CN104549261A - Catalyst for preparing unsaturated nitrile from alkane - Google Patents
Catalyst for preparing unsaturated nitrile from alkane Download PDFInfo
- Publication number
- CN104549261A CN104549261A CN201310512660.3A CN201310512660A CN104549261A CN 104549261 A CN104549261 A CN 104549261A CN 201310512660 A CN201310512660 A CN 201310512660A CN 104549261 A CN104549261 A CN 104549261A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- solution
- preparation
- precipitation
- catalyst according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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 for preparing unsaturated nitrile from alkane, a preparation method of the catalyst and application of the catalyst in ammoxidation synthesis of unsaturated nitrile by virtue of low carbon alkane. According to the catalyst, the preparation method and the application, the problems that the operation load of the catalyst is low, the propane conversion rate is low, and the stability is poor in the prior art are mainly solved. The catalyst comprises an active component in the following formula according to the atomic ratio: VaA1.00Ox, wherein A is at least one in the elements of Fe, Ca, Mg, Ni, Al and Zr, the value range of a is 0.1-1.0, and x meets the total number of oxygen atoms required by the valence of each element in the catalyst. According to the technical scheme, the problems are well solved. The catalyst can be applied to the industrial production for preparing unsaturated nitrile from low carbon alkane through ammoxidation.
Description
Technical field
The present invention relates to the catalyst of alkane unsaturated nitrile, preparation method and the application in low-carbon alkanes ammoxidation synthesis unsaturated nitrile thereof.
Background technology
Acrylonitrile is the important monomer of synthetic fibers, synthetic rubber and synthetic resin, is the important source material of basic organic industry.Through development for many years, acrylonitrile industrial production technology has reached its maturity and perfect.At present, the acrylonitrile commercial 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 acrylonitrile, all actively drops into acrylonitrile (methacrylonitrile) synthesis technique that exploitation is raw material with propane (iso-butane), 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 acrylonitrile commercial plant of raw material with propane and successfully goes into operation.
At present, propane (iso-butane) ammoxidation synthesis of acrylonitrile (methacrylonitrile) catalyst mainly contains the large catalyst system and catalyzing 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
xcatalyst is furtherd investigate, and thinks that (chemical formula is Mo to this catalyst 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.
Anderson type heteropolyacid salt (NH
4)
6teMo
6o
24nH
2o has material impact for the performance improving Mo-V series catalysts, but it is formed with the pH value of slurry in preparation process, mixing temperature and follow-up heat treatment process closely related.Therefore, the Mo-V series catalysts structure that different researchers obtains, phase composition difference are comparatively large, cause catalyst performance difference very large.
In patent US 6063728, US 6143916 pairs of Mo-V-Nb-Te (Sb) catalyst XRD collection of illustrative plates 2
θ=27.3
°± 0.3
°p1 peak intensity and 2
θ=28.2
°± 0.3
°p2 peak intensity analyze, design parameter 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 catalyst containing Te, find the prolongation with the reaction time, catalyst activity and acrylonitrile yield reduce gradually, and in reactor, add the activator containing Mo, Te by timing, to improve the stability of catalyst, this method brings adverse effect for the continuous seepage of industrialized unit.
Patent CN 1344584A discloses the preparation method of a kind of Mo-V-Nb-Te (Sb) catalyst, although acrylonitrile yield is higher, but this catalyst preparation process is complicated, the particularly acquisition methods of Nb raw material, the amplification for catalyst is produced and is brought difficulty.
Compared with Mo-V series catalysts, Sb-V catalyst mostly adopts aluminium oxide to be carrier, and therefore its BET specific surface area is larger than Mo-V system.The chemical formula that Sb-V catalyst 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 catalyst can by V
2o
5and Sb
2o
3at high temperature there is solid phase reaction preparation, also can be mixed by V, Sb slurry and co-precipitation preparation, V, Sb valence state now in catalyst, 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, in Sb-V catalyst, Mg, Al, W and Zr ion is introduced.XRD characterization result shows, and there is AlSbO in catalyst
4and MgSb
2o
6crystalline phase, and do not find VSbO
4phase.The activity influence added for Sb-V catalyst 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.
