The technical scheme is shown as follows: the catalyst comprises a silicon dioxide carrier and a composition, the composition is represented by the following general formula: by atomic ratio, A[a]B[b]C[c]Fe[d]Ni[e]Mg[f]Bi[g]Mo[12]O[x], wherein A is at least one selected from the group consisting of Li, Na, K, Rb and Cs, B is one selected from the group consisting of Ca, Mn, Co, Cr, W and Ba, and C is selected from Nd or a mixture of Nd and at least one selected from La, Ce or Pr.
Description
Technical field
The present invention relates to a kind of low temperature high load capacity catalyst for the olefin ammoxidation reaction.
Background technology
Acrylonitrile is important Organic Chemicals, and it reacts production by ammoxidation of propylene.For obtaining the fluid catalyst of high activity, high selectivity, people, through constantly exploring, have carried out a series of improvement.These improve and mostly relate to the catalyst activity composition, focus on the collocation between catalyst activity component, improve the activity of catalyst with selective, thereby reach the raising of acrylonitrile once through yield, and produce the raising of loading.
Ammonia oxidation is produced acrylonitrile through the development of more than 40 years, and the production capacity of factory and the market demand have approached balance.The current Main Trends of The Development of acrylonitrile process, by newly-built large-scale device or extend former small-scale device and make unit scale production, further to cut down the consumption of raw materials and energy consumption, increase production capacity.
When original acrylonitrile installation expands energy, the useful load of requirement catalyst can not be too many, requires the catalyst of using instead under higher propylene load for this reason, keeps high acrylonitrile yield.After reactor size and production capacity are determined, the how many and catalyst of reactor charge catalyst can bear load relevant, i.e. WWH.Its definition is catalyst per ton, per hour can process the tonnage of propylene.When the reactor feed amount increases, if the load of catalyst is constant, the catalyst loading amount is also wanted corresponding increase.But cooling water pipe insufficient height in intrinsic fluidized-bed reactor, so the fluid height of catalyst reactor likely surpasses the height of cooling water pipe.In addition, because the reactor feed amount increases, so operating linear velocity also significantly improves.The combined influence of these two variations likely makes reactor dilute phase temperature rise, and causes carbon dioxide production to increase, and acrylonitrile selectively descends, and therefore the catalyst of higher WWH can prevent the problems referred to above.
Simultaneously, under the low-temp reaction condition, be unfavorable for that the accessory substance of easy polymerization generates, thereby contribute to the spatter property of production process, improve the refine and reclaim rate of device.
The WWH that improves in theory catalyst should increase the adsorption activation ability of catalyst to propylene, but there is no at present certain element in catalyst, can improve the report to propylene adsorption activation ability.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 in document US5093299 and US5212137.In this patent, introduce, its catalyst can operate under usually lower slightly reaction temperature, and it has higher catalytic activity and good oxidation-reduction stability, thereby compares conditional operation applicable to lower air/propylene.But it should be noted, the investigation condition of above-mentioned patent working example is fixed bed, 430 ℃ of reaction temperatures, do not mention reaction pressure concrete in experimental implementation and operational load situation data, more do not relate to catalyst reaction performance under high load capacity.
Introduced a kind of manufacture method of acrylonitrile in 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 in document embodiment is normal pressure.
With regard to the acrylonitrile yield of initial reaction stage, in above-mentioned patent document, disclosed catalyst has had larger improvement.But not only do not relate to catalyst acrylonitrile yield data under higher propylene load in above-mentioned all patents, more do not relate to catalyst acrylonitrile yield data under higher propylene load and lower reaction temperature.
A kind of catalyst that contains the preparing acrylonitrile by allylamine oxidation of at least one at least one in molybdenum, bismuth, cerium, iron, nickel, magnesium or zinc, potassium or caesium or rubidium is disclosed in document JP9401312 and CN1121321A.In this patent, introduce, its catalyst can prevent that acrylonitrile yield from reducing effectively in the situation that extend the reaction time, 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 invention provides a kind of new low temperature high load capacity catalyst for the olefin ammoxidation reaction, this catalyst not only has higher acrylonitrile yield under higher propylene load, and still there is higher acrylonitrile yield under higher propylene load and lower reaction temperature, improve the refine and reclaim rate of device simultaneously.
