CN106582696A - High selectivity catalyst for production of acrylonitrile by propylene ammoxidation - Google Patents
High selectivity catalyst for production of acrylonitrile by propylene ammoxidation Download PDFInfo
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Abstract
The invention relates to a high selectivity catalyst for production of acrylonitrile by propylene ammoxidation, and mainly solves the problems of low yield of useful byproducts acetonitrile and hydrocyanic acid and high yield of acrolein in previous technologies. The high selectivity catalyst for production of acrylonitrile by propylene ammoxidation adopted by the invention comprises a silica carrier and a composition with a chemical general formula shown as AaBbCcFedNieBifMo12Ox in an atomic ratio, wherein A is selected from at least one of Li, Na, K, Rb and Cs, B is selected from at least one of Ca, P, Mn, Co, Mg, Cr, W, Nb, Ge and Ba, and C is selected from at least one of rare earth elements. Technical scheme well solves the technical problem, and can be applied to industrial production of acrylonitrile.
Description
Technical field
The present invention relates to the catalyst for propylene ammoxidation to acrylonitrile of high selectivity.
Background technology
Acrylonitrile is important Organic Chemicals, and it is produced by ammoxidation of propylene reaction.To obtain high activity, height
Selective fluid catalyst, people have carried out a series of improvement through constantly exploration.These improvement are directed to greatly catalysis
Agent activity composition, focuses on the collocation between catalyst activity component to improve the activity and selectivity of catalyst, so as to reach
The raising of acrylonitrile once through yield, and the raising of produce load.
Ammonia oxidation produces development of the acrylonitrile through more than 50 years, and in recent years acrylonitrile demand is still jagged, current acrylonitrile
The Main Trends of The Development of production, causes unit scale metaplasia to produce, further to cut down the consumption of raw materials by newly-built large-scale device
And energy consumption, increasing production capacity, domestic acrylonitrile new device production capacity is expected to be doubled, and builds up the production capacity of rear factory
With the market demand by close balance.Therefore, the competition of acrylonitrile in future factory economy benefit is not only in that the production effect of acrylonitrile
Rate, and be the competition of valuable by-product acetonitrile and hydrocyanic acid yield, while acrylonitrile yield is ensured, Fu Chanyi
Nitrile and hydrocyanic acid seem more urgent, improve the whole economic efficiency of device, while lowering acrylic aldehyde yield, improve device
Recovery of acrylonitrile.
Original acrylonitrile installation requires that the useful load of catalyst can not be too many when expanding energy, requires the catalyst used instead higher for this
Propylene load under, keep high acrylonitrile yield.After reactor size and production capacity determine, reactor filling catalysis
Agent it is how many with catalyst can bearing load it is relevant, i.e. WWH.Its definition is catalyst per ton, and third can be processed per hour
The tonnage of alkene.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, therefore the fluid height of catalyst reactor is possible to super
The height of supercooling water pipe.Further, since the increase of reactor feed amount, so operating linear velocity is also significantly improved.This two changes
The combined influence of change there is a possibility that reactor dilute phase temperature rises, and cause carbon dioxide production to increase, under acrylonitrile selectivity
Drop, therefore the catalyst of higher WWH can prevent the problems referred to above.
Meanwhile, under high load capacity reaction condition, in the case where high acrylonitrile yield is kept, it is valuable that richness produces acetonitrile and hydrocyanic acid etc.
Value by-product, contributes to reducing per-unit production energy consumption, so as to improve production efficiency and economic benefit.
Improving the WWH of catalyst in theory should increase adsorption activation ability of the catalyst to propylene, but at present still
The report to propylene adsorption activation ability can be improved without certain element in catalyst.Document US5093299 and US5212137
In describe the catalyst of a kind of use molybdenum, bismuth, ferrum, nickel, magnesium, potassium and caesium system and carry out preparing acrylonitrile by allylamine oxidation
Catalyst.Introduce in the patent, its catalyst can be operated under generally lower slightly reaction temperature, and it has higher catalysis
Active and excellent oxidation-reduction stability, thus be applicable to relatively low air/propylene and compare conditional operation.It should be noted that
It is that the investigation condition of above-mentioned patent Example is fixed bed, and 430 DEG C of reaction temperatures do not refer to specific in experimental implementation
Reaction pressure and operational load situation data, more without reference to catalyst reaction performance under high pressure high load capacity.