In addition, the catalyst of prior art is mostly less than 0.1 h at load
-1under condition, operation is (as CN 101616732 A, CN 101678326 A, CN101678327 A, CN 101878194 A, CN101970109 A and CN 102176966 A), and under high-load condition, there is the problem of the low and poor stability of conversion of propane.
Summary of the invention
One of technical problem to be solved by this invention is low, the poor stability of conversion of propane and the low problem of operational load in the catalyst of alkane ammoxidation unsaturated nitrile in prior art, a kind of catalyst of alkane unsaturated nitrile is provided, this catalyst has that conversion of propane is high, good stability and the feature of high load operation condition can be adapted to.
Two of technical problem to be solved by this invention is preparation methods of the catalyst 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 ammoxidation synthesis unsaturated nitrile of the described catalyst 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:
The catalyst of alkane unsaturated nitrile, comprises the active constituent of following general formula according to atomic ratio:
V
aA
1.00O
x
A is at least one in Fe, Ca, Mg, Ni, Al, Zr element;
The span of a is 0.1 ~ 1.0;
X is for meeting the oxygen atom sum in catalyst 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 catalyst described in the technical scheme of one of above-mentioned technical problem, 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 the corresponding salt of at least one in aequum Fe, Ca, Mg, Ni, Al, Zr element;
3) pH value of (I) solution is regulated to be 1.5 ~ 5.0 with inorganic acid, solution (II) is joined in solution (I), form the mixed solution of (I) and (II), carry out co-precipitation with inorganic base as precipitating reagent subsequently, precipitation pH value is at the end 3.5 ~ 6.0; The precipitation that obtains through filtering, washing, dry or moist, be roasting 0.5 ~ 8 hour in the atmosphere of 400 ~ 800 DEG C in temperature, thus obtain catalyst; Wherein dry temperature is 100 ~ 150 DEG C.
In technique scheme, described inorganic acid is preferably inorganic middle strong acid; More preferably at least one in sulfuric acid, nitric acid and hydrochloric acid.
In technique scheme, described inorganic base is at least one in ammoniacal liquor, potassium hydroxide and NaOH.
In technique scheme, be preferably 0 ~ 24 hour drying time, optimum is 2 ~ 10 hours.
In technique scheme, sintering temperature is preferably 500 ~ 700 DEG C.
In technique scheme, roasting time is preferably 2 ~ 4 hours.
In technique scheme, roasting gas atmosphere is preferably at least one in ammonia, helium, nitrogen or argon gas.
For solve the problems of the technologies described above three, technical scheme of the present invention is as follows: the catalyst described in the technical scheme of one of above-mentioned technical problem low-carbon alkanes ammoxidation synthesis unsaturated nitrile in application.
One of above-mentioned preferred technical scheme is the application in propane ammoxidation Reactive Synthesis acrylonitrile.
Above-mentioned preferred technical scheme two is the application in iso-butane ammoxidation reaction synthesize methyl acrylic nitrile.
In technique scheme, propane or iso-butane 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 iso-butane is preferably between 0.8 ~ 2.0, is preferably 1.0 ~ 1.5, and the mol ratio of air and propane or iso-butane is preferably 8.0 ~ 16.0, is preferably 10.0 ~ 15.0.
V raw material in catalyst is preferably corresponding sulfate or its ammonium salt, and the corresponding salt of Fe, Ca, Mg, Ni, Al, Zr element at least one is preferably corresponding halide, nitrate or sulfate.
Catalyst of the present invention by adding the pH value of inorganic acid control V solution, adding inorganic base and carries out co-precipitation and control precipitation pH value at the end in preparation process.Simple and the needed raw material of this preparation technology is easy to get, and the low-carbon alkanes ammoxidation catalyst prepared can stable operation under high load operation condition.
Catalyst of the present invention is evaluate in the fixed bed reactors of 8 millimeters at internal diameter, and loaded catalyst is 1.0 grams, and reaction temperature is 450 ~ 550 DEG C, is preferably 460 ~ 500 DEG C.