Summary of the invention
Technical problem to be solved by this invention be in conventional art under the low temperature high-load condition the low problem of acrylonitrile yield, a kind of new low temperature high load capacity catalyst for the olefin ammoxidation reaction is provided.This catalyst not only has higher acrylonitrile yield under higher propylene load, and still has advantages of higher acrylonitrile yield under higher propylene load and lower reaction temperature.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows, and a kind of low temperature high load capacity catalyst for olefin ammoxidation reaction contains silica supports and the following composition with the atomic ratio measuring chemical general formula:
A
aB
bC
cFe
dNi
eMg
fBi
gMo
12O
x
In formula, A is selected from least one in Li, Na, K, Rb and Cs;
B is selected from a kind of in Ca, Mn, Co, Cr, W and Ba;
C is selected from Nd or Nd and is selected from least one the mixture in La, Ce or Pr;
The span of a is 0.01～2.5;
The span of b is 0.00～5;
The span of c is 0.01～5;
The span of d is 0.01～5;
The span of e is 0.01～10;
The span of f is 0.01～5;
The span of g is 0.01～3;
X meets the required oxygen atom sum of each element valence in catalyst;
Wherein catalyst carrier is selected from silica, and its consumption is 30～70% by weight percentage.
In technique scheme, the value preferable range of a is 0.05～1.5, the value preferable range of b is 0.01～4, the value preferable range of c is 0.1～2.5, the value preferable range of d is 0.1～4, the value preferable range of e is 0.1～8, the value preferable range that the value preferable range of f is 0.1～4, g is 0.1～2.5.The preferred silica of catalyst carrier, its consumption preferable range is 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 to solution, then be mixed and made into slurry with carrier, 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 manufacturing catalyst of the present invention is:
Molybdenum oxide or ammonium molybdate for the molybdenum component in catalyst.
The most handy its nitrate of all the other each components, oxalates, hydroxide, oxide maybe can be decomposed into the salt of oxide.
Raw material as carrier silica can be used Ludox, silicon gel or both mixtures.If use Ludox, its quality will meet the requirement of CN1005248C.
It is 45～55% rear spray-dryings that the slurry heating prepared is concentrated to solid content.Spray dryer available pressure formula, two streamings or centrifugal turntable formula, but, with centrifugal better, can guarantee that the catalyst of making has good size distribution.
The roasting of catalyst can be divided into two stages and carry out: the decomposition of each element salt and high-temperature roasting in catalyst.The catabolic phase temperature is preferably 200～300 ℃, and the time is 0.5～2 hour.Sintering temperature is 500～800 ℃, is preferably 520～700 ℃; Roasting time is 20 minutes to 2 hours.Above-mentioned decomposition and roasting are carried out respectively in two roasters, also can in a stove, be divided into two zones, also can in the continous way rotary roasting furnace, complete simultaneously and decompose and roasting.To pass into appropriate air in catalyst decomposes and roasting process, to generate Catalytic active phase, and prevent that catalyst is by over reduction.
Adopt the specification of catalyst manufacture acrylonitrile of the present invention required propylene, ammonia and molecular oxygen identical with other ammoxidation catalyst of use.Although the low molecule saturated hydrocarbon content in raw material propylene there is no impact to reaction, from economic point of view consider density of propylene 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 due to some operational reason must with higher air than the time, can increase to 11, reaction is not had to significant impact.But, from security consideration, the excess of oxygen in reacting gas can not be greater than 7% (volume), preferably is not more than 4%.
When catalyst of the present invention is used for fluidized-bed reactor, reaction temperature is 400～470 ℃, is preferably 410～450 ℃.Therefore catalyst of the present invention is a kind of catalyst that is applicable to lower temperature, higher load, and in process units, reaction temperature can be more than 400 ℃, for example, and 400～430 ℃.Reaction pressure can be at 0.06 ~ 0.14MPa, if reaction pressure does not have any adverse effect lower than 0.06MPa yet, acrylonitrile yield can further improve.
The propylene load (WWH) of catalyst of the present invention is 0.045～0.15 hour
-1, be preferably 0.06～0.13 hour
-1.The too low catalyst of not only wasting of loading, also can make carbon dioxide production increase, and selective decline, be disadvantageous.Loading does not too highly have practical significance, because the catalyst addition is very few, can makes in catalyst layer the heat transfer area of cooling water pipe be less than and remove the required area of reaction heat, causes reaction temperature uncontrollable.
Manufacture the product purification and recover technique of acrylonitrile with catalyst of the present invention, available existing production technology, do not need to do any transformation.The eluting gas that is fluidized-bed reactor is removed unreacted ammonia through neutralizing tower, then by water at low temperature, whole organic products is absorbed.Absorption liquid, through extractive distillation, obtains high-purity propylene nitrile product after dehydrogenation cyanic acid and processed.