A kind of manufacture method of acrylonitrile is described in the flat 8-27089 of document, it adopts molybdenum, bismuth, ferrum, magnesium and tungsten system
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 improvement.But
In above-mentioned all patents not only without reference to catalyst under higher propylene load acrylonitrile yield data, more without reference to urging
Agent acrylonitrile yield data under higher propylene load and higher reaction pressure.
The method and catalyst of production acrylonitrile, acetonitrile and hydrocyanic acid are described in document CN102892496, preparation technology is multiple
It is miscellaneous, and it is also in underload 0.06h to evaluate process conditions-1With carry out under low pressure 10psig.
A kind of containing in molybdenum, bismuth, cerium, ferrum, nickel, magnesium or zinc at least is disclosed in document JP9401312 and CN1121321A
A kind of catalyst of the preparing acrylonitrile by allylamine oxidation of, potassium or at least one of caesium or rubidium.Introduce in the patent, its catalysis
Agent can be effectively prevented acrylonitrile yield in the case where the response time is extended and reduce, but its evaluating catalyst is at a fairly low
Carry out under the conditions of reaction pressure and low operational load.
It is where the fluid catalyst of present invention ammoxidation of propylene production acrylonitrile different from the past：The present invention provides one
The catalyst for propylene ammoxidation to acrylonitrile of kind new high selectivity, the catalyst not only have under higher propylene load compared with
High acrylonitrile yield, and while higher acetonitrile and hydrocyanic acid yield is obtained, the production efficiency and economy for improving device is imitated
Benefit, while acrylic aldehyde yield is relatively low, the recovery of acrylonitrile of device is higher.
The content of the invention
One of the technical problem to be solved is to provide a kind of ammoxidation of propylene acrylonitrile production of new high selectivity and urges
Agent, the catalyst not only has higher acrylonitrile yield under higher propylene load, and while obtains higher second
Nitrile and hydrocyanic acid yield, improve the production efficiency and economic benefit of device, while acrylic aldehyde yield is relatively low, the acrylonitrile of device
The response rate is higher.
The two of the technical problem to be solved are to provide the preparation method of one of above-mentioned technical problem catalyst.
In order to solve one of above-mentioned technical problem, technical scheme is as follows：The ammoxidation of propylene propylene of high selectivity
Nitrile catalyst, including silica supports and containing with the following compositionss of atomic ratio measuring chemical general formula：
AaBbCcFedNieBifMo12Ox
At least one of the A in Li, Na, K, Rb and Cs in formula；
At least one of the B in Ca, P, Mn, Co, Mg, Cr, W, Nb, Ge and Ba；
At least one of the C in rare earth element；
The span of a is 0.01～2.5；
The span of b is 0.1～10；
The span of c is 0.01～5；
The span of d is 0.01～5；
The span of e is 1～10；
The span of d/ (b+d+e+f) is 0.01～0.7；
The span of f is 0.01～5；
X to meet catalyst in oxygen atom sum needed for each element quantivalence；
Described carrier consumption is by weight percentage 30～70wt%.
In above-mentioned technical proposal, the span of a is preferably 0.05～1.5.
In above-mentioned technical proposal, the span of b is preferably 0.3～8.
In above-mentioned technical proposal, the span of c is preferably 0.1～3.
In above-mentioned technical proposal, the span of d is preferably 0.05～3.5.
In above-mentioned technical proposal, the span of e is preferably 2.5～9.
In above-mentioned technical proposal, the span of d/ (b+d+e+f) is preferably 0.02～0.6.
In above-mentioned technical proposal, the span of f is preferably 0.05～3.0.
In above-mentioned technical proposal, carrier consumption is preferably by weight percentage 35%～65wt%.