The conversion ratio of propane, the selective of acrylonitrile and be defined as follows time of contact:
When catalyst of the present invention is used for propane ammoxidation reaction, 0.90 h can be greater than at load
-1more than operate, especially when load is 1.24 h
-1time, conversion of propane, and can stable operation more than 100 hours up to 62.9 %, 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.
Detailed description of the invention
[embodiment 1]
0.8 gram of ammonium metavanadate is dissolved in the water of 228.0 grams 80 DEG C, obtained solution (I); 5.0 grams of aluminum nitrates (containing nine crystallizations water, being called for short nine water, lower same) are dissolved in the water of 130.0 grams 30 DEG C, form solution (II); Prepare the salpeter solution (III) of 0.1 mol/L; Prepare the ammonia spirit (IV) of 0.1 mol/L.
Solution (I), in 80 DEG C of whipping process, dropwise adds salpeter solution (III), makes its pH value be 1.5; Subsequently solution (II) is joined in solution (I), finally dropwise adding ammonia spirit (IV) carries out co-precipitation, precipitating at the end pH value is 5.5, the precipitation obtained is after filtering, washing, be in the baking oven of 120 DEG C dry 2 hours in temperature, roasting 2 hours in the ammonia atmosphere of 600 DEG C subsequently, obtains V
0.51al
1.00o
xcatalyst.
This catalyst is got 60 ~ 80 order powder and is used for propane ammoxidation reaction after compressing tablet, screening, and reaction temperature is 510 DEG C, and reaction pressure is normal pressure, and in unstripped gas, the mol ratio of propane, ammonia and air is 1.0/1.3/12.0, and load is 1.24 h
-1, acquired results is as shown in table 1.
[embodiment 2]
0.8 gram of ammonium metavanadate is dissolved in the water of 228.0 grams 80 DEG C, obtained solution (I); 11.0 grams of ferric nitrates (nine water) are dissolved in the water of 265.0 grams 30 DEG C, form solution (II); Prepare the salpeter solution (III) of 0.1 mol/L; Prepare the ammonia spirit (IV) of 0.1 mol/L.
Solution (I), in 80 DEG C of whipping process, dropwise adds salpeter solution (III), makes its pH value be 2.0; Subsequently solution (II) is joined in solution (I), finally dropwise adding ammonia spirit (IV) carries out co-precipitation, precipitating at the end pH value is 6.0, the precipitation obtained is after filtering, washing, be in the baking oven of 110 DEG C dry 5 hours in temperature, roasting 2 hours in the high pure nitrogen atmosphere of 600 DEG C subsequently, obtains V
0.25fe
1.00o
xcatalyst.
This catalyst is got 60 ~ 80 order powder and is used for propane ammoxidation reaction after compressing tablet, screening, and reaction temperature is 500 DEG C, and reaction pressure is normal pressure, and in unstripped gas, the mol ratio of propane, ammonia and air is 1.0/1.2/10.0, and load is 1.93 h
-1, acquired results is as shown in table 1.
[embodiment 3]
0.8 gram of ammonium metavanadate is dissolved in the water of 228.0 grams 80 DEG C, obtained solution (I); 8.2 grams of calcium nitrate (four water) are dissolved in the water of 340.0 grams 30 DEG C, form solution (II); Prepare the sulfuric acid solution (III) of 0.1 mol/L; Prepare the potassium hydroxide solution (IV) of 0.1 mol/L.
Solution (I), in 80 DEG C of whipping process, dropwise adds sulfuric acid solution (III), makes its pH value be 3.5; Subsequently solution (II) is joined in solution (I), finally dropwise adding potassium hydroxide solution (IV) carries out co-precipitation, precipitating at the end pH value is 4.0, the precipitation obtained is after filtering, washing, be in the baking oven of 120 DEG C dry 5 hours in temperature, roasting 2 hours in the high-pure helium atmosphere of 650 DEG C is enclosed subsequently, obtains V
0.20ca
1.00o
xcatalyst.
This catalyst is got 60 ~ 80 order powder and is used for propane ammoxidation reaction after compressing tablet, screening, and reaction temperature is 490 DEG C, and reaction pressure is normal pressure, and in unstripped gas, the mol ratio of propane, ammonia and air is 1.0/1.1/14.3, and load is 1.44 h
-1, acquired results is as shown in table 1.