According to the isolation of Selective Oxidation active sites and alternate cooperative effect, catalyst of the present invention has been introduced suitable active sites isolation element and the mutually synergistic element of activity in forming, make to make in catalyst existing mutual cooperative effect between each phase, promote propylene to transform, there is again phase to play suitable buffer action to active sites, propylene is transformed to generating the acrylonitrile direction, thereby greatly reduce the deep oxidation accessory substance.Use the catalyst in the present invention to carry out the ammoxidation of propylene reaction, can load 0.085 hour at higher propylene
-1Obtain higher acrylonitrile yield 81.5% under 420 ℃ of lower reaction temperatures, obtained technique effect preferably.
In the fluidized-bed reactor that the activity examination of catalyst of the present invention is is 38 millimeters at internal diameter, carry out.Loaded catalyst 400 grams, reaction temperature 400-430 ℃, reaction pressure 0.084MPa, the raw material proportioning (mole) being propylene: ammonia: air=1: 1.25: 9.7, the propylene load (WWH) of catalyst is 0.085 hour
-1.
Selective and the once through yield of propylene conversion, acrylonitrile is defined as follows in the present invention:
The propylene molal quantity of reaction
Propylene conversion (%)=
* 100
The propylene feed molal quantity
Generate the acrylonitrile molal quantity
Acrylonitrile selective (%)=
* 100
The propylene molal quantity of reaction
Generate the acrylonitrile molal quantity
Acrylonitrile once through yield (%)=
* 100
The propylene feed molal quantity
Below by embodiment, the present invention is further elaborated.
The specific embodiment
[embodiment 1]
1.5 gram NaOH and 3.8 gram potassium hydroxide dissolve with adding after water 11 grams also heat, and obtain material (A); 789.0 gram ammonium molybdates are dissolved in 60～90 ℃ of hot water of 800 gram, obtain material (B); 153.6 gram bismuth nitrates, 132.0 gram manganese nitrates, 547.2 gram nickel nitrates, 304.1 gram ferric nitrates, 143.3 gram magnesium nitrates are mixed, add water 340 grams, after heating for dissolving, as material (C), take 64.7 gram neodymium nitrates and 22.6 gram chromic nitrates, add water 15 grams, obtain material (D).
The Ludox that is 40% with 2500 gram weight concentration by material (A) mixes, under agitation add successively material (B), (C) and (D), obtain slurry after fully stirring, according to well-established law, the slurry of making is carried out to the framboid moulding in spray dryer, at internal diameter, it is finally 89 millimeters, in 590 ℃ of roastings 2.0 hours, make and consist of in the rotary roasting furnace that length is 1700 millimeters (89 * 1700 millimeters of φ):
50%K
0.15Na
0.1Fe
2.0Ni
5.0Mn
1.0Mg
1.5Cr
0.6Nd
0.4Bi
0.85Mo
12.0O
x＋50%SiO
2。
[embodiment 2～6 and comparative example 1～4]
Adopt method preparation substantially the same manner as Example 1 to there are the different catalyst that form in following table, and carry out the reaction that ammoxidation of propylene generates acrylonitrile with prepared catalyst under following reaction condition, the results are shown in Table 1.
The reaction condition of above-described embodiment and comparative example is:
38 millimeters fluidized-bed reactors of φ
Reaction temperature 400-430 ℃
Reaction pressure 0.084MPa
Loaded catalyst 400 grams
Catalyst propylene load (WWH) 0.085 hour
-1
The raw material proportioning (mole) C
3 =/ NH
3/ air=1/1.25/9.7
Table 1
Claims (9)
1. the low temperature high load capacity catalyst for olefin ammoxidation reaction, contain the composition following with the atomic ratio measuring chemical general formula:
A
aB
bC
cFe
dNi
eMg
fBi
gMo
12O
x
In formula, A is selected from least one in Li, Na, K, Rb and Cs;
B is selected from a kind of in Ca, Mn, Co, Cr, W and Ba;
C is selected from Nd or Nd and is selected from least one the mixture in La, Ce or Pr;
The span of a is 0.01～2.5;
The span of b is 0.00～5;
The span of c is 0.01～5;
The span of d is 0.01～5;
The span of e is 0.01～10;
The span of f is 0.01～5;
The span of g is 0.01～3;
X meets the required oxygen atom sum of each element valence in catalyst;
Wherein catalyst carrier is selected from silica, and its consumption is 30～70% by weight percentage.
2. according to claim 1 for the low temperature high load capacity catalyst of olefin ammoxidation reaction, the span that it is characterized in that a is 0.05～1.5.
3. according to claim 1 for the low temperature high load capacity catalyst of olefin ammoxidation reaction, the span that it is characterized in that b is 0.01～4.
4. according to claim 1 for the low temperature high load capacity catalyst of olefin ammoxidation reaction, the span that it is characterized in that c is 0.1～2.5.
5. according to claim 1 for the low temperature high load capacity catalyst of olefin ammoxidation reaction, the span that it is characterized in that d is 0.1～4.
6. according to claim 1 for the low temperature high load capacity catalyst of olefin ammoxidation reaction, the span that it is characterized in that e is 0.1～8.
7. according to claim 1 for the low temperature high load capacity catalyst of olefin ammoxidation reaction, the span that it is characterized in that f is 0.1～4.
8. according to claim 1 for the low temperature high load capacity catalyst of olefin ammoxidation reaction, the span that it is characterized in that g is 0.1～2.5.
9. according to claim 1 for the low temperature high load capacity catalyst of olefin ammoxidation reaction, it is characterized in that catalyst carrier is silica, its consumption is 40～60% by weight percentage.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104923248A (en) * | 2014-03-17 | 2015-09-23 | 中国石油化工股份有限公司 | High-pressure high-load catalyst for olefin ammoxidation reaction |
| CN106299342A (en) * | 2016-10-28 | 2017-01-04 | 长沙矿冶研究院有限责任公司 | Lithium-rich anode material of K ion doping and high-voltage spinel/carbon double-coating and preparation method thereof |
| CN109772356A (en) * | 2019-03-07 | 2019-05-21 | 营口市向阳催化剂有限责任公司 | A kind of acrylonitrile catalyst and its preparation method and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5658842A (en) * | 1993-08-10 | 1997-08-19 | Asahi Kasei Kogyo Kabushiki Kaisha | Ammoxidation catalyst composition, and process for producing acrylonitrile or methacrylonitrile using the same |
| CN1507946A (en) * | 2002-12-17 | 2004-06-30 | 中国石油化工股份有限公司 | Fluidized bed catalyst for preparing acrylonitrile by ammonia oxidation of propene |
| CN101121128A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Fluidized bed catalyst for ammoxidating propylene to produce acrylonitrile |
| CN101147868A (en) * | 2006-09-20 | 2008-03-26 | 中国石油化工股份有限公司 | Fluid bed catalyst for acrylonitrile production |
| CN101767014A (en) * | 2009-01-07 | 2010-07-07 | 中国石油化工股份有限公司 | Fluidized bed catalyst for producing acrylonitrile by propylene ammoxidation |
-
2012
- 2012-05-16 CN CN2012101504923A patent/CN103418403A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5658842A (en) * | 1993-08-10 | 1997-08-19 | Asahi Kasei Kogyo Kabushiki Kaisha | Ammoxidation catalyst composition, and process for producing acrylonitrile or methacrylonitrile using the same |
| CN1507946A (en) * | 2002-12-17 | 2004-06-30 | 中国石油化工股份有限公司 | Fluidized bed catalyst for preparing acrylonitrile by ammonia oxidation of propene |
| CN101121128A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Fluidized bed catalyst for ammoxidating propylene to produce acrylonitrile |
| CN101147868A (en) * | 2006-09-20 | 2008-03-26 | 中国石油化工股份有限公司 | Fluid bed catalyst for acrylonitrile production |
| CN101767014A (en) * | 2009-01-07 | 2010-07-07 | 中国石油化工股份有限公司 | Fluidized bed catalyst for producing acrylonitrile by propylene ammoxidation |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104923248A (en) * | 2014-03-17 | 2015-09-23 | 中国石油化工股份有限公司 | High-pressure high-load catalyst for olefin ammoxidation reaction |
| CN106299342A (en) * | 2016-10-28 | 2017-01-04 | 长沙矿冶研究院有限责任公司 | Lithium-rich anode material of K ion doping and high-voltage spinel/carbon double-coating and preparation method thereof |
| CN109772356A (en) * | 2019-03-07 | 2019-05-21 | 营口市向阳催化剂有限责任公司 | A kind of acrylonitrile catalyst and its preparation method and application |
| CN109772356B (en) * | 2019-03-07 | 2020-06-02 | 营口市向阳催化剂有限责任公司 | Acrylonitrile catalyst and preparation method and application thereof |
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