In order to solve the two of above-mentioned technical problem, technical scheme is as follows：One of above-mentioned technical problem technical side
The preparation method of catalyst any one of case, comprises the following steps：
(1) material I is obtained after the material dissolution of A used by；
(2) material II is obtained after the material dissolution of molybdenum used by；
(3) material III is obtained after the raw material of B used by and the material dissolution of Fe, Bi, Ni；
(4) material IV is obtained after the material dissolution of C used by；
(5) material I is mixed with carrier colloidal sol, material II, material III and material IV is sequentially added under stirring and is catalyzed
Agent slurry；
(6) catalyst pulp is spray-dried and obtains catalyst precarsor；
(7) catalyst precarsor obtains catalyst in 0.25～4 hour in oxidizing atmosphere in 500～700 DEG C of roastings.The oxygen
The property the changed preferred air of atmosphere.
At least one in above-mentioned technical proposal, in the preferred molybdenum oxide of raw material of molybdenum or ammonium molybdate.
Most handy its nitrate of the raw material of the raw material of A, the raw material of B, the raw material of C, the raw material of Fe, the raw material of Ni and Bi,
Oxalates, hydroxide, oxide can be analyzed to the salt of oxide.
The specification of the propylene, ammonia and molecular oxygen needed for acrylonitrile is manufactured using catalyst of the present invention and other ammoxidation systems third are used
Alkene nitrile catalyst is identical.Although the low molecule saturated hydrocarbon content in raw material propylene has no impact to reaction, examine from economic point of view
Density of propylene is considered more preferably greater than 85% (mole).Ammonia can use fertilizer grade liquefied ammonia.Reaction desired molecule oxygen can be with pure from technical standpoint
Oxygen, oxygen-enriched and air, but from the most handy air of economy and security consideration.
The Product recycling process for refining of acrylonitrile is manufactured with catalyst of the present invention, existing production technology can be used, be not required to do any
Transformation.That is the neutralized tower of eluting gas of fluidized-bed reactor removes unreacted ammonia, then is inhaled whole organic products with water at low temperature
Receive.The extractive distillation of absorbing liquid Jing, obtains high-purity propylene nitrile product after dehydrogenation cyanic acid and processed.
The activity examination of catalyst of the present invention is what is carried out in the fluidized-bed reactor that internal diameter is 38 millimeters.Catalyst packing
400 grams of amount, reaction temperature 420-440 DEG C, reaction pressure 0.084-0.14MPa, proportioning raw materials (mole) are propylene: ammonia:
Air=1: 1.25: 9.7, the propylene load (WWH) of catalyst is 0.085 hour-1。
In the present invention propylene conversion, acrylonitrile selectivity and once through yield are defined as follows：
Suitable active sites isolation element and the mutually synergistic element of activity are introduced in catalyst composition of the present invention, makes to be obtained
The alternate existing mutual cooperative effect of each thing in catalyst, promotes propylene conversion, has thing relative activity position to play again and is properly isolated from work
With propylene being made to acrylonitrile and acetonitrile and the conversion of hydrocyanic acid direction is generated, so as to greatly reduce the oxygen of deep oxidation by-product one
Change carbon and carbon dioxide yield.Ammoxidation of propylene reaction is carried out using the catalyst in the present invention, can be negative in higher propylene
Lotus 0.085 hour-1Higher acrylonitrile yield 83.2%, acetonitrile yield are obtained under higher reaction pressure 0.084MPa
2.1%th, hydrocyanic acid yield 3.9% and relatively low acrylic aldehyde yield 0.2%.
Below by embodiment, the invention will be further elaborated.
Specific embodiment
1st, catalyst preparation
【Embodiment 1】
0.3 gram of sodium hydroxide and 3.6 grams of potassium hydroxide add water and 11 grams and dissolve after heating, and obtain material I；By 748.7 gram seven
Ammonium molybdate (NH4)6Mo7O24·4H2O is dissolved in 800 grams of 80 DEG C of hot water, obtains material II；By 145.0 grams of bismuth nitrate
Bi(NO3)3·5H2O, 49.8 grams of 50wt% manganese nitrate solutions, 619.8 grams of nitric acid nickel (NO3)2·6H2O, 373.1 grams of nitric acid
Ferrum Fe (NO3)3·9H2O, 135.2 grams of magnesium nitrate Mg (NO3)2·2H2O, 8.3 grams of calcium nitrate Ca (NO3)2·4H2O, 71.1 grams
Chromic nitrate Cr (NO3)3·9H2O mixes, and adds water 340 grams, as material III after heating for dissolving；Weigh 137.5 grams of neodymium nitrates
Nd(NO3)3·6H2O adds water 30 grams after dissolving to obtain material IV.
