CN104549224A - Unsaturated nitrile catalyst and preparation method thereof - Google Patents
Unsaturated nitrile catalyst and preparation method thereof Download PDFInfo
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- CN104549224A CN104549224A CN201310512199.1A CN201310512199A CN104549224A CN 104549224 A CN104549224 A CN 104549224A CN 201310512199 A CN201310512199 A CN 201310512199A CN 104549224 A CN104549224 A CN 104549224A
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- 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 an unsaturated nitrile catalyst and a preparation method thereof, and mainly aims to solve the problems of low catalyst yield, poor selectivity and poor stability in the prior art. The problem can be well solved by adopting a technical scheme that the unsaturated nitrile catalyst comprises an active ingredient as shown in the general formula of Mo1.00VaNbbSbcOx according to an atomic ratio, wherein the value range of a is 0.1-1.0, the value range of b is 0.01-1.0, the value range of c is 0.01-1.0, and x fulfills the total number of oxygen atoms required by element valences in the catalyst. The unsaturated nitrile catalyst can be applied to industrial production of unsaturated nitrile production by low-carbon alkane ammmoxidation.
Description
Technical field
The present invention relates to unsaturated nitrile catalyst and preparation method thereof.Especially the catalyzer of propane ammoxidation Reactive Synthesis vinyl cyanide and Trimethylmethane oxidative ammonolysis synthesize methyl acrylic nitrile is adapted to.
Background technology
Vinyl cyanide is the important monomer of synthon, synthetic rubber and synthetic resins, is the important source material of basic organic industry.Through development for many years, vinyl cyanide industrial production technology has reached its maturity and perfect.At present, the vinyl cyanide full scale plant of the whole world 95 more than % all adopts BP/Ineos company to take propylene as the Sohio method technique of raw material.
In recent years, along with the development and utilization of large-scale shale gas, between propane and propylene, define huge price difference.The whole world main production firm of vinyl cyanide, all actively drops into vinyl cyanide (methacrylonitrile) synthesis technique that exploitation is raw material with propane (Trimethylmethane), to reducing production cost, improves product competitiveness.In February, 2013, Japanese Asahi Kasei company builds up first 200,000 tons/year, the cover in the whole world in Thailand and is the vinyl cyanide full scale plant of raw material with propane and successfully goes into operation.
At present, propane (Trimethylmethane) ammonia oxidation synthesis of acrylonitrile (methacrylonitrile) catalyzer mainly contains the large catalyst system of Mo-V-Nb-Te (Sb) and Sb-V two.
Grasselli etc. ([1]. Robert K. Grasselli. Advances and future trends in selective oxidation and ammoxidation catalysis. Catalysis Today, 1999, 49:141-153. [2]. Robert K. Grasselli. Selectivity issues in (amm) oxidation catalysis. Catalysis Today, 2005, 99:23-31. [3]. Robert K. Grasselli, Douglas J. Buttrey, James D. Burrington, et al. Active centers, catalytic behavior, symbiosis and redox properties of MoV (Nb, Ta) TeO ammoxidation catalysts. Topics in Catalysis, 2006, 38 (1-3): 6-16.) to Mo-V-Nb-Te (Sb)-O
xcatalyzer is furtherd investigate, and thinks that (chemical formula is Mo to this catalyzer by club shaped structure orthorhombic phase M1
7.8v
1.95nb
0.86te
1.33o
x, or { TeO}
1-x(Mo, V, Nb)
10o
28, TeO} inserts the component in skeleton duct), (chemical formula is Mo to the accurate hexagon phase M2 of slab construction
1.0v
0.28/0.31nb
0.08te
0.27-0.39o
4.24, or { TeO}
2-x(Mo, V, Nb)
6o
18) and trace monocline crystalline phase TeMo
5o
16composition.Wherein M1 is propane activation phase, and M2 is the active phase of converting propylene, and when the two ratio is 3/2, acrylonitrile yield reaches as high as 62%, but the preparation of simple M1 and M2 phase is complicated.
In patent US 6063728, US 6143916 pairs of Mo-V-Nb-Te (Sb) catalyzer XRD figure spectrum 2
θ=27.3
°± 0.3
°p1 peak intensity and 2
θ=28.2
°± 0.3
°p2 peak intensity analyze, design variable R=P1/ (P1+P2), draws when catalyst performance is optimum, and R is between 0.40 < R < 0.75, and this is that the exploitation of Mo-V series catalysts provides reference.