[embodiment 4]
0.8 gram of ammonium metavanadate is dissolved in the water of 228.0 grams 80 DEG C, obtained solution (I); 12.0 grams of nickel nitrates (six water) are dissolved in the water of 375.0 grams 30 DEG C, form solution (II); Prepare the hydrochloric acid solution (III) of 0.1 mol/L; Prepare the sodium hydroxide solution (IV) of 0.1 mol/L.
Solution (I), in 80 DEG C of whipping process, dropwise adds hydrochloric acid solution (III), makes its pH value be 4.5; Subsequently solution (II) is joined in solution (I), finally dropwise adding sodium hydroxide solution (IV) carries out co-precipitation, precipitating at the end pH value is 5.5, the precipitation obtained is after filtering, washing, be in the baking oven of 130 DEG C dry 2 hours in temperature, roasting 3 hours in the high-purity argon gas atmosphere of 550 DEG C subsequently, obtains V
0.17ca
1.00o
xcatalyst.
This catalyst is got 60 ~ 80 order powder and is used for propane ammoxidation reaction after compressing tablet, screening, and reaction temperature is 510 DEG C, and reaction pressure is normal pressure, and in unstripped gas, the mol ratio of propane, ammonia and air is 1.0/1.5/15.0, and load is 0.94 h
-1, acquired results is as shown in table 1.
[embodiment 5]
0.8 gram of ammonium metavanadate is dissolved in the water of 228.0 grams 80 DEG C, obtained solution (I); 15.0 grams of magnesium nitrates (six water) are dissolved in the water of 550.0 grams 30 DEG C, form solution (II); Prepare the salpeter solution (III) of 0.1 mol/L; Prepare the sodium hydroxide solution (IV) of 0.1 mol/L.
Solution (I), in 80 DEG C of whipping process, dropwise adds salpeter solution (III), makes its pH value be 3.5; Subsequently solution (II) is joined in solution (I), finally dropwise adding sodium hydroxide solution (IV) carries out co-precipitation, precipitating at the end pH value is 4.5, the precipitation obtained is after filtering, washing, be in the baking oven of 100 DEG C dry 8 hours in temperature, roasting 2 hours in the ammonia atmosphere of 650 DEG C subsequently, obtains V
0.12mg
1.00o
xcatalyst.
This catalyst is got 60 ~ 80 order powder and is used for propane ammoxidation reaction after compressing tablet, screening, and reaction temperature is 480 DEG C, and reaction pressure is normal pressure, and in unstripped gas, the mol ratio of propane, ammonia and air is 1.0/1.5/14.3, and load is 1.40 h
-1, acquired results is as shown in table 1.
[embodiment 6]
0.8 gram of ammonium metavanadate is dissolved in the water of 228.0 grams 80 DEG C, obtained solution (I); 19.0 grams of zirconium nitrates (five water) are dissolved in the water of 440.0 grams 30 DEG C, form solution (II); Prepare the salpeter solution (III) of 0.1 mol/L; Prepare the ammonia spirit (IV) of 0.1 mol/L.
Solution (I), in 80 DEG C of whipping process, dropwise adds salpeter solution (III), makes its pH value be 2.0; Subsequently solution (II) is joined in solution (I), finally dropwise adding ammonia spirit (IV) carries out co-precipitation, precipitating at the end pH value is 3.0, the precipitation obtained is after filtering, washing, be in the baking oven of 110 DEG C dry 8 hours in temperature, roasting 2 hours in the high pure nitrogen atmosphere of 600 DEG C subsequently, obtains V
0.12mg
1.00o
xcatalyst.
This catalyst is got 60 ~ 80 order powder and is used for propane ammoxidation reaction after compressing tablet, screening, and reaction temperature is 500 DEG C, and reaction pressure is normal pressure, and in unstripped gas, the mol ratio of propane, ammonia and air is 1.0/1.3/12.0, and load is 1.33 h
-1, acquired results is as shown in table 1.