Material I is mixed with the Ludox that 2500 gram weight concentration are 40%, sequentially add under agitation material II, III and
IV, slurry is obtained Jing after being sufficiently stirred for, and framboid molding is carried out in spray dryer according to well-established law slurry by made by, is finally existed
Internal diameter is 89 millimeters, length in the rotary roasting furnace of 1700 millimeters (89 × 1700 millimeters of φ) in 585 DEG C of roastings 2.0 hours,
Make catalyst to consist of：
50%K0.15Na0.02Fe2.6Ni6.0Mn0.4Ca0.1Mg1.5Cr0.5Nd0.9Bi0.85Mo12.0Ox+ 50%SiO2
【Embodiment 2】
6.07 grams of rubidium nitrates and 4.2 grams of potassium hydroxide add water and 15 grams and dissolve after heating, and obtain material I；By 877.1 gram seven
Ammonium molybdate (NH4)6Mo7O24·4H2O is dissolved in 900 grams of 80 DEG C of hot water, obtains material II；By 199.8 grams of bismuth nitrate
Bi(NO3)3·5H2O, 145.9 grams of 50wt% manganese nitrate solutions, 181.5 grams of nitric acid nickel (NO3)2·6H2O, 16.8 grams of nitric acid
Ferrum Fe (NO3)3·9H2O, 71.8 grams of anhydrous ammonium metatungstate (NH4)6H2W12O40With 83.3 grams of chromic nitrate Cr (NO3)3·9H2O
Mixing, adds water 340 grams, as material III after heating for dissolving；Weigh 89.5 grams of neodymium nitrate Nd (NO3)3·6H2O adds water 15
Gram dissolving after material IV.
Material I is mixed with the Ludox that 2500 gram weight concentration are 40%, sequentially add under agitation material II, III and
IV, slurry is obtained Jing after being sufficiently stirred for, and framboid molding is carried out in spray dryer according to well-established law slurry by made by, is finally existed
Internal diameter is 89 millimeters, length in the rotary roasting furnace of 1700 millimeters (89 × 1700 millimeters of φ) in 580 DEG C of roastings 1.0 hours,
Make catalyst to consist of：
50%K0.15Rb0.1Fe0.1Ni1.5Mn1.0W0.7Cr0.5Nd0.5Bi1.0Mo12.0Ox+ 50%SiO2
【Embodiment 3】
0.9 gram of sodium hydroxide and 6.6 grams of cesium nitrates add water and 11 grams and dissolve after heating, and obtain material I；By 479.4 gram of seven molybdenum
Sour ammonium (NH4)6Mo7O24·4H2O is dissolved in 500 grams of 80 DEG C of hot water, obtains material II；By 131.1 grams of bismuth nitrate
Bi(NO3)3·5H2O, 264.6 grams of nitric acid nickel (NO3)2·6H2O, 284.8 grams of ferric nitrate Fe (NO3)3·9H2O, 52.0 grams of nitre
Sour magnesium Mg (NO3)2·2H2O, 27.9 grams of niobium oxalate Nb2(C2O4)5Mixing, adds water 240 grams, as material after heating for dissolving
III；Weigh 14.7 grams of neodymium nitrate Nd (NO3)3·6H2O adds water 15 grams after dissolving to obtain material IV.
Material I is mixed with the Ludox that 3500 gram weight concentration are 40%, sequentially add under agitation material II, III and
IV, slurry is obtained Jing after being sufficiently stirred for, and framboid molding is carried out in spray dryer according to well-established law slurry by made by, is finally existed
Internal diameter is 89 millimeters, length in the rotary roasting furnace of 1700 millimeters (89 × 1700 millimeters of φ) in 580 DEG C of roastings 0.5 hour,
Make catalyst to consist of：
30%Na0.1Cs0.15Fe3.1Ni4.0Mg0.9Nb0.4Nd0.15Bi1.2Mo12.0Ox+ 70%SiO2
【Embodiment 4】
1.6 grams of potassium nitrate and 7.0 grams of rubidium nitrates add water and 11 grams and dissolve after heating, and obtain material I；By 672.8 gram of seven molybdic acid
Ammonium (NH4)6Mo7O24·4H2O is dissolved in 600 grams of 80 DEG C of hot water, obtains material II；By 130.3 grams of bismuth nitrate Bi (NO3)3·5H2O、
324.9 grams of nitric acid nickel (NO3)2·6H2O, 257.9 grams of ferric nitrate Fe (NO3)3·9H2O, 40.5 grams of magnesium nitrates
Mg(NO3)2·2H2O, 3.3 grams of germanium dioxide mixing, add water 340 grams, as material III after heating for dissolving；Weigh 340.2
Gram praseodymium nitrate Pr (NO3)3·6H2O and 328.4 gram of Lanthanum (III) nitrate La (NO3)3·6H2O adds water 400 grams after dissolving to obtain material IV.
Material I is mixed with the Ludox that 2500 gram weight concentration are 40%, sequentially add under agitation material II, III and
IV, slurry is obtained Jing after being sufficiently stirred for, and framboid molding is carried out in spray dryer according to well-established law slurry by made by, is finally existed
Internal diameter is 89 millimeters, length in the rotary roasting furnace of 1700 millimeters (89 × 1700 millimeters of φ) in 580 DEG C of roastings 1.0 hours,
Make catalyst to consist of：
50%K0.05Rb0.15Fe2.0Ni3.5Mg0.5Ge0.1Pr2.5La2.4Bi0.85Mo12.0Ox+ 50%SiO2
【Embodiment 5】
7.5 grams of potassium nitrate add water and 10 grams and dissolve after heating, and obtain material I；By 1064.3 grams of ammonium heptamolybdates
(NH4)6Mo7O24·4H2O is dissolved in 1100 grams of 80 DEG C of hot water, obtains material II；By 109.1 grams of bismuth nitrate Bi (NO3)3·5H2O、
367.1 grams of nitric acid nickel (NO3)2·6H2O, 714.1 grams of ferric nitrate Fe (NO3)3·9H2O, 14.5 grams of cobalt nitrates
Co(NO3)2·6H2O, 11.8 grams of calcium nitrate Ca (NO3)2·4H2O, 12.9 grams of Zr (NO3)4·5H2O mixes, and adds water 350 grams,
As material III after heating for dissolving；Weigh 129.2 grams of praseodymium nitrate Pr (NO3)3·6H2O adds water 50 grams after dissolving to obtain material IV.
Material I is mixed with the Ludox that 2000 gram weight concentration are 40%, sequentially add under agitation material II, III and
IV, slurry is obtained Jing after being sufficiently stirred for, and framboid molding is carried out in spray dryer according to well-established law slurry by made by, is finally existed
Internal diameter is 89 millimeters, length in the rotary roasting furnace of 1700 millimeters (89 × 1700 millimeters of φ) in 550 DEG C of roastings 0.6 hour,
Make catalyst to consist of：
60%Zr0.06K0.15Fe3.5Ni2.5Co0.1Ca0.1Pr0.6Bi0.45Mo12.0Ox+ 40%SiO2
【Embodiment 6】
8.8 grams of potassium nitrate add water and 10 grams and dissolve after heating, and obtain material I；By 1242.1 grams of ammonium heptamolybdates
(NH4)6Mo7O24·4H2O is dissolved in 1300 grams of 80 DEG C of hot water, obtains material II；By 14.1 grams of bismuth nitrate Bi (NO3)3·5H2O、
342.8 grams of nitric acid nickel (NO3)2·6H2O, 1190.5 grams of ferric nitrate Fe (NO3)3·9H2O, 34.0 grams of cobalt nitrates
Co(NO3)2·4H2O mixes, and adds water 500 grams, as material III after heating for dissolving；Weigh 76.0 grams of cerous nitrates
Ce(NO3)3·6H2O and 101.0 gram of Lanthanum (III) nitrate La (NO3)3·6H2O adds water 50 grams after dissolving to obtain material IV.
Material I is mixed with the Ludox that 1500 gram weight concentration are 40%, sequentially add under agitation material II, III and
IV, slurry is obtained Jing after being sufficiently stirred for, and framboid molding is carried out in spray dryer according to well-established law slurry by made by, is finally existed
Internal diameter is 89 millimeters, length in the rotary roasting furnace of 1700 millimeters (89 × 1700 millimeters of φ) in 540 DEG C of roastings 3 hours,
Make catalyst to consist of：
70%K0.15Fe5.0Ni2.0Co0.2La0.4Ce0.3Bi0.05Mo12.0Ox+ 30%SiO2
【Comparative example 1】
0.3 gram of sodium hydroxide and 3.8 grams of potassium hydroxide add water and 11 grams and dissolve after heating, and obtain material I；By 805.1 gram seven
Ammonium molybdate (NH4)6Mo7O24·4H2O is dissolved in 800 grams of 80 DEG C of hot water, obtains material II；By 155.9 grams of bismuth nitrate
Bi(NO3)3·5H2O, 53.6 grams of 50wt% manganese nitrate solutions, 666.5 grams of nitric acid nickel (NO3)2·6H2O, 12.3 grams of ferric nitrates
Fe(NO3)3·9H2O, 145.4 grams of magnesium nitrate Mg (NO3)2·2H2O, 8.9 grams of calcium nitrate Ca (NO3)2·4H2O, 76.4 grams of nitre
Sour chromium Cr (NO3)3·9H2O mixes, and adds water 340 grams, as material III after heating for dissolving；Weigh 147.8 grams of neodymium nitrates
Nd(NO3)3·6H2O adds water 50 grams after dissolving to obtain material IV.
Material I is mixed with the Ludox that 2500 gram weight concentration are 40%, sequentially add under agitation material II, III and
IV, slurry is obtained Jing after being sufficiently stirred for, and framboid molding is carried out in spray dryer according to well-established law slurry by made by, is finally existed
Internal diameter is 89 millimeters, length in the rotary roasting furnace of 1700 millimeters (89 × 1700 millimeters of φ) in 585 DEG C of roastings 2.0 hours,
Make catalyst to consist of：
50%K0.15Na0.02Fe0.08Ni6.0Mn0.4Ca0.1Mg1.5Cr0.5Nd0.9Bi0.85Mo12.0Ox+ 50%SiO2
【Comparative example 2】
0.2 gram of sodium hydroxide and 2.3 grams of potassium hydroxide add water and 11 grams and dissolve after heating, and obtain material I；By 478.6 gram seven
Ammonium molybdate (NH4)6Mo7O24·4H2O is dissolved in 500 grams of 80 DEG C of hot water, obtains material II；By 92.7 grams of bismuth nitrate
Bi(NO3)3·5H2O, 31.9 grams of 50wt% manganese nitrate solutions, 396.2 grams of nitric acid nickel (NO3)2·6H2O, 2100.9 grams of nitric acid
Ferrum Fe (NO3)3·9H2O, 86.5 grams of magnesium nitrate Mg (NO3)2·2H2O, 5.3 grams of calcium nitrate Ca (NO3)2·4H2O, 45.4 grams
Chromic nitrate Cr (NO3)3·9H2O mixes, and adds water 1000 grams, as material III after heating for dissolving；Weigh 87.9 grams of neodymium nitrates
Nd(NO3)3·6H2O adds water 50 grams after dissolving to obtain material IV.