Patent CN 1220258A discloses a kind of Mo-V catalyzer containing Te, find the prolongation with the reaction times, catalyst activity and acrylonitrile yield reduce gradually, and in reactor, add the activator containing Mo, Te by timing, to improve the stability of catalyzer, this method brings disadvantageous effect for the continuous seepage of industrialized unit.
Patent CN 1344584A discloses the preparation method of a kind of Mo-V-Nb-Te (Sb) catalyzer, although acrylonitrile yield is higher, but this catalyst preparation process is complicated, the particularly acquisition methods of Nb raw material, the amplification for catalyzer is produced and is brought difficulty.
Compared with Mo-V series catalysts, Sb-V catalyzer mostly adopts aluminum oxide to be carrier, and therefore its BET specific surface area is larger than Mo-V system.The chemical formula that Sb-V catalyzer is not fixed, comprises the VSbO with rutile structure in its crystal phase structure
4with α-Sb
2o
4association phase, wherein at VSbO
4in, Sb is mainly with Sb
5+, V is mainly with V
3+form exists (also has a small amount of V in addition
4+), therefore VSbO
4(V can be used
3+-V
4+) Sb
1-xo
4represent.When Sb/V is greater than 1.0, excessive Sb is with α-Sb
2o
4be covered in VSbO
4surface, in catalytic reaction process, Sb is from α-Sb
2o
4association moves to SbVO mutually
4in, form Sb
5+-V
3+/ V
4+ammoxidation of propylene chain carrier, catalyst performance starts to promote (S. Albonetti, G. Blanchard, P. Burattin, T.J. Cassidy, S.Masetti, F. Trifir ò. Mechanism of ammoxidation of propane on a Sb/V/O system. Catalysis Letters, 1997,45:119-123.).
Sb-V catalyzer can by V
2o
5and Sb
2o
3at high temperature there is solid state reaction preparation, also can be mixed by V, Sb slurry and co-precipitation preparation, V, Sb valence state now in catalyzer, crystal phase structure and catalytic performance relevant with its preparation method, such as Sb/V atomic ratio, metal-modified ionic species, mix and blend temperature and heat-treat condition etc.
(the Shahid Shaikh such as Shaikh, Kathleen Bethke, Edouard Mamedov. Propane ammoxidation on bulk, diluted and supported VSb oxides. Topics in Catalysis, 2006,38 (4): 241-249.) by coprecipitation method, in Sb-V catalyzer, Mg, Al, W and Zr ion is introduced.XRD characterization result shows, and there is AlSbO in catalyzer
4and MgSb
2o
6crystalline phase, and do not find VSbO
4phase.The activity influence added for Sb-V catalyzer of Zr and Mg is not obvious; And the adding of Al, catalyst activity significantly rises, and Propylene Selectivity significantly reduces, and its reason may be the interpolation of Sb and V due to Al, makes the two at VSbO
4well isolated in oxide structure.
But the catalyzer of prior art exists, and yield is low, poor selectivity, and the problem of poor stability.
Summary of the invention
One of technical problem to be solved by this invention is that the catalyzer yield existed in prior art is low, poor selectivity, and the problem of poor stability, there is provided a kind of unsaturated nitrile catalyst, this catalyzer has that yield is high, selectivity is high, and the feature of good stability.
Two of technical problem to be solved by this invention is preparation methods of the catalyzer described in one of above-mentioned technical problem.
Three of technical problem to be solved by this invention is the application in low-carbon alkanes ammonia oxidation synthesis unsaturated nitrile of the described catalyzer of one of above-mentioned technical problem.
For one of solving the problems of the technologies described above, technical scheme of the present invention is as follows:
Unsaturated nitrile catalyst, comprises the active constituent of following general formula according to atomic ratio:
Mo
1.00V
aNb
bSb
cO
x
The span of a is 0.1 ~ 1.0;
The span of b is 0.01 ~ 1.0;
The span of c is 0.01 ~ 1.0;
X is for meeting the Sauerstoffatom sum in catalyzer needed for each element valence.
In order to solve the problems of the technologies described above two, technical scheme of the present invention is as follows: the preparation method of catalyzer described in claim 1, comprises the following steps:
1) solution (I) is made by soluble in water for corresponding for aequum V salt;
2) solution (II) is made by soluble in water for corresponding for aequum Mo salt;
3) solution (III) is made by soluble in water for corresponding for aequum Nb salt;
4) pH value of (I) solution is regulated to be 1.5 ~ 5.0 with mineral acid, the oxide powder of Sb is joined in solution (I) and mix, stir at least 2 hours at 80 ~ 100 DEG C, add solution (II) and (III) more successively, finally add reductive agent and obtain mixture paste, wherein reductive agent molecule is 0 ~ 0.42 with Mo atomic molar ratio, mixture paste stirs at least 2 hours at 80 ~ 100 DEG C, the thick slurry obtained, dry or moist, it is roasting 0.5 ~ 8 hour in the inert atmosphere of 400 ~ 800 DEG C in temperature, thus obtain catalyzer.Wherein dry temperature is preferably 100 ~ 150 DEG C.
