CN106582695A - Catalyst used in preparation of acrylonitrile through propylene ammoxidation and capable of realizing high hydrocyanic acid yield - Google Patents

Catalyst used in preparation of acrylonitrile through propylene ammoxidation and capable of realizing high hydrocyanic acid yield Download PDF

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Publication number
CN106582695A
CN106582695A CN201510660631.0A CN201510660631A CN106582695A CN 106582695 A CN106582695 A CN 106582695A CN 201510660631 A CN201510660631 A CN 201510660631A CN 106582695 A CN106582695 A CN 106582695A
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China
Prior art keywords
catalyst
grams
span
acrylonitrile
nitrate
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张顺海
姜家乐
吴粮华
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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 catalyst used in preparation of acrylonitrile through propylene ammoxidation and capable of realizing the high hydrocyanic acid yield and mainly aims to solve the problem of the low useful byproduct hydrocyanic acid yield in the prior art. The technical scheme is as follows: the catalyst used in preparation of acrylonitrile through propylene ammoxidation and capable of realizing the high hydrocyanic acid yield is prepared from a silicon dioxide carrier and composition with the general chemical formula in terms of atomic ratio as follows: AaBbCcFedNieBifMo12Ox, wherein A is selected from one of Li, Na, K, Rb and Cs; B is selected from Ca, P, Mn, Co, Mg, Cr, W, Nb, Ge and Ba; C is selected from at least two of rare earth elements, so that the technical problem is better solved, and the catalyst can be applied to industrial production of acrylonitrile.

Description

Richness produces the catalyst for propylene ammoxidation to acrylonitrile of hydrocyanic acid
Technical field
The present invention relates to the rich catalyst for propylene ammoxidation to acrylonitrile for producing hydrocyanic acid.
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.
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, richness produces the valuable by-products such as hydrocyanic acid Thing, 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 new rich catalyst for propylene ammoxidation to acrylonitrile for producing hydrocyanic acid is planted, the catalyst not only has under higher propylene load Higher acrylonitrile yield, and while the higher hydrocyanic acid yield of acquisition, improves the production efficiency and economic benefit of device.
The content of the invention
One of the technical problem to be solved is to provide a kind of new rich ammoxidation of propylene acrylonitrile production for producing hydrocyanic acid Catalyst, the catalyst not only has higher acrylonitrile yield under higher propylene load, and while obtains higher Hydrocyanic acid yield, improves the production efficiency and economic benefit of device.
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：Richness produces the ammoxidation of propylene system third of hydrocyanic acid Alkene 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；
C is selected from least two 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 e/ (b+d+e+f) is 0.18～0.80；
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 e/ (b+d+e+f) is preferably 0.20～0.78.
In above-mentioned technical proposal, the span of f is preferably 0.05～3.0.
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.
Manufacture the specification of the propylene, ammonia and molecular oxygen needed for acrylonitrile and be catalyzed using other ammoxidations using catalyst of the present invention Agent is identical.Although the low molecule saturated hydrocarbon content in raw material propylene has no impact to reaction, consider that propylene is dense from economic point of view Degree 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, 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 active mutually synergistic element and various are introduced in catalyst of the present invention composition Rare earth element, makes that the alternate existing mutual cooperative effect of each thing in catalyst is obtained, and promotes propylene conversion, there is thing relative activity again The effect of being properly isolated from is played in position, propylene is made to acrylonitrile and the conversion of hydrocyanic acid direction is generated, so as to greatly reduce deep oxidation Byproducts of carbon monoxide and carbon dioxide yield.Carry out ammoxidation of propylene reaction using the catalyst in the present invention, can compared with High propylene load 0.085 hour-1The higher He of acrylonitrile yield 83.0% is obtained under higher reaction pressure 0.084MPa Hydrocyanic acid yield 4.3%.
Below by embodiment, the invention will be further elaborated.
Specific embodiment
1st, catalyst preparation
【Embodiment 1】
0.7 gram of sodium hydroxide and 3.72 grams of potassium hydroxide add water and 11 grams and dissolve after heating, and obtain material I；By 779.3 grams Ammonium heptamolybdate (NH4)6Mo7O24·4H2O is dissolved in 800 grams of 80 DEG C of hot water, obtains material II；By 150.9 grams of bismuth nitrate Bi(NO3)3·5H2O, 64.8 grams of 50wt% manganese nitrate solutions, 655.9 grams of nitric acid nickel (NO3)2·6H2O, 253.9 grams of nitric acid Ferrum Fe (NO3)3·9H2O, 140.8 grams of magnesium nitrate Mg (NO3)2·2H2O, 73.97 grams of chromic nitrate Cr (NO3)3·9H2O mixes, Add water 300 grams, as material III after heating for dissolving；Weigh 79.5 grams of neodymium nitrate Nd (NO3)3·6H2O and 15.8 gram of nitric acid Praseodymium Pr (NO3)3·6H2O adds water 20 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 590 DEG C of roastings 2.0 hours, Make catalyst to consist of：
50wt%K0.15Na0.05Fe1.7Ni6.1Mn0.5Mg1.5Cr0.5Nd0.5Pr0.1Bi0.85Mo12.0Ox+ 50wt%SiO2
【Embodiment 2】
4.71 grams of rubidium nitrates and 3.25 grams of potassium hydroxide add water and 15 grams and dissolve after heating, and obtain material I；By 680.3 gram seven Ammonium molybdate (NH4)6Mo7O24·4H2O is dissolved in 750 grams of 80 DEG C of hot water, obtains material II；By 310.0 grams of bismuth nitrate Bi(NO3)3·5H2O, 226.4 grams of 50wt% manganese nitrate solutions, 525.6 grams of nitric acid nickel (NO3)2·6H2O, 234.7 grams of nitric acid Ferrum Fe (NO3)3·9H2O, 39.75 grams of anhydrous ammonium metatungstate (NH4)6H2W12O40Mixing, adds water 300 grams, after heating for dissolving As material III；Weigh 27.8 grams of neodymium nitrate Nd (NO3)3·6H2O, 55.0 grams of praseodymium nitrate Pr (NO3)3·6H2O and 27.7 gram Lanthanum (III) nitrate La (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 580 DEG C of roastings 1.0 hours, Make catalyst to consist of：
50wt%K0.15Rb0.1Fe1.8Ni5.6Mn2.0W0.5Nd0.2Pr0.4La0.2Bi2.0Mo12.0Ox+ 50wt%SiO2
【Embodiment 3】
1.4 grams of sodium hydroxide and 4.6 grams of cesium nitrates add water and 11 grams and dissolve after heating, and obtain material I；By 512.3 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 140.0 grams of bismuth nitrate Bi(NO3)3·5H2O, 141.4 grams of nitric acid nickel (NO3)2·6H2O, 196.4 grams of ferric nitrate Fe (NO3)3·9H2O, 185.1 grams Magnesium nitrate Mg (NO3)2·2H2O, 7.5 grams of niobium oxalate Nb2(C2O4)5Mixing, adds water 240 grams, as material after heating for dissolving III；Weigh 26.1 grams of neodymium nitrate Nd (NO3)3·6H2O and 5.2 gram of cerous nitrate Ce (NO3)3·6H2O adds water 15 grams and obtained after dissolving 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：
30wt%Na0.15Cs0.1Fe2.0Ni2.0Mg3.0Nb0.1Ce0.05Nd0.25Bi1.2Mo12.0Ox+ 70wt%SiO2
【Embodiment 4】
1.8 grams of potassium nitrate and 5.2 grams of rubidium nitrates add water and 11 grams and dissolve after heating, and obtain material I；By 754.0 gram of seven molybdic acid Ammonium (NH4)6Mo7O24·4H2O is dissolved in 800 grams of 80 DEG C of hot water, obtains material II；By 146.0 grams of bismuth nitrate Bi (NO3)3·5H2O、 572.2 grams of nitric acid nickel (NO3)2·6H2O, 144.5 grams of ferric nitrate Fe (NO3)3·9H2O, 181.6 grams of magnesium nitrates Mg(NO3)2·2H2O, 3.7 grams of germanium dioxide mixing, add water 340 grams, as material III after heating for dissolving；Weigh 76.7 Gram Lanthanum (III) nitrate La (NO3)3·6H2O and 230.7 gram 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 580 DEG C of roastings 1.0 hours, Make catalyst to consist of：
50%K0.05Rb0.1Fe1.0Ni5.5Mg2.0Ge0.1La0.4Nd1.5Bi0.85Mo12.0Ox+ 50%SiO2
【Embodiment 5】
4.1 grams of potassium hydroxide add water and 10 grams and dissolve after heating, and obtain material I；By 866.5 grams of ammonium heptamolybdates (NH4)6Mo7O24·4H2O is dissolved in 1000 grams of 80 DEG C of hot water, obtains material II；By 69.1 grams of bismuth nitrate Bi (NO3)3·5H2O、 777.1 grams of nitric acid nickel (NO3)2·6H2O, 415.2 grams of ferric nitrate Fe (NO3)3·9H2O, 211.6 grams of barium nitrate Ba (NO3)2、 8.7 grams of Zr (NO3)4·5H2O mixes, and adds water 340 grams, as material III after heating for dissolving；Weigh 53.0 grams of cerous nitrates Ce(NO3)3·6H2O and 122.7 gram of praseodymium nitrate Pr (NO3)3·6H2O adds water 40 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%Zr0.05K0.15Fe2.5Ni6.5Ba2.0Pr0.7Ce0.3Bi0.35Mo12.0Ox+ 40%SiO2
【Embodiment 6】
8.7 grams of potassium nitrate add water and 10 grams and dissolve after heating, and obtain material I；By 1226.8 grams of ammonium heptamolybdates (NH4)6Mo7O24·4H2O is dissolved in 1200 grams of 80 DEG C of hot water, obtains material II；By 41.9 grams of bismuth nitrate Bi (NO3)3·5H2O、 1015.6 grams of nitric acid nickel (NO3)2·6H2O, 352.7 grams of ferric nitrate Fe (NO3)3·9H2O, 6.8 grams of calcium nitrates Ca(NO3)2·4H2O mixes, and adds water 360 grams, as material III after heating for dissolving；Weigh 75.1 grams of cerous nitrates Ce(NO3)3·6H2O and 99.8 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%K0.15Fe1.5Ni6.0Ca0.05La0.4Ce0.3Bi0.15Mo12.0Ox+ 30%SiO2
【Comparative example 1】
0.8 gram of sodium hydroxide and 4.3 grams of potassium hydroxide add water and 11 grams and dissolve after heating, and obtain material I；By 904.1 gram seven Ammonium molybdate (NH4)6Mo7O24·4H2O is dissolved in 800 grams of 80 DEG C of hot water, obtains material II；By 175.1 grams of bismuth nitrate Bi(NO3)3·5H2O, 75.2 grams of 50wt% manganese nitrate solutions, 124.7 grams of nitric acid nickel (NO3)2·6H2O, 294.6 grams of nitric acid Ferrum Fe (NO3)3·9H2O, 163.3 grams of magnesium nitrate Mg (NO3)2·2H2O, 85.8 grams of chromic nitrate Cr (NO3)3·9H2O mixes, Add water 300 grams, as material III after heating for dissolving；Weigh 92.2 grams of neodymium nitrate Nd (NO3)3·6H2O and 18.3 gram of nitric acid Praseodymium Pr (NO3)3·6H2O adds water 20 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 590 DEG C of roastings 2.0 hours, Make catalyst to consist of：
50%K0.15Na0.05Fe1.7Ni1.0Mn0.5Mg1.5Cr0.5Nd0.5Pr0.1Bi0.85Mo12.0Ox+ 50%SiO2
【Comparative example 2】
0.5 gram of sodium hydroxide and 2.6 grams of potassium hydroxide add water and 11 grams and dissolve after heating, and obtain material I；By 550.0 gram seven Ammonium molybdate (NH4)6Mo7O24·4H2O is dissolved in 800 grams of 80 DEG C of hot water, obtains material II；By 106.5 grams of bismuth nitrate Bi(NO3)3·5H2O, 45.8 grams of 50wt% manganese nitrate solutions, 1631.6 grams of nitric acid nickel (NO3)2·6H2O, 179.2 grams of nitric acid Ferrum Fe (NO3)3·9H2O, 99.3 grams of magnesium nitrate Mg (NO3)2·2H2O, 52.2 grams of chromic nitrate Cr (NO3)3·9H2O mixes, plus 300 grams of water, as material III after heating for dissolving；Weigh 56.1 grams of neodymium nitrate Nd (NO3)3·6H2O and 11.1 gram of praseodymium nitrate Pr(NO3)3·6H2O adds water 20 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 590 DEG C of roastings 2.0 hours, Make catalyst to consist of：
50%K0.15Na0.05Fe1.7Ni21.5Mn0.5Mg1.5Cr0.5Nd0.5Pr0.1Bi0.85Mo12.0Ox+ 50%SiO2
【Comparative example 3】
5.6 grams of potassium hydroxide add water and 11 grams and dissolve after heating, and obtain material I；By 1163.0 grams of ammonium heptamolybdates (NH4)6Mo7O24·4H2O is dissolved in 1050 grams of 80 DEG C of hot water, obtains material II；By 39.7 grams of bismuth nitrate Bi (NO3)3·5H2O、 1251.7 grams of nitric acid nickel (NO3)2·6H2O, 334.4 grams of ferric nitrate Fe (NO3)3·9H2O, 6.4 grams of calcium nitrates Ca(NO3)2·4H2O mixes, and adds water 300 grams, as material III after heating for dissolving；Weigh 94.6 grams of Lanthanum (III) nitrates La(NO3)3·6H2O and 71.2 gram of cerous nitrate Ce (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 560 DEG C of roastings 5.0 hours, Make catalyst to consist of：
70%K0.15Fe1.5Ni7.8Ca0.05La0.4Ce0.3Bi0.15Mo12.0Ox+ 30%SiO2
【Comparative example 4】
3.2 grams of sodium hydroxide and 12.1 grams of potassium nitrate add water and 15 grams and dissolve after heating, and obtain material I；By 17714.3 grams Ammonium heptamolybdate (NH4)6Mo7O24·4H2O is dissolved in 2000 grams of 80 DEG C of hot water, obtains material II；By 332.0 grams of bismuth nitrate Bi(NO3)3·5H2O, 28.5 grams of 50wt% manganese nitrate solutions, 354.8 grams of nitric acid nickel (NO3)2·6H2O, 65.7 grams of ferric nitrates Fe(NO3)3·9H2O, 20.0 grams of anhydrous ammonium metatungstate (NH4)6H2W12O40Mixing, adds water 340 grams, conduct after heating for dissolving Material III；Weigh 174.8 grams of cerous nitrate Ce (NO3)3·6H2O and 173.4 gram of praseodymium nitrate Pr (NO3)3·6H2O adds water 100 Gram dissolving after 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%K0.15Na0.1Fe0.2Ni1.5Mn0.1W0.1Ce0.5Pr0.5Bi0.85Mo12.0Ox+ 10%SiO2
【Comparative example 5】
1.3 grams of sodium hydroxide and 3.4 grams of potassium hydroxide add water and 11 grams and dissolve after heating, and obtain material I；By 712.9 gram seven Ammonium molybdate (NH4)6Mo7O24·4H2O is dissolved in 800 grams of 80 DEG C of hot water, obtains material II；By 243.6 grams of bismuth nitrate Bi(NO3)3·5H2O, 177.9 grams of 50wt% manganese nitrate solutions, 88.5 grams of nitric acid nickel (NO3)2·6H2O, 437.3 grams of nitric acid Ferrum Fe (NO3)3·9H2O, 128.8 grams of magnesium nitrate Mg (NO3)2·2H2O, 81.2 grams of chromic nitrate Cr (NO3)3·9H2O mixes, Add water 340 grams, as material III after heating for dissolving；Weigh 201.9 grams of praseodymium nitrate Pr (NO3)3·6H2O and 145.4 gram of nitric acid Cerium Ce (NO3)3·6H2O adds water 100 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 590 DEG C of roastings 2 hours, Make catalyst to consist of：
50%K0.15Na0.1Fe3.2Ni0.9Mn1.5Mg1.5Cr0.6Pr1.4Ce1.0Bi1.5Mo12.0Ox+ 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 rich catalyst for propylene ammoxidation to acrylonitrile for producing hydrocyanic acid, including silica supports and containing with atomic ratio measuring Learn 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；
C is selected from least two 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 e/ (b+d+e+f) is 0.18～0.80；
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 e/ (b+d+e+f) is 0.20～0.78.
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 catalyst carrier is silicon dioxide, and its consumption is with weight Percentages are 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.
CN201510660631.0A 2015-10-14 2015-10-14 Catalyst used in preparation of acrylonitrile through propylene ammoxidation and capable of realizing high hydrocyanic acid yield Pending CN106582695A (en)

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Application publication date: 20170426