Material I is mixed with the Ludox that 2500 gram weight concentration are 40%, sequentially add under agitation material II, III and
IV, slurry is obtained Jing after being sufficiently stirred for, and framboid molding is carried out in spray dryer according to well-established law slurry by made by, is finally existed
Internal diameter is 89 millimeters, length in the rotary roasting furnace of 1700 millimeters (89 × 1700 millimeters of φ) in 585 DEG C of roastings 2.0 hours,
Make catalyst to consist of：
50%K0.15Na0.02Fe22.9Ni6.0Mn0.4Ca0.1Mg1.5Cr0.5Nd0.9Bi0.85Mo12.0Ox+ 50%SiO2。
【Comparative example 3】
6.2 grams of rubidium nitrates add water 10 grams and dissolved after heating, and obtain material I；By 898.6 grams of ammonium heptamolybdates
(NH4)6Mo7O24·4H2O is dissolved in 900 grams of 80 DEG C of hot water, obtains material II；By 30.7 grams of bismuth nitrate Bi (NO3)3·5H2O、
15.0 grams of 50wt% manganese nitrate solutions, 124.0 grams of nitric acid nickel (NO3)2·6H2O, 861.2 grams of ferric nitrate Fe (NO3)3·9H2O、
10.5 grams of anhydrous ammonium metatungstate (NH4)6H2W12O40Mixing, adds water 300 grams, as material III after heating for dissolving；Weigh
128.3 grams of neodymium nitrate Nd (NO3)3·6H2O adds water 50 grams after dissolving to obtain material IV.
Material I is mixed with the Ludox that 2500 gram weight concentration are 40%, sequentially add under agitation material II, III and
IV, slurry is obtained Jing after being sufficiently stirred for, and framboid molding is carried out in spray dryer according to well-established law slurry by made by, is finally existed
Internal diameter is 89 millimeters, length in the rotary roasting furnace of 1700 millimeters (89 × 1700 millimeters of φ) in 560 DEG C of roastings 5.0 hours,
Make catalyst to consist of：
50%Rb0.1Fe5.0Ni1.0Mn0.1W0.1Nd0.7Bi0.15Mo12.0Ox+ 50%SiO2。
【Comparative example 4】
3.5 grams of sodium hydroxide and 13.1 grams of potassium nitrate add water and 15 grams and dissolve after heating, and obtain material I；By 1855.0 gram seven
Ammonium molybdate (NH4)6Mo7O24·4H2O is dissolved in 1900 grams of 80 DEG C of hot water, obtains material II；By 359.2 grams of bismuth nitrate
Bi(NO3)3·5H2O, 30.9 grams of 50wt% manganese nitrate solutions, 383.9 grams of nitric acid nickel (NO3)2·6H2O, 71.1 grams of ferric nitrates
Fe(NO3)3·9H2O mixes, and adds water 340 grams, as material III after heating for dissolving；Weigh 37.8 grams of cerous nitrates
Ce(NO3)3·6H2O adds water 30 grams after dissolving to obtain material IV.
Material I is mixed with the Ludox that 500 gram weight concentration are 40%, material II, III and IV is sequentially added under agitation,
Slurry is obtained Jing after being sufficiently stirred for, framboid molding is carried out in spray dryer according to well-established law slurry by made by, finally in internal diameter
For 89 millimeters, length in the rotary roasting furnace of 1700 millimeters (89 × 1700 millimeters of φ) in 590 DEG C of roastings 2.0 hours, system
Consist of into catalyst：
90%K0.15Na0.1Fe0.2Ni1.5Mn0.1Ce0.1Bi0.85Mo12.0Ox+ 10%SiO2。
【Comparative example 5】
1.2 grams of sodium hydroxide and 2.9 grams of potassium hydroxide add water and 10 grams and dissolve after heating, and obtain material I；By 616.0 gram seven
Ammonium molybdate (NH4)6Mo7O24·4H2O is dissolved in 700 grams of 80 DEG C of hot water, obtains material II；By 701.7 grams of bismuth nitrate
Bi(NO3)3·5H2O, 51.3 grams of 50wt% manganese nitrate solutions, 425.0 grams of nitric acid nickel (NO3)2·6H2O, 11.8 grams of ferric nitrates
Fe(NO3)3·9H2O, 111.3 grams of magnesium nitrate Mg (NO3)2·2H2O, 70.2 grams of chromic nitrate Cr (NO3)3·9H2O mixes, plus
340 grams of water, as material III after heating for dissolving；Weigh 49.8 grams of praseodymium nitrate Pr (NO3)3·6H2O adds water 20 grams after dissolving
Obtain material IV.
Material I is mixed with the Ludox that 2500 gram weight concentration are 40%, sequentially add under agitation material II, III and
IV, slurry is obtained Jing after being sufficiently stirred for, and framboid molding is carried out in spray dryer according to well-established law slurry by made by, is finally existed
Internal diameter is 89 millimeters, length in the rotary roasting furnace of 1700 millimeters (89 × 1700 millimeters of φ) in 590 DEG C of roastings 2 hours,
Make catalyst to consist of：
50%K0.15Na0.1Fe0.1Ni5.0Mn0.5Mg1.5Cr0.6Pr0.4Bi5.0Mo12.0Ox+ 50%SiO2。
2nd, evaluating catalyst
Above-described embodiment is with the reaction condition of comparative example：
38 millimeters of fluidized-bed reactors of φ
430 DEG C of reaction temperature
Reaction pressure 0.10MPa
400 grams of loaded catalyst
Catalyst propylene load (WWH) 0.085 hour-1
Proportioning raw materials (mole) C3H6/NH3/ air=1/1.25/9.7.
The results are shown in Table 1.
As can be seen that the catalyst obtained in preparation method of the present invention achieves best result from the result of table 1.
Table 1
Claims (10)
1. the catalyst for propylene ammoxidation to acrylonitrile of high selectivity, including silica supports and containing with atomic ratio measuring chemistry
The following compositionss of formula：
AaBbCcFedNieBifMo12Ox
At least one of the A in Li, Na, K, Rb and Cs in formula；
At least one of the B in Ca, P, Mn, Co, Mg, Cr, W, Nb, Ge and Ba；
At least one of the C in rare earth element；
The span of a is 0.01～2.5；
The span of b is 0.1～10；
The span of c is 0.01～5；
The span of d is 0.01～5；
The span of e is 1～10；
The span of d/ (b+d+e+f) is 0.01～0.7；
The span of f is 0.01～5；
X to meet catalyst in oxygen atom sum needed for each element quantivalence；
Described carrier consumption is by weight percentage 30～70wt%.
2. catalyst according to claim 1, it is characterised in that the span of a is 0.05～1.5.
3. catalyst according to claim 1, it is characterised in that the span of b is 0.3～8.
4. catalyst according to claim 1, it is characterised in that the span of c is 0.1～3.
5. catalyst according to claim 1, it is characterised in that the span of d is 0.05～3.5.
6. catalyst according to claim 1, it is characterised in that the span of e is 2.5～9.
7. catalyst according to claim 1, it is characterised in that the span of d/ (b+d+e+f) is 0.02～0.6.
8. catalyst according to claim 1, it is characterised in that the span of f is 0.05～3.0.
9. catalyst according to claim 1, it is characterised in that carrier consumption by weight percentage for 35%～
65wt%.
10. the preparation method of catalyst any one of claim 1 to 9, comprises the following steps：
(1) material I is obtained after the material dissolution of A used by；
(2) material II is obtained after the material dissolution of molybdenum used by；
(3) material III is obtained after the raw material of B used by and the material dissolution of Fe, Bi, Ni；
(4) material IV is obtained after the material dissolution of C used by；
(5) material I is mixed with carrier colloidal sol, material II, material III and material IV is sequentially added under stirring and is catalyzed
Agent slurry；
(6) catalyst pulp is spray-dried and obtains catalyst precarsor；
(7) catalyst precarsor obtains catalyst in 0.25～4 hour in oxidizing atmosphere in 500～700 DEG C of roastings.
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| CN113828337A (en) * | 2020-06-24 | 2021-12-24 | 中国石油化工股份有限公司 | Catalyst for preparing acrylonitrile by propylene ammoxidation, preparation method and application thereof |
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