[comparative example 1]
As different from Example 1, do not add nitric acid in catalyst preparation process, detailed process is:
0.8 gram of ammonium metavanadate is dissolved in the water of 228.0 grams 80 DEG C, obtained solution (I); 5.0 grams of aluminum nitrates (nine water) are dissolved in the water of 130.0 grams 30 DEG C, form solution (II); Prepare the ammonia spirit (IV) of 0.1 mol/L.
Solution (I) is in 80 DEG C of whipping process, slowly add solution (II), dropwise add ammonia spirit (IV) subsequently and carry out co-precipitation, precipitating at the end pH value is 5.5, the precipitation obtained is after filtering, washing, be in the baking oven of 120 DEG C dry 2 hours in temperature, roasting 2 hours in the ammonia atmosphere of 600 DEG C subsequently, obtains V
0.51al
1.00o
xcatalyst.
This catalyst is got 60 ~ 80 order powder and is used for propane ammoxidation reaction after compressing tablet, screening, and reaction temperature is 510 DEG C, and reaction pressure is normal pressure, and in unstripped gas, the mol ratio of propane, ammonia and air is 1.0/1.3/12.0, and load is 1.24 h
-1, acquired results is as shown in table 1.
[comparative example 2]
As different from Example 2, do not add nitric acid in catalyst preparation process, detailed process is:
0.8 gram of ammonium metavanadate is dissolved in the water of 228.0 grams 80 DEG C, obtained solution (I); 11.0 grams of ferric nitrates (nine water) are dissolved in the water of 265.0 grams 30 DEG C, form solution (II); Prepare the ammonia spirit (IV) of 0.1 mol/L.
Solution (I) is in 80 DEG C of whipping process, slowly add solution (II), dropwise add ammonia spirit (IV) subsequently and carry out co-precipitation, precipitating at the end pH value is 6.0, the precipitation obtained is after filtering, washing, be in the baking oven of 110 DEG C dry 5 hours in temperature, roasting 2 hours in the high pure nitrogen atmosphere of 600 DEG C subsequently, obtains V
0.25fe
1.00o
xcatalyst.
This catalyst is got 60 ~ 80 order powder and is used for propane ammoxidation reaction after compressing tablet, screening, and reaction temperature is 500 DEG C, and reaction pressure is normal pressure, and in unstripped gas, the mol ratio of propane, ammonia and air is 1.0/1.2/10.0, and load is 1.93 h
-1, acquired results is as shown in table 1.
[comparative example 3]
As different from Example 3, do not add sulfuric acid in catalyst preparation process, detailed process is:
0.8 gram of ammonium metavanadate is dissolved in the water of 228.0 grams 80 DEG C, obtained solution (I); 8.2 grams of calcium nitrate (four water) are dissolved in the water of 340.0 grams 30 DEG C, form solution (II); Prepare the potassium hydroxide solution (IV) of 0.1 mol/L.
Solution (I) is in 80 DEG C of whipping process, slowly add solution (II), dropwise add potassium hydroxide solution (IV) subsequently and carry out co-precipitation, precipitating at the end pH value is 4.0, the precipitation obtained is after filtering, washing, be in the baking oven of 120 DEG C dry 5 hours in temperature, roasting 2 hours in the high-pure helium atmosphere of 650 DEG C is enclosed subsequently, obtains V
0.20ca
1.00o
xcatalyst.
This catalyst is got 60 ~ 80 order powder and is used for propane ammoxidation reaction after compressing tablet, screening, and reaction temperature is 490 DEG C, and reaction pressure is normal pressure, and in unstripped gas, the mol ratio of propane, ammonia and air is 1.0/1.1/14.3, and load is 1.44 h
-1, acquired results is as shown in table 1.
