CN103894203B - High-load catalyst for olefin ammoxidation reactions - Google Patents
High-load catalyst for olefin ammoxidation reactions Download PDFInfo
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- CN103894203B CN103894203B CN201210575745.1A CN201210575745A CN103894203B CN 103894203 B CN103894203 B CN 103894203B CN 201210575745 A CN201210575745 A CN 201210575745A CN 103894203 B CN103894203 B CN 103894203B
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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 invention relates to a high-load catalyst for olefin ammoxidation reactions in order to solve a problem that the acrylonitrile yield of previous technologies is low. The high-load catalyst comprises a silica carrier and a composition represented by AaBbCcCadNieMgfFegBihMo13.6Ox, wherein A is selected from at least one of Li, Na, K, Rb, Cs and Tl, B is selected from at least one of La, Ce, Pr and Nd, and C is at least one or a mixture of Cr and W. The catalyst has an excellent redox stability, and can still realize a high acrylonitrile yield when the catalyst is used under high propylene load conditions, so the problem is solved, thereby the production efficiency and the production economy of acrylonitrile are substantially improved, and the catalyst can be used in industrial production.
Description
Technical field
The present invention relates to a kind of olefin ammoxidation reacts high load capacity catalyst.
Background technology
Acrylonitrile is important Organic Chemicals, and it is to react by ammoxidation of propylene to produce.For obtain high activity,
The fluid catalyst of high selectivity, people explore through continuous, have carried out a series of improvement.These improve and are directed to greatly be catalyzed
Agent activity composition, focusing on the collocation between catalyst activity component, improving activity and the selectivity of catalyst, thus reaching third
The raising of alkene nitrile once through yield, and the raising of produce load.
Ammonia oxidation produces the development that acrylonitrile was through more than 40 years, and the production capacity of factory and the market demand are close to flat
Weighing apparatus.The Main Trends of The Development of acrylonitrile process at present, makes device by newly-built large-scale device or the former small-scale device of enlarging
Large-scale production, to cut down the consumption of raw materials further and energy consumption, increases production capacity.
The useful load that original acrylonitrile installation expands requirement catalyst during energy can not be too many, requires the catalyst used instead to exist for this
Under higher propylene load, keep high acrylonitrile yield.After reactor size and production capacity determine, reactor filling is urged
Agent how many with catalyst can bearing load relevant, i.e. WWH.Its definition is catalyst per ton, can process propylene per hour
Tonnage.When reactor feed amount increases, if the load of catalyst is constant, catalyst useful load also will accordingly increase.But
Cooling water pipe insufficient height in intrinsic fluidized-bed reactor, the fluid height of therefore catalyst reactor is possible to exceed
The height of cooling water pipe.Further, since reactor feed amount increases, so operating linear velocity also significantly improves.This two changes
Combined influence there is a possibility that reactor dilute phase temperature rises, and causes carbon dioxide production to increase, acrylonitrile selectivity declines, because
The catalyst of this higher WWH can prevent the problems referred to above.
Meanwhile, at reaction conditions, it is unfavorable for that the accessory substance being easily polymerized generates, thus contributing to the cleaning of production process
Property, improve the refined recovery rate of device.
The WWH improving catalyst in theory should increase the adsorption activation ability to propylene for the catalyst, but at present
There is no certain element in catalyst can improve the report to propylene adsorption activation ability.Document US5093299 and US5212137
In describe a kind of use molybdenum, bismuth, iron, nickel, the catalyst of magnesium, potassium and caesium system carry out urging of preparing acrylonitrile by allylamine oxidation
Agent.Introduce in this patent, its catalyst can operate under generally lower slightly reaction temperature, its have higher catalysis activity and
Excellent oxidation-reduction stability, thus be applicable to relatively low air/propylene and compare conditional operation.It is noted that, on
The investigation condition stating patent Example is fixed bed, and 430 DEG C of reaction temperatures do not refer to specific reaction pressure in experimental implementation
With operational load situation data, more without reference to catalyst reaction performance under high load capacity.
A kind of manufacture method of acrylonitrile is described, it adopts molybdenum, bismuth, iron, magnesium and tungsten system in the flat 8-27089 of document
Catalyst carries out ammoxidation of propylene reaction, and the investigation condition in document embodiment is normal pressure.
For the acrylonitrile yield of initial reaction stage, the catalyst disclosed in above-mentioned patent document there has been larger changing
Enter.But in above-mentioned all patents not only without reference to catalyst under higher propylene load acrylonitrile yield data, more do not have
It is related to catalyst acrylonitrile yield data under higher propylene load and relatively low reaction temperature.
A kind of containing at least one in molybdenum, bismuth, cerium, iron, nickel, magnesium or zinc is disclosed in document JP9401312 and CN1121321A
The catalyst of the preparing acrylonitrile by allylamine oxidation of kind, potassium or at least one of caesium or rubidium.Introduce in this patent, its catalyst exists
Acrylonitrile yield can be effectively prevented in the case of extending the reaction time reduce, but its evaluating catalyst is at a fairly low reaction
Carry out under the conditions of pressure and low operational load.
The place that present invention ammoxidation of propylene different from the past produces the fluid catalyst of acrylonitrile is：The present invention carries
For a kind of new olefin ammoxidation reaction high load capacity catalyst, this catalyst has higher propylene under higher propylene load
Nitrile yield, and improve the refined recovery rate of device simultaneously.
Content of the invention
The technical problem to be solved is to provide a kind of new olefin ammoxidation reaction high load capacity catalyst, and this is urged
Agent has higher acrylonitrile yield under higher propylene load, and improves the refined recovery rate of device simultaneously.This
The technical scheme of bright employing is as follows, and a kind of olefin ammoxidation reacts high load capacity catalyst, containing silica supports with atom
The composition following than meter chemical general formula：
AaBbCcCadNieMgfFegBihMo13.6Ox
In formula, A is selected from least one in Li, Na, K, Rb, Cs and Tl；
B is selected from least one in La, Ce, Pr, Nd；
C is selected from least one or its mixture in Cr, W；
The span of a is 0.01～2.5；
The span of b is 0.01～5；
The span of c is 0.01～5；
The span of d is 0.005～0.1；
The span of e is 0.1～10；
The span of f is 0.1～5；
The span of g is 0.1～5；
The span of h is 0.01～3；
X is to meet the oxygen atom sum needed for each element chemical valence in catalyst；
Wherein catalyst carrier is selected from silica, and its consumption is 30～70% by weight percentage.
In technique scheme, the value preferred scope of a is the value preferred scope of 0.05～1.5, b for 0.1～3, c
Value preferred scope is the value preferred scope of 0.05～3, d is the value preferred scope of 0.01～0.08, e for 0.5～9, f
The value preferred scope for 0.5～4, g for the value preferred scope is the value preferred scope of 0.5～4, h is 0.2～2.5.Catalyst
Carrier is silica, preferably uses Ludox, and its consumption preferred scope is 40%～60% by weight percentage.
The manufacture method of catalyst of the present invention has no particular/special requirement, can carry out by well-established law.First by catalyst each component system
Become solution, then be mixed and made into slurry with carrier, spray-dried be shaped to microspheroidal, catalyst is made in last roasting.Slurry
Prepare and preferably carry out by CN1005248C method.
Manufacture catalyst of the present invention raw material be：
Molybdenum component molybdenum oxide in catalyst or ammonium molybdate.
Remaining each component is preferably with its nitrate, oxalates, hydroxide, oxide or the salt that can be analyzed to oxide
Class.
Raw material as carrier silicas can be with Ludox, Silica hydrogel or both mixtures.If using Ludox, its
Quality will meet the requirement of CN1005248C.
It is spray drying after 47～55% that the slurry heating preparing is concentrated to solid content.Spray dryer available pressure formula,
Two streamings or centrifugal turntable formula, but with centrifugal preferable, can guarantee that the catalyst made has good size distribution.
The roasting of catalyst can be divided into two stages to carry out：The decomposition of each element salt and high-temperature roasting in catalyst.Point
Preferably 200～300 DEG C of solution phase temperature, the time is 0.5～2 hour.Sintering temperature is 500～800 DEG C, preferably 520～
700℃；Roasting time is 20 minutes to 2 hours.Above-mentioned decomposition and roasting are carried out in two roasters respectively, also can be at one
It is divided into two regions in stove, also can complete to decompose and roasting in continous way rotary roasting furnace simultaneously.Decompose in catalyst and roast
Appropriate air to be passed through during burning, to generate catalysis activity phase, and prevent catalyst by over reduction.
The specification of the propylene, ammonia and molecular oxygen needed for acrylonitrile is manufactured and using other ammoxidations using catalyst of the present invention
Catalyst is identical.Although the low molecule saturated hydrocarbon content in raw material propylene has no impact to reaction, consider third from economic point of view
Alkene concentration is more preferably greater than 85% (mole).Ammonia can use fertilizer grade liquefied ammonia.Reaction desired molecule oxygen can use pure oxygen from technical standpoint, rich
Oxygen and air, but from economy and the most handy air of security consideration.
The mol ratio of the ammonia and propylene that enter fluidized-bed reactor is between 0.8～1.5 preferably 1.0～1.3.Air
Mol ratio with propylene is 8～10.5, preferably 8.8～9.8.If because some operational reasons must use higher air ratio
When, 11 can be increased to, there is no significant impact to reaction.But the excess of oxygen from security consideration, reacting gas can not be more than 7%
(volume), desirably no more than 4%.
When catalyst of the present invention is used for fluidized-bed reactor, reaction temperature is 400～470 DEG C, preferably 410～450 DEG C.
Catalyst of the present invention is a kind of catalyst being applied to higher load, therefore in process units reaction temperature can 400 DEG C with
On, for example, 410～440 DEG C.Reaction pressure can be in 0.06～0.14MPa, if reaction pressure there will not be less than 0.06MPa
Any adverse effect, acrylonitrile yield can further improve.
The propylene load (WWH) of catalyst of the present invention is 0.045～0.15 hour-1, preferably 0.06～0.13 hour-1.
Load is too low not only to waste catalyst, carbon dioxide production also can be made to increase, selectively decline, be unfavorable.Load is too high
There is no practical significance, because catalyst charge is very few, the heat transfer area of cooling water pipe in catalyst layer can be made to be less than and remove instead
Answer the area needed for heat, cause reaction temperature uncontrollable.
Manufacture the Product recycling process for refining of acrylonitrile with catalyst of the present invention, can use existing production technology, be not required to do
Any transformation.I.e. the neutralized tower of the eluting gas of fluidized-bed reactor removes unreacted ammonia, then is inhaled whole organic products with water
Receive.Absorbing 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, it is suitable to introduce in catalyst composition of the present invention
Active sites isolation element element mutually synergistic with activity, make in catalyst each thing alternate existing mutually collaborative effect is obtained
Should, promote propylene conversion, have thing relative activity position to play the effect of being properly isolated from again, so that propylene is converted to generating acrylonitrile direction,
Thus greatly reducing deep oxidation accessory substance.Carry out ammoxidation of propylene reaction using the catalyst in the present invention, can be relatively
High propylene load 0.085 hour-1Obtain higher acrylonitrile yield 83.0% with 430 DEG C relatively low of reaction temperature.
The activity examination of catalyst of the present invention be internal diameter be 38 millimeters fluidized-bed reactor in carry out.Catalyst fills
400 grams of the amount of filling out, 430 DEG C of reaction temperature, reaction pressure 0.084MPa, raw material proportioning (mole) is propylene: ammonia: air=1: 1.25
: 9.7, 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 supplied propylene of reaction
Propylene conversion (%)=×100
Propylene feed molal quantity
Generate acrylonitrile molal quantity
Acrylonitrile selectivity (%)=×100
The supplied propylene of reaction
Generate acrylonitrile molal quantity
Acrylonitrile once through yield (%)=×100
Propylene feed molal quantity
Below by embodiment, the present invention is further elaborated.
Specific embodiment
【Embodiment 1】
1.5 grams of NaOH and 3.9 grams of potassium hydroxide and add water 11 grams and dissolving after heating, obtain material (A)；Will
933.3 grams of ammonium molybdates are dissolved in 764 grams of 60～90 DEG C of hot water, obtain material (B)；By 159.5 grams of bismuth nitrates, 1.5 grams of calcium nitrate,
568.1 grams of nickel nitrates, 315.7 grams of ferric nitrates, 148.8 grams of magnesium nitrate mixing, add water 340 grams, as material after heating for dissolving
(C), weigh 67.2 grams of neodymium nitrates and 23.4 grams of chromic nitrates, add water 20 grams, obtain material (D).
Material (A) is mixed with the Ludox that 2750 gram weight concentration are 40%, sequentially add under agitation material (B),
(C) and (D), after being sufficiently stirred for slurry, the slurry made is carried out in spray dryer framboid shaping according to well-established law,
It is 89 millimeters in internal diameter afterwards, length is little in 580 DEG C of roastings 2.0 in the rotary roasting furnace of 1700 millimeters (89 × 1700 millimeters of φ)
When, make and consist of：
50%K0.15Na0.1Nd0.4Cr0.6Ca0.01Ni5.0Mg1.5Fe2.0Bi0.85Mo13.6Ox+ 50%SiO2.
【Embodiment 2～6 and comparative example 1～4】
There are the catalyst of different compositions in following table using method preparation substantially the same manner as Example 1, and with obtained
Catalyst carry out under following reaction conditions ammoxidation of propylene generate acrylonitrile reaction, the results are shown in Table 1.
Above-described embodiment with the reaction condition of comparative example is：
38 millimeters of fluidized-bed reactors of φ
430 DEG C of reaction temperature
Reaction pressure 0.084MPa
400 grams of loaded catalyst
Catalyst propylene load (WWH) 0.085 hour-1
Raw material proportioning (mole) C3 =/NH3/ air=1/1.25/9.7
Table 1
Claims (7)
1. a kind of high load capacity catalyst of olefin ammoxidation reaction, described catalyst is by catalyst carrier with containing with atomic ratio measuring
The following composition composition of chemical general formula：
AaBbCcCadNieMgfFegBihMo13.6Ox
In formula, A is selected from least one in Li, Na, K, Rb, Cs and Tl；
B is selected from least one in La, Ce, Pr, Nd；
C is selected from least one or its mixture in Cr, W；
The span of a is 0.05～1.5；
The span of b is 0.1～3；
The span of c is 0.01～5；
The span of d is 0.005～0.01；
The span of e is 0.1～10；
The span of f is 0.1～5；
The span of g is 0.1～5；
The span of h is 0.01～3；
X is to meet the oxygen atom sum needed for each element chemical valence in catalyst；
Or, described catalyst is made up of catalyst carrier and following composition
Na0.05Rb0.15Ce0.05Cr0.1Ca0.05Fe2.0Ni5.0Mg3.5Bi1.2Mo13.6Ox、
K0.15Rb0.1La0.4Pr0.1W3.0Ca0.02Fe1.5Ni4.0Mg4.0Bi0.05Mo13.6OxWith
Rb1.5Pr0.4Ce0.3Cr0.2Ca0.1Ni6.0Mg2.5Fe2.5Bi0.35Mo13.6OxIn at least one；
Wherein catalyst carrier is selected from silica, and its consumption is 30～70% by weight percentage.
2. high load capacity catalyst according to claim 1 is it is characterised in that the span of c is 0.05～3.
3. high load capacity catalyst according to claim 1 is it is characterised in that the span of e is 0.5～9.
4. high load capacity catalyst according to claim 1 is it is characterised in that the span of f is 0.5～4.0.
5. high load capacity catalyst according to claim 1 is it is characterised in that the span of g is 0.5～4.0.
6. high load capacity catalyst according to claim 1 is it is characterised in that the span of h is 0.2～2.5.
7. high load capacity catalyst according to claim 1 it is characterised in that catalyst carrier be silica, its consumption with
Percentage by weight is calculated as 40%～60%.
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| CN201210575745.1A CN103894203B (en) | 2012-12-27 | 2012-12-27 | High-load catalyst for olefin ammoxidation reactions |
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| CN201210575745.1A CN103894203B (en) | 2012-12-27 | 2012-12-27 | High-load catalyst for olefin ammoxidation reactions |
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| CN103894203B true CN103894203B (en) | 2017-02-08 |
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| CN105597774A (en) * | 2014-11-20 | 2016-05-25 | 中国石油化工股份有限公司 | Catalyst used for preparing acrylonitrile |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294943A (en) * | 1999-11-03 | 2001-05-16 | 中国石油化工集团公司 | Fluid bed catalyst for acrylonitrile production |
| CN1450934A (en) * | 2000-08-17 | 2003-10-22 | 标准石油公司 | Improved catalyst for the manufacture of 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 |
| CN101172234A (en) * | 2006-11-02 | 2008-05-07 | 中国石油化工股份有限公司 | Fluid bed catalyzer for producing vinyl cyanide |
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- 2012-12-27 CN CN201210575745.1A patent/CN103894203B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294943A (en) * | 1999-11-03 | 2001-05-16 | 中国石油化工集团公司 | Fluid bed catalyst for acrylonitrile production |
| CN1450934A (en) * | 2000-08-17 | 2003-10-22 | 标准石油公司 | Improved catalyst for the manufacture of 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 |
| CN101172234A (en) * | 2006-11-02 | 2008-05-07 | 中国石油化工股份有限公司 | Fluid bed catalyzer for producing vinyl cyanide |
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