In technique scheme, described mineral acid is preferably inorganic middle strong acid; More preferably at least one in sulfuric acid, nitric acid and hydrochloric acid or its mixture.
In technique scheme, described reductive agent is preferably at least one in oxalic acid, citric acid and tartrate or its mixture.In technique scheme, described reductive agent reductive agent and Mo atomic molar are than being preferably > 0 and below 0.42.
In technique scheme, be preferably 0 ~ 24 hour time of drying, optimum is 2 ~ 10 hours.
In technique scheme, maturing temperature is preferably 500 ~ 700 DEG C.
In technique scheme, inert atmosphere is preferably at least one in helium, nitrogen or argon gas.
In technique scheme, roasting time is preferably 2 ~ 4 hours.
For solve the problems of the technologies described above three, technical scheme of the present invention is as follows: the catalyzer described in the technical scheme of one of above-mentioned technical problem low-carbon alkanes ammonia oxidation synthesis unsaturated nitrile in application.
One of above-mentioned preferred technical scheme is the application in propane ammoxidation Reactive Synthesis vinyl cyanide.
Above-mentioned preferred technical scheme two is the application in Trimethylmethane oxidative ammonolysis synthesize methyl acrylic nitrile.
In technique scheme, propane or Trimethylmethane are preferably industrial gasses purity, and molecular oxygen is pure oxygen, and oxygen enrichment and air, be preferably air.
In unstripped gas, the mol ratio of ammonia and propane or Trimethylmethane is preferably between 0.8 ~ 2.0, is preferably 1.0 ~ 1.5, and the mol ratio of air and propane or Trimethylmethane is preferably 8.0 ~ 16.0, is preferably 10.0 ~ 15.0.
Mo raw material in catalyzer is preferably corresponding oxide compound or its ammonium salt, and V raw material is preferably corresponding oxide compound or its ammonium salt, and Sb raw material is preferably corresponding oxide compound, and Nb raw material is preferably corresponding oxide compound, oxyhydroxide, nitrate or oxalate.
Catalyzer of the present invention controls the pH value of solution in preparation process by adding mineral acid, add the oxidation state that reductive agent regulates oxide compound, preparation technology is simple, and repeatability, stability are better, and desired raw material is easy to get, the low-carbon alkanes ammoxidation catalyst of excellent property can be prepared.
Catalyzer of the present invention is evaluate in the fixed-bed reactor of 8 millimeters at internal diameter, and loaded catalyst is 3.0 grams, and temperature of reaction is 370 ~ 460 DEG C, is preferably 390 ~ 450 DEG C.
The transformation efficiency of propane, the selectivity of vinyl cyanide and be defined as follows duration of contact:
When catalyzer of the present invention is used for propane ammoxidation reaction, conversion of propane is up to 43.9%, and acrylonitrile selectivity can reach more than 29.0%; After reaction in 198 hours, conversion of propane is 43.9%, and acrylonitrile selectivity is 28.9%, and catalyst performance is comparatively stable, achieves good technique effect.
Below by specific embodiment, the invention will be further elaborated, but the present invention is not limited by the following examples.
Accompanying drawing explanation
Fig. 1 represents the stability experiment data of embodiment 1 and comparative example on year-on-year basis thereof.
Embodiment
[embodiment 1]
1.92 grams of ammonium meta-vanadates are dissolved in the water of 60.0 grams 80 DEG C, obtained solution (I); 10.00 grams of Ammonium Heptamolybdates (containing four crystal water, being called for short four water, lower same) are dissolved in the water of 60.0 grams 30 DEG C, obtained solution (II); ((III), prepares the salpeter solution (IV) of 0.1 mol/L 1.08 grams of oxalic acid hydrate niobiums to be dissolved in 10.0 grams of water formation solution; 2.50 grams of oxalic acid (two water) are dissolved in 5.0 grams of water and form solution (V); Wherein oxalic acid molecule and molybdenum atom mol ratio are 0.35.
Solution (I), in 80 DEG C of whipping process, adds salpeter solution (IV) gradually, makes the pH value of solution (I) be finally 3.0; Add 1.16 grams of antimonous oxide powder subsequently, stir 5 hours at 90 DEG C, successively solution (II) and solution (III) are joined in solution (I) subsequently, finally add oxalic acid solution (V), obtain mixture paste.
This slurry stirs after 2 hours at 90 DEG C, puts into the oven drying 5 hours of 120 DEG C, and roasting 2 hours in the high pure nitrogen atmosphere of 600 DEG C subsequently, finally obtains Mo
1.00v
0.29nb
0.03sb
0.14o
xcatalyzer.
This catalyzer is got 60 ~ 80 order powder and is used for propane ammoxidation reaction after compressing tablet, screening, temperature of reaction is 440 DEG C, reaction pressure is normal pressure, in unstripped gas, the mol ratio of propane, ammonia and air is 1.0/1.2/10.0, duration of contact is 1.91 grams minutes/milliliters, and acquired results is as shown in table 1.
[embodiment 2]
2.06 grams of ammonium meta-vanadates are dissolved in the water of 60.0 grams 80 DEG C, obtained solution (I); 10.00 grams of Ammonium Heptamolybdates (four water) are dissolved in the water of 60.0 grams 30 DEG C, obtained solution (II); ((III), prepares the sulphuric acid soln (IV) of 0.1 mol/L 5.50 grams of oxalic acid hydrate niobiums to be dissolved in 10.0 grams of water formation solution; 3.00 grams of oxalic acid (two water) are dissolved in 10.0 grams of water and form solution (V); Wherein oxalic acid molecule and molybdenum atom mol ratio are 0.42.
Solution (I), in 80 DEG C of whipping process, adds sulphuric acid soln (IV) gradually, makes the pH value of solution (I) be finally 2.0; Add 1.65 grams of antimonous oxide powder subsequently, stir 2 hours at 90 DEG C, successively solution (II) and solution (III) are joined in solution (I) subsequently, finally add oxalic acid solution (V), obtain mixture paste.
This slurry stirs after 2 hours at 90 DEG C, puts into the oven drying 8 hours of 120 DEG C, and roasting 3 hours in the high-pure helium atmosphere of 650 DEG C is enclosed subsequently, finally obtains Mo
1.00v
0.31nb
0.18sb
0.20o
xcatalyzer.
This catalyzer is got 60 ~ 80 order powder and is used for propane ammoxidation reaction after compressing tablet, screening, temperature of reaction is 430 DEG C, reaction pressure is normal pressure, in unstripped gas, the mol ratio of propane, ammonia and air is 1.0/1.3/10.0, duration of contact is 1.71 grams minutes/milliliters, and acquired results is as shown in table 1.
[embodiment 3]
1.33 grams of ammonium meta-vanadates are dissolved in the water of 60.0 grams 80 DEG C, obtained solution (I); 10.00 grams of Ammonium Heptamolybdates (four water) are dissolved in the water of 60.0 grams 30 DEG C, obtained solution (II); ((III), prepares the hydrochloric acid soln (IV) of 0.1 mol/L 4.58 grams of oxalic acid hydrate niobiums to be dissolved in 10.0 grams of water formation solution; 1.80 grams of citric acids (water) are dissolved in 10.0 grams of water and form solution (V); Wherein citric acid molecule and molybdenum atom mol ratio are 0.15.
Solution (I), in 80 DEG C of whipping process, adds hydrochloric acid soln (IV) gradually, makes the pH value of solution (I) be finally 4.5; Add 1.90 grams of antimonous oxide powder subsequently, stir 5 hours at 90 DEG C, successively solution (II) and solution (III) are joined in solution (I) subsequently, finally add citric acid solution (V), obtain mixture paste.
This slurry stirs after 5 hours at 90 DEG C, puts into the oven drying 10 hours of 120 DEG C, and roasting 4 hours in the high-purity argon gas atmosphere of 550 DEG C subsequently, finally obtains Mo
1.00v
0.20nb
0.15sb
0.23o
xcatalyzer.
This catalyzer is got 60 ~ 80 order powder and is used for propane ammoxidation reaction after compressing tablet, screening, temperature of reaction is 420 DEG C, reaction pressure is normal pressure, in unstripped gas, the mol ratio of propane, ammonia and air is 1.0/1.1/10.0, duration of contact is 2.00 grams minutes/milliliters, and acquired results is as shown in table 1.
[embodiment 4]
2.32 grams of ammonium meta-vanadates are dissolved in the water of 60.0 grams 80 DEG C, obtained solution (I); 10.00 grams of Ammonium Heptamolybdates (four water) are dissolved in the water of 60.0 grams 30 DEG C, obtained solution (II); ((III), prepares the salpeter solution (IV) of 0.1 mol/L 6.70 grams of oxalic acid hydrate niobiums to be dissolved in 10.0 grams of water formation solution; 2.13 grams of L-TARTARIC ACIDs are dissolved in 5.0 grams of water and form solution (V); Wherein L-TARTARIC ACID molecule and molybdenum atom mol ratio are 0.25.
Solution (I), in 80 DEG C of whipping process, adds salpeter solution (IV) gradually, makes the pH value of solution (I) be finally 4.5; Add 2.07 grams of antimonous oxide powder subsequently, stir 8 hours at 80 DEG C, successively solution (II) and solution (III) are joined in solution (I) subsequently, finally add L-TARTARIC ACID solution (V), obtain mixture paste.
This slurry stirs after 2 hours at 80 DEG C, puts into the oven drying 12 hours of 100 DEG C, and roasting 2 hours in the high pure nitrogen atmosphere of 600 DEG C subsequently, finally obtains Mo
1.00v
0.35nb
0.22sb
0.25o
xcatalyzer.
This catalyzer is got 60 ~ 80 order powder and is used for propane ammoxidation reaction after compressing tablet, screening, temperature of reaction is 410 DEG C, reaction pressure is normal pressure, in unstripped gas, the mol ratio of propane, ammonia and air is 1.0/1.5/15.0, duration of contact is 1.91 grams minutes/milliliters, and acquired results is as shown in table 1.
[embodiment 5]
1.92 grams of ammonium meta-vanadates are dissolved in the water of 60.0 grams 80 DEG C, obtained solution (I); 10.00 grams of Ammonium Heptamolybdates (four water) are dissolved in the water of 60.0 grams 30 DEG C, obtained solution (II); ((III), prepares the salpeter solution (IV) of 0.1 mol/L 4.57 grams of oxalic acid hydrate niobiums to be dissolved in 10.0 grams of water formation solution; 1.50 grams of oxalic acid (two water) are dissolved in 5.0 grams of water and form solution (V); Wherein oxalic acid molecule and molybdenum atom mol ratio are 0.21.
Solution (I), in 80 DEG C of whipping process, adds salpeter solution (IV) gradually, makes the pH value of solution (I) be finally 5.0; Add 2.07 grams of antimonous oxide powder subsequently, stir 12 hours at 95 DEG C, successively solution (II) and solution (III) are joined in solution (I) subsequently, finally add oxalic acid solution (V), obtain mixture paste.
This slurry stirs after 4 hours at 95 DEG C, puts into the oven drying 10 hours of 110 DEG C, and roasting 3 hours in the high-pure helium atmosphere of 650 DEG C is enclosed subsequently, finally obtains Mo
1.00v
0.29nb
0.15sb
0.25o
xcatalyzer.
This catalyzer is got 60 ~ 80 order powder and is used for propane ammoxidation reaction after compressing tablet, screening, temperature of reaction is 450 DEG C, reaction pressure is normal pressure, in unstripped gas, the mol ratio of propane, ammonia and air is 1.0/1.5/14.3, duration of contact is 2.00 grams minutes/milliliters, and acquired results is as shown in table 1.
[embodiment 6]
1.92 grams of ammonium meta-vanadates are dissolved in the water of 60.0 grams 80 DEG C, obtained solution (I); 10.00 grams of Ammonium Heptamolybdates (four water) are dissolved in the water of 60.0 grams 30 DEG C, obtained solution (II); ((III), prepares the salpeter solution (IV) of 0.1 mol/L 6.10 grams of oxalic acid hydrate niobiums to be dissolved in 10.0 grams of water formation solution; 0.50 gram of oxalic acid (two water) is dissolved in 5.0 grams of water and forms solution (V); Wherein oxalic acid molecule and molybdenum atom mol ratio are 0.07.
Solution (I), in 80 DEG C of whipping process, adds salpeter solution (IV) gradually, makes the pH value of solution (I) be finally 3.5; Add 1.49 grams of antimonous oxide powder subsequently, stir 7 hours at 95 DEG C, successively solution (II) and solution (III) are joined in solution (I) subsequently, finally add oxalic acid solution (V), obtain mixture paste.
This slurry stirs after 2 hours at 95 DEG C, puts into the oven drying 5 hours of 150 DEG C, and roasting 2 hours in the high-purity argon gas atmosphere of 650 DEG C subsequently, finally obtains Mo
1.00v
0.29nb
0.20sb
0.18o
xcatalyzer.
This catalyzer is got 60 ~ 80 order powder and is used for propane ammoxidation reaction after compressing tablet, screening, temperature of reaction is 430 DEG C, reaction pressure is normal pressure, in unstripped gas, the mol ratio of propane, ammonia and air is 1.0/1.2/10.0, duration of contact is 2.10 grams minutes/milliliters, and acquired results is as shown in table 1.
[comparative example 1]
As different from Example 1, do not add nitric acid and oxalic acid solution in catalyst preparation process, detailed process is:
1.92 grams of ammonium meta-vanadates are dissolved in the water of 60.0 grams 80 DEG C, obtained solution (I); 10.00 grams of Ammonium Heptamolybdates (four water) are dissolved in the water of 60.0 grams 30 DEG C, obtained solution (II); 1.08 grams of oxalic acid hydrate niobiums are dissolved in 10.0 grams of water and form solution ((III).
Solution (I) is in 80 DEG C of whipping process, add 1.16 grams of antimonous oxide powder, stir 5 hours at 90 DEG C, successively solution (II) and solution (III) are joined in solution (I) subsequently, obtain mixture paste.
This slurry stirs after 2 hours at 90 DEG C, puts into the oven drying 5 hours of 120 DEG C, and roasting 2 hours in the high pure nitrogen atmosphere of 600 DEG C subsequently, finally obtains Mo
1.00v
0.29nb
0.03sb
0.14o
xcatalyzer.
This catalyzer is got 60 ~ 80 order powder and is used for propane ammoxidation reaction after compressing tablet, screening, temperature of reaction is 440 DEG C, reaction pressure is normal pressure, in unstripped gas, the mol ratio of propane, ammonia and air is 1.0/1.2/10.0, duration of contact is 1.91 grams minutes/milliliters, and acquired results is as shown in table 1.
[comparative example 2]
As different from Example 2, do not add sulfuric acid and oxalic acid solution in catalyst preparation process, detailed process is:
2.06 grams of ammonium meta-vanadates are dissolved in the water of 60.0 grams 80 DEG C, obtained solution (I); 10.00 grams of Ammonium Heptamolybdates (four water) are dissolved in the water of 60.0 grams 30 DEG C, obtained solution (II); 5.50 grams of oxalic acid hydrate niobiums are dissolved in 10.0 grams of water and form solution ((III).
Solution (I) is in 80 DEG C of whipping process, add 1.65 grams of antimonous oxide powder, stir 2 hours at 90 DEG C, successively solution (II) and solution (III) are joined in solution (I) subsequently, obtain mixture paste.
This slurry stirs after 2 hours at 90 DEG C, puts into the oven drying 8 hours of 120 DEG C, and roasting 3 hours in the high-pure helium atmosphere of 650 DEG C is enclosed subsequently, finally obtains Mo
1.00v
0.31nb
0.18sb
0.20o
xcatalyzer.
This catalyzer is got 60 ~ 80 order powder and is used for propane ammoxidation reaction after compressing tablet, screening, temperature of reaction is 430 DEG C, reaction pressure is normal pressure, in unstripped gas, the mol ratio of propane, ammonia and air is 1.0/1.3/10.0, duration of contact is 1.71 grams minutes/milliliters, and acquired results is as shown in table 1.
[comparative example 3]
As different from Example 3, do not add hydrochloric acid and citric acid solution in catalyst preparation process, detailed process is:
1.33 grams of ammonium meta-vanadates are dissolved in the water of 60.0 grams 80 DEG C, obtained solution (I); 10.00 grams of Ammonium Heptamolybdates (four water) are dissolved in the water of 60.0 grams 30 DEG C, obtained solution (II); 4.58 grams of oxalic acid hydrate niobiums are dissolved in 10.0 grams of water and form solution ((III).
Solution (I) is in 80 DEG C of whipping process, add 1.90 grams of antimonous oxide powder, stir 5 hours at 90 DEG C, successively solution (II) and solution (III) are joined in solution (I) subsequently, obtain mixture paste.
This slurry stirs after 5 hours at 90 DEG C, puts into the oven drying 10 hours of 120 DEG C, and roasting 4 hours in the high-purity argon gas atmosphere of 550 DEG C subsequently, finally obtains Mo
1.00v
0.20nb
0.15sb
0.23o
xcatalyzer.
This catalyzer is got 60 ~ 80 order powder and is used for propane ammoxidation reaction after compressing tablet, screening, temperature of reaction is 420 DEG C, reaction pressure is normal pressure, in unstripped gas, the mol ratio of propane, ammonia and air is 1.0/1.1/10.0, duration of contact is 2.00 grams minutes/milliliters, and acquired results is as shown in table 1.
[comparative example 4]
As different from Example 1, only add nitric acid in catalyst preparation process and do not add oxalic acid, detailed process is:
1.92 grams of ammonium meta-vanadates are dissolved in the water of 60.0 grams 80 DEG C, obtained solution (I); 10.00 grams of Ammonium Heptamolybdates (four water) are dissolved in the water of 60.0 grams 30 DEG C, obtained solution (II); ((III) prepares the salpeter solution (IV) of 0.1 mol/L 1.08 grams of oxalic acid hydrate niobiums to be dissolved in 10.0 grams of water formation solution.
Solution (I), in 80 DEG C of whipping process, adds salpeter solution (IV) gradually, makes the pH value of solution (I) be finally 3.0; Add 1.16 grams of antimonous oxide powder subsequently, stir 5 hours at 90 DEG C, successively solution (II) and solution (III) are joined in solution (I) subsequently, obtain mixture paste.
This slurry stirs after 2 hours at 90 DEG C, puts into the oven drying 5 hours of 120 DEG C, and roasting 2 hours in the high pure nitrogen atmosphere of 600 DEG C subsequently, finally obtains Mo
1.00v
0.29nb
0.03sb
0.14o
xcatalyzer.
This catalyzer is got 60 ~ 80 order powder and is used for propane ammoxidation reaction after compressing tablet, screening, temperature of reaction is 440 DEG C, reaction pressure is normal pressure, in unstripped gas, the mol ratio of propane, ammonia and air is 1.0/1.2/10.0, duration of contact is 1.91 grams minutes/milliliters, and acquired results is as shown in table 1.
[comparative example 5]
As different from Example 1, do not add nitric acid in catalyst preparation process and only add oxalic acid, detailed process is:
1.92 grams of ammonium meta-vanadates are dissolved in the water of 60.0 grams 80 DEG C, obtained solution (I); 10.00 grams of Ammonium Heptamolybdates (four water) are dissolved in the water of 60.0 grams 30 DEG C, obtained solution (II); ((III), be dissolved in 5.0 grams of water by 2.50 grams of oxalic acid (two water) and form solution (V), wherein oxalic acid molecule and molybdenum atom mol ratio are 0.35 1.08 grams of oxalic acid hydrate niobiums to be dissolved in 10.0 grams of water formation solution.
Solution (I) is in 80 DEG C of whipping process, add 1.16 grams of antimonous oxide powder, stir 5 hours at 90 DEG C, successively solution (II) and solution (III) are joined in solution (I) subsequently, finally add oxalic acid solution (V), obtain mixture paste.
This slurry stirs after 2 hours at 90 DEG C, puts into the oven drying 5 hours of 120 DEG C, and roasting 2 hours in the high pure nitrogen atmosphere of 600 DEG C subsequently, finally obtains Mo
1.00v
0.29nb
0.03sb
0.14o
xcatalyzer.
This catalyzer is got 60 ~ 80 order powder and is used for propane ammoxidation reaction after compressing tablet, screening, temperature of reaction is 440 DEG C, reaction pressure is normal pressure, in unstripped gas, the mol ratio of propane, ammonia and air is 1.0/1.2/10.0, duration of contact is 1.91 grams minutes/milliliters, and acquired results is as shown in table 1.
Table 1
| Catalyzer forms | Preparation committed step | |
| Embodiment 1 | Mo 1.00V 0.29Nb 0.03Sb 0.14O x | Nitric acid adjusts pH=3.0, and oxalic acid is reductive agent |
| Embodiment 2 | Mo 1.00V 0.31Nb 0.18Sb 0.20O x | Sulfuric acid adjusts pH=2.0, and oxalic acid is reductive agent |
| Embodiment 3 | Mo 1.00V 0.20Nb 0.15Sb 0.23O x | Hydrochloric acid adjusts pH=4.5, and citric acid is reductive agent |
| Embodiment 4 | Mo 1.00V 0.35Nb 0.22Sb 0.25O x | Nitric acid adjusts pH=4.5, and tartrate is reductive agent |
| Embodiment 5 | Mo 1.00V 0.29Nb 0.15Sb 0.25O x | Nitric acid adjusts pH=6.0, and oxalic acid is reductive agent |
| Embodiment 6 | Mo 1.00V 0.29Nb 0.20Sb 0.18O x | Nitric acid adjusts pH=3.5, and oxalic acid is reductive agent |
| Comparative example 1 | Mo 1.00V 0.29Nb 0.06Sb 0.14O x | PH is adjusted, without oxalic acid without nitric acid |
| Comparative example 2 | Mo 1.00V 0.31Nb 0.18Sb 0.20O x | PH is adjusted, without oxalic acid without sulfuric acid |
| Comparative example 3 | Mo 1.00V 0.20Nb 0.15Sb 0.23O x | PH is adjusted, without citric acid without hydrochloric acid |
| Comparative example 4 | Mo 1.00V 0.29Nb 0.06Sb 0.14O x | Nitric acid adjusts pH=3.0, without oxalic acid |
| Comparative example 5 | Mo 1.00V 0.29Nb 0.06Sb 0.14O x | Adjust pH without nitric acid, oxalic acid is reductive agent |
Table 1(continues)
| Principal reaction condition | Conversion of propane (%) | Acrylonitrile selectivity (%) | |
| Embodiment 1 | 440 DEG C, normal pressure, C 3H 8/NH 3/Air=1.0/1.2/10.0 | 43.9 | 31.4 |
| Embodiment 2 | 430 DEG C, normal pressure, C 3H 8/NH 3/Air=1.0/1.3/12.0 | 40.6 | 29.4 |
| Embodiment 3 | 420 DEG C, normal pressure, C 3H 8/NH 3/Air=1.0/1.1/14.3 | 41.8 | 30.2 |
| Embodiment 4 | 410 DEG C, normal pressure, C 3H 8/NH 3/Air=1.0/1.5/15.0 | 40.6 | 28.8 |
| Embodiment 5 | 450 DEG C, normal pressure, C 3H 8/NH 3/Air=1.0/1.5/14.3 | 45.2 | 30.5 |
| Embodiment 6 | 430 DEG C, normal pressure, C 3H 8/NH 3/Air=1.0/1.2/10.0 | 42.4 | 29.0 |
| Comparative example 1 | With embodiment 1 | 28.6 | 15.3 |
| Comparative example 2 | With embodiment 2 | 25.8 | 11.3 |
| Comparative example 3 | With embodiment 3 | 24.3 | 9.7 |
| Comparative example 4 | With embodiment 1 | 33.8 | 10.4 |
| Comparative example 5 | With embodiment 1 | 18.3 | 12.5 |
Claims (9)
1. unsaturated nitrile catalyst, comprises the active constituent of following general formula according to atomic ratio:
Mo
1.00V
aNb
bSb
cO
x
The span of a is 0.1 ~ 1.0;
The span of b is 0.01 ~ 1.0;
The span of c is 0.01 ~ 1.0;
X is for meeting the Sauerstoffatom sum in catalyzer needed for each element valence.
2. the preparation method of catalyzer described in claim 1, comprises the following steps:
1) solution (I) is made by soluble in water for corresponding for aequum V salt;
2) solution (II) is made by soluble in water for corresponding for aequum Mo salt;
3) solution (III) is made by soluble in water for corresponding for aequum Nb salt;
4) pH value of (I) solution is regulated to be 1.5 ~ 5.0 with mineral acid, the oxide powder of Sb is joined in solution (I) and mix, stir at least 2 hours at 80 ~ 100 DEG C, add solution (II) and (III) more successively, finally add reductive agent and obtain mixture paste, wherein reductive agent is 0 ~ 0.42 with Mo atomic molar ratio, mixture paste stirs at least 2 hours at 80 ~ 100 DEG C, the thick slurry obtained, dry or moist, be roasting 0.5 ~ 8 hour in the inert atmosphere of 400 ~ 800 DEG C in temperature, thus obtain catalyzer.
3. the preparation method of catalyzer according to claim 2, is characterized in that mineral acid is at least one in sulfuric acid, nitric acid and hydrochloric acid or its mixture.
4. the preparation method of catalyzer according to claim 2, is characterized in that reductive agent is at least one in oxalic acid, citric acid and tartrate or its mixture.
5. the preparation method of catalyzer according to claim 2, is characterized in that time of drying is 0 ~ 24 hour.
6. the preparation method of catalyzer according to claim 2, is characterized in that maturing temperature is 500 ~ 700 DEG C.
7. the preparation method of catalyzer according to claim 2, is characterized in that roasting time is 2 ~ 4 hours.
8. the preparation method of catalyzer according to claim 2, is characterized in that inert atmosphere is at least one in helium, nitrogen or argon gas.
9. the application of catalyzer according to claim 1 in low-carbon alkanes ammonia oxidation synthesis unsaturated nitrile.
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| CN107282036A (en) * | 2016-04-13 | 2017-10-24 | 中国石油化工股份有限公司 | Low-carbon alkanes ammoxidation catalyst |
| CN107282058A (en) * | 2016-04-13 | 2017-10-24 | 中国石油化工股份有限公司 | Composite oxide catalysts |
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