1(is continued for table)
| Catalyst forms | Preparation committed step | |
| Embodiment 1 | V 0.51Al 1.00O x | Nitric acid adjusts pH=1.5, and ammoniacal liquor adjusts pH=5.5 |
| Embodiment 2 | V 0.25Fe 1.00O x | Nitric acid adjusts pH=2.0, and ammoniacal liquor adjusts pH=6.0 |
| Embodiment 3 | V 0.20Ca 1.00O x | Sulfuric acid adjusts pH=3.5, and pH=4.0 adjusted by potassium hydroxide |
| Embodiment 4 | V 0.17Ni 1.00O x | Hydrochloric acid adjusts pH=4.5, and NaOH adjusts pH=5.5 |
| Embodiment 5 | V 0.12Mg 1.00O x | Nitric acid adjusts pH=3.5, and NaOH adjusts pH=4.5 |
| Embodiment 6 | V 0.15Zr 1.00O x | Nitric acid adjusts pH=2.0, and ammoniacal liquor adjusts pH=3.0 |
| Comparative example 1 | V 0.51Al 1.00O x | Adjust pH without nitric acid, ammoniacal liquor adjusts pH=5.5 |
| Comparative example 2 | V 0.25Fe 1.00O x | Adjust pH without nitric acid, ammoniacal liquor adjusts pH=6.0 |
| Comparative example 3 | V 0.20Ca 1.00O x | Adjust pH without sulfuric acid, pH=4.0 adjusted by potassium hydroxide |
Table 1(continues)
Claims (9)
1. the catalyst of alkane unsaturated nitrile, comprises the active constituent of following general formula according to atomic ratio:
V
aA
1.00O
x
A is Fe, Ca, Mg, Ni, Al, Zr element at least one;
The span of a is 0.1 ~ 1.0;
X is for meeting the oxygen atom sum in catalyst needed for each element valence.
2. the preparation method of catalyst 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 the corresponding salt of at least one in aequum Fe, Ca, Mg, Ni, Al, Zr element;
3) pH value of (I) solution is regulated to be 1.5 ~ 5.0 with inorganic acid, solution (II) is joined in solution (I), form the mixed solution of (I) and (II), carry out co-precipitation with inorganic base as precipitating reagent subsequently, precipitation pH value is at the end 3.5 ~ 6.0; The precipitation that obtains through filtering, washing, dry or moist, be roasting 0.5 ~ 8 hour in the atmosphere of 400 ~ 800 DEG C in temperature, thus obtain catalyst; Wherein dry temperature is 100 ~ 150 DEG C.
3. the preparation method of catalyst according to claim 2, is characterized in that inorganic acid is at least one in sulfuric acid, nitric acid and hydrochloric acid.
4. the preparation method of catalyst according to claim 2, is characterized in that inorganic base is at least one in ammoniacal liquor, potassium hydroxide and NaOH.
5. the preparation method of catalyst according to claim 2, is characterized in that drying time is 0 ~ 24 hour.
6. the preparation method of catalyst according to claim 2, is characterized in that sintering temperature is 500 ~ 700 DEG C.
7. the preparation method of catalyst according to claim 2, is characterized in that roasting gas atmosphere is at least one in ammonia, helium, nitrogen or argon gas.
8. the preparation method of catalyst according to claim 2, is characterized in that roasting time is 2 ~ 4 hours.
9. the application of catalyst according to claim 1 in low-carbon alkanes ammoxidation synthesis unsaturated nitrile.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310512660.3A CN104549261B (en) | 2013-10-28 | 2013-10-28 | The catalyst of alkane unsaturated nitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310512660.3A CN104549261B (en) | 2013-10-28 | 2013-10-28 | The catalyst of alkane unsaturated nitrile |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104549261A true CN104549261A (en) | 2015-04-29 |
| CN104549261B CN104549261B (en) | 2017-07-14 |
Family
ID=53066967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310512660.3A Active CN104549261B (en) | 2013-10-28 | 2013-10-28 | The catalyst of alkane unsaturated nitrile |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104549261B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112691678A (en) * | 2019-10-22 | 2021-04-23 | 中国石油化工股份有限公司 | Catalyst for preparing butadiene by oxidative dehydrogenation of butylene and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1426834A (en) * | 2001-12-21 | 2003-07-02 | 沙地基本工业公司 | Catalyst composition for ammoxidation of parafins and olefins, and preparing process and use thereof |
| US20060122055A1 (en) * | 2004-12-06 | 2006-06-08 | Gaffney Anne M | (Amm)oxidation catalyst and catalytic (amm)oxidation process for conversion of lower alkanes |
-
2013
- 2013-10-28 CN CN201310512660.3A patent/CN104549261B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1426834A (en) * | 2001-12-21 | 2003-07-02 | 沙地基本工业公司 | Catalyst composition for ammoxidation of parafins and olefins, and preparing process and use thereof |
| US20060122055A1 (en) * | 2004-12-06 | 2006-06-08 | Gaffney Anne M | (Amm)oxidation catalyst and catalytic (amm)oxidation process for conversion of lower alkanes |
Non-Patent Citations (3)
| Title |
|---|
| DELIA GAZZOLI ET AL.: "Bulk and surface structures of V2O5/ZrO2 catalysts for n-butane oxidative dehydrogenation", 《JOURNAL OF MOLECULAR CATALYSIS A：CHEMICAL》 * |
| E.ROMBI ET AL.: "Toluene ammoxidation on α-Fe2O3-based catalysts", 《APPLIED CATALYSIS A：GENERAL》 * |
| O.V.SAFONOVA ET AL.: "Local environment of vanadium in V/Al/O-mixed oxide catalyst for propane ammoxidation：Characterization by in situ valence-to-core X-ray emission spectroscopy and X-ray absorption spectroscopy", 《JOURNAL OF CATALYSIS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112691678A (en) * | 2019-10-22 | 2021-04-23 | 中国石油化工股份有限公司 | Catalyst for preparing butadiene by oxidative dehydrogenation of butylene and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104549261B (en) | 2017-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104549373B (en) | Low-carbon alkanes ammoxidation catalyst | |
| CN103752319B (en) | Anti-carbon Ni methylmethane vapor reforming hydrogen production catalyst and preparation method thereof | |
| CN107486234B (en) | Catalyst for preparing light aromatic hydrocarbon by directly converting synthesis gas and preparation method thereof | |
| CN103657659B (en) | Catalyst for preparing butadiene by oxidative dehydrogenation of butene and preparation method of catalyst | |
| CN110280250B (en) | Preparation method and application of zeolite imidazole framework material derived metal oxide | |
| CN101966460B (en) | Supported catalyst for synthesis of dimethyl carbonate, preparation method and using method thereof | |
| CN110694656A (en) | Hydrotalcite-based nickel phosphide catalyst and application thereof in preparation of cyclane through guaiacol conversion | |
| CN112774674A (en) | Supported ruthenium cluster catalyst for ammonia synthesis, and preparation method and application thereof | |
| CN110193368B (en) | Preparation method of spinel type catalytic material | |
| CN104549224B (en) | Unsaturated nitrile catalyst and preparation method thereof | |
| CN104979555A (en) | Submicron-scale cobalt-manganese composite oxide material and preparation method thereof | |
| CN113842914A (en) | Catalyst for synthesizing methanol from carbon dioxide, and preparation method and application thereof | |
| CN102294251B (en) | Nano-oxide catalyst for preparing propylene by oxidative dehydrogenation of propane and preparation method thereof | |
| CN104549261A (en) | Catalyst for preparing unsaturated nitrile from alkane | |
| CN111185186A (en) | Single-phase composite metal oxide catalyst, preparation method and application thereof | |
| CN107282036A (en) | Low-carbon alkanes ammoxidation catalyst | |
| CN115837275A (en) | Perovskite type high-entropy oxide and preparation method and application thereof | |
| CN105312067A (en) | Light alkane ammoxidation catalyst | |
| CN107282058B (en) | Composite oxide catalyst | |
| CN111974409A (en) | Flaky porous manganese-doped nickel oxide catalyst, preparation method and application thereof | |
| CN111057030A (en) | Preparation method and application of hydrotalcite-based sulfide catalyst for synthesizing gamma-valerolactone | |
| KR101353220B1 (en) | Catalyst for promoting formation of element sulfur in high temperature and method for producing the same | |
| CN112125809B (en) | Method for continuously preparing pentanediamine by decarboxylation of lysine | |
| CN115672299B (en) | Titanium dioxide nanowire and preparation method thereof, denitration catalyst and preparation method thereof, and flue gas denitration method | |
| CN114011471B (en) | MnCO 3 Modified catalyst @ ZIF-8, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |