CN104549224B - Unsaturated nitrile catalyst and preparation method thereof - Google Patents
Unsaturated nitrile catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to unsaturated nitrile catalyst and preparation method thereof, mainly solve that catalyst yield present in prior art is low, poor selectivity, and stability it is poor the problem of.The present invention includes the active constituent of general formula according to atomic ratio by using unsaturated nitrile catalyst：Mo1.00VaNbbSbcOx；A span is 0.1~1.0；B span is 0.01~1.0；C span is 0.01~1.0；X preferably solves the problem, in the industrial production available for low-carbon alkanes ammoxidation unsaturated nitrile for the technical scheme of the oxygen atom sum needed for meeting each element chemical valence in catalyst.
Description
Technical field
The present invention relates to unsaturated nitrile catalyst and preparation method thereof.It is specially adapted to propane ammoxidation reaction synthesis propylene
The catalyst of nitrile and iso-butane ammoxidation reaction synthesizing methyl acrylonitrile.
Background technology
Acrylonitrile is the important monomer of synthetic fibers, synthetic rubber and synthetic resin, is the important of basic organic industry
Raw material.By development for many years, acrylonitrile industrial production technology has reached its maturity and perfect.At present, more than the % of the whole world 95
Acrylonitrile commercial plant all use Sohio method technique of BP/Ineos companies using propylene as raw material.
In recent years, with the development and utilization of large-scale shale gas, huge price difference is formd between propane and propylene.Entirely
The main production firm of ball acrylonitrile, all actively input exploitation is closed with propane (iso-butane) for the acrylonitrile (methacrylonitrile) of raw material
Into technique, to reduce production cost, product competitiveness is improved.2 months 2013, Japanese Asahi Kasei companies were in Thailand
State builds up acrylonitrile commercial plant of global first 200,000 tons/year of the set using propane as raw material and successfully gone into operation.
At present, propane (iso-butane) ammoxidation synthesis of acrylonitrile (methacrylonitrile) catalyst mainly has Mo-V-Nb-Te
And the big catalyst system and catalyzings of Sb-V two (Sb).
([1] Robert K. Grasselli. Advances and future trends in such as Grasselli
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)-OxCatalyst is deeply ground
Study carefully, it is believed that by club shaped structure orthorhombic phase M1, (chemical formula is Mo to the catalyst7.8V1.95Nb0.86Te1.33Ox, or { TeO }1-x
(Mo,V,Nb)10O28, { TeO } is the component inserted in skeleton duct), (chemical formula is six side phase M2 of slab construction standard
Mo1.0V0.28/0.31Nb0.08Te0.27-0.39O4.24, or { TeO }2-x (Mo,V,Nb)6O18) and trace monocline crystalline phase TeMo5O16Group
Into.Wherein M1 is that propane activates phase, and M2 is propylene activity of conversion phase, and when the two ratio is 3/2, acrylonitrile yield is reached as high as
62%, however, the preparation of simple M1 and M2 phases is complicated.
Patent US 6063728, US 6143916 is in Mo-V-Nb-Te (Sb) catalyst XRD spectrum 2θ = 27.3°±
0.3°P1 peak intensities and 2θ = 28.2°± 0.3°P2 peak intensities analyzed, design parameter R=P1/ (P1+P2) is obtained
Go out when catalyst performance is optimal, R is 0.40< R <Between 0.75, this provides reference for the exploitation of Mo-V series catalysts.
Patent CN 1220258A disclose a kind of Mo-V catalyst containing Te, find the extension with the reaction time, catalysis
Agent activity and acrylonitrile yield are gradually reduced, and add the activator containing Mo, Te into reactor by timing, to improve catalysis
The stability of agent, this method brings adverse effect for the continuous production of industrialized unit.
Patent CN 1344584A disclose a kind of preparation method of Mo-V-Nb-Te (Sb) catalyst, although acrylonitrile is received
Rate is higher, but the catalyst preparation process is complicated, particularly the acquisition methods of Nb raw materials, and the amplification for catalyst produces band
Come difficult.
Compared with Mo-V series catalysts, Sb-V catalyst mostly uses aluminum oxide for carrier, therefore its BET specific surface area ratio
Mo-V systems are big.The VSbO with rutile structure is included in the chemical formula that Sb-V catalyst is not fixed, its crystal phase structure4With α-
Sb2O4Association phase, wherein in VSbO4In, Sb is mainly with Sb5+, V is mainly with V3+Form is present (in addition with a small amount of V4+), therefore
VSbO4(V can be used3+-V4+ )Sb1-xO4Represent.When Sb/V is more than 1.0, excessive Sb is with α-Sb2O4It is covered in VSbO4Table
In face, catalytic reaction process, Sb is from α-Sb2O4Association mutually moves to SbVO4In, form Sb5+-V3+/V4+Ammoxidation of propylene reacts
Activated centre, catalyst performance starts to lift (S. Albonetti, G. Blanchard, P. Burattin, T.J.
Cassidy, S.Masetti, F. Trifirò. Mechanism of ammoxidation of propane on a Sb/
V/O system. Catalysis Letters, 1997, 45:119-123.)。
Sb-V catalyst can be by V2O5And Sb2O3Solid phase reaction occurs at high temperature to prepare, can also be mixed by V, Sb slurry
Close and be prepared by co-precipitation, now V, Sb valence state in catalyst, crystal phase structure and catalytic performance are relevant with its preparation method,
Such as Sb/V atomic ratios, metal-modified ionic species, mixing temperature and heat treatment condition etc..
(Shahid Shaikh, Kathleen Bethke, the Edouard Mamedov. Propane such as Shaikh
ammoxidation on bulk, diluted and supported VSb oxides. Topics in Catalysis,
2006, 38(4):241-249.) by coprecipitation, Mg, Al, W and Zr ion are introduced in Sb-V catalyst.XRD is characterized
As a result show there is AlSbO in catalyst4And MgSb2O6Crystalline phase, and VSbO is not found4Phase.Zr and Mg addition is for Sb-V
The activity influence of catalyst is not obvious；And Al addition, catalyst activity is substantially increased, and Propylene Selectivity is greatly reduced,
Its reason is probably Sb and V due to Al addition so that the two is in VSbO4Isolated well in oxide structure.
But the catalyst of prior art is present, and yield is low, poor selectivity, and stability it is poor the problem of.
The content of the invention
One of technical problems to be solved by the invention are that catalyst yield present in prior art is low, poor selectivity,
And there is provided a kind of unsaturated nitrile catalyst the problem of stability difference, the catalyst has high income, selectivity high, Yi Jiwen
Qualitative good the characteristics of.
The two of the technical problems to be solved by the invention are the preparation methods of the catalyst described in one of above-mentioned technical problem.
The three of the technical problems to be solved by the invention are one of above-mentioned technical problem catalyst in low-carbon alkanes ammonia
Application in oxidative synthesis unsaturated nitrile.
To solve one of above-mentioned technical problem, technical scheme is as follows：
Unsaturated nitrile catalyst, the active constituent of general formula is included according to atomic ratio：
Mo1.00VaNbbSbcOx
A span is 0.1~1.0；
B span is 0.01~1.0；
C span is 0.01~1.0；
X is the oxygen atom sum needed for meeting each element chemical valence in catalyst.
In order to solve the above-mentioned technical problem two, technical scheme is as follows：Catalyst described in claim 1
Preparation method, comprises the following steps：
1) solution (I) is made by the corresponding salt of aequum V is soluble in water；
2) solution (II) is made by the corresponding salt of aequum Mo is soluble in water；
3) solution (III) is made by the corresponding salt of aequum Nb is soluble in water；
4) pH value that (I) solution is adjusted with inorganic acid is 1.5 ~ 5.0, and Sb oxide powder is added in solution (I)
It is well mixed, stirred at least 2 hours at 80 ~ 100 DEG C, sequentially add solution (II) and (III), be eventually adding reducing agent and obtain
Mixture paste, wherein reduction agent molecule is 0 ~ 0.42 with Mo atomic molars ratio, mixture paste stirs at least 2 at 80 ~ 100 DEG C
Hour, obtained thick slurry is dry or moist, and roasting 0.5 ~ 8 is small in temperature is 400 ~ 800 DEG C of inert atmosphere
When, so as to obtain catalyst.Wherein dry temperature is preferably 100 ~ 150 DEG C.
In above-mentioned technical proposal, the inorganic acid is preferably inorganic middle strong acid；More preferably in sulfuric acid, nitric acid and hydrochloric acid
At least one or its mixture.
In above-mentioned technical proposal, the reducing agent be preferably at least one of oxalic acid, citric acid and tartaric acid or its
Mixture.In above-mentioned technical proposal, the reducing agent reducing agent is with Mo atomic molars than preferably ＞ 0 and below 0.42.
In above-mentioned technical proposal, drying time is preferably 0 ~ 24 hour, and optimal is 2 ~ 10 hours.
In above-mentioned technical proposal, sintering temperature is preferably 500 ~ 700 DEG C.
In above-mentioned technical proposal, inert atmosphere is preferably at least one of helium, nitrogen or argon gas.
In above-mentioned technical proposal, roasting time is preferably 2 ~ 4 hours.
To solve the three of above-mentioned technical problem, technical scheme is as follows：The technical side of one of above-mentioned technical problem
Application of the catalyst in low-carbon alkanes ammoxidation synthesizes unsaturated nitrile described in case.
One of above-mentioned preferred technical scheme, is the application in propane ammoxidation reaction synthesis of acrylonitrile.
The two of above-mentioned preferred technical scheme, are the applications in iso-butane ammoxidation reaction synthesizing methyl acrylonitrile.
In above-mentioned technical proposal, propane or iso-butane are preferably industrial gasses purity, and molecular oxygen is pure oxygen, oxygen-enriched and sky
Gas, preferably air.
The mol ratio of ammonia and propane or iso-butane is preferably between 0.8~2.0 preferably 1.0~1.5 in unstripped gas, empty
The mol ratio of gas and propane or iso-butane is preferably 8.0~16.0, and preferably 10.0~15.0.
Mo raw materials in catalyst are preferably corresponding oxide or its ammonium salt, V raw materials be preferably corresponding oxide or
Its ammonium salt, Sb raw materials are preferably corresponding oxide, and Nb raw materials are preferably corresponding oxide, hydroxide, nitrate or grass
Hydrochlorate.
The catalyst of the present invention controls the pH value of solution in preparation process by adding inorganic acid, adds reducing agent regulation
The oxidation state of oxide, preparation technology is simple, and repeatability, stability are preferable, and required raw material is easy to get, and can prepare performance
Excellent low-carbon alkanes ammoxidation catalyst.
Catalyst of the present invention is evaluated in internal diameter is 8 millimeters of fixed bed reactors, and loaded catalyst is 3.0
Gram, reaction temperature is 370~460 DEG C, preferably 390~450 DEG C.
The conversion ratio of propane, the selectivity of acrylonitrile and time of contact are defined as follows：
When the catalyst of the present invention is used for propane ammoxidation reaction, conversion of propane is up to 43.9%, and acrylonitrile selectivity can
Up to more than 29.0%；After 198 hours react, conversion of propane is 43.9%, and acrylonitrile selectivity is 28.9%, catalyst performance
Can be relatively stable, achieve preferable technique effect.
Below by specific embodiment, the invention will be further elaborated, but the present invention is not limited by the following examples.
Brief description of the drawings
Fig. 1 represents embodiment 1 and its on year-on-year basis the stability experiment data of comparative example.
Embodiment
【Embodiment 1】
In the water that 1.92 grams of ammonium metavanadates are dissolved in 60.0 grams 80 DEG C, obtained solution (I)；10.00 grams of ammonium heptamolybdates (are contained
Four crystallizations water, referred to as four water, similarly hereinafter) be dissolved in 60.0 grams 30 DEG C of water, obtained solution (II)；By 1.08 grams of oxalic acid hydrate niobiums
Being dissolved in 10.0 grams of water formation solution, ((III) prepares the salpeter solution (IV) of 0.1 mol/L；2.50 grams of oxalic acid (two water) are dissolved in
Solution (V) is formed in 5.0 grams of water；Wherein oxalic acid molecule and molybdenum atom mol ratio are 0.35.
Solution (I) is gradually added into salpeter solution (IV) in 80 DEG C of whipping process so that the pH value of solution (I) is finally
3.0；1.16 grams of antimony oxide powder are subsequently added, are stirred 5 hours at 90 DEG C, then successively by solution (II) and solution (III)
It is added in solution (I), is eventually adding oxalic acid solution (V), obtains mixture paste.
The slurry is put into 120 DEG C of oven drying 5 hours, then in 600 DEG C of High Purity Nitrogen after 90 DEG C are stirred 2 hours
Atmosphere encloses middle roasting 2 hours, finally gives Mo1.00V0.29Nb0.03Sb0.14OxCatalyst.
The catalyst takes 60 ~ 80 mesh powder to be used for propane ammoxidation reaction after tabletting, screening, and reaction temperature is 440
DEG C, reaction pressure is that the mol ratio of propane, ammonia and air in normal pressure, unstripped gas is 1.0/1.2/10.0, and time of contact is
1.91 grams of minute/milliliters, acquired results are as shown in table 1.
【Embodiment 2】
In the water that 2.06 grams of ammonium metavanadates are dissolved in 60.0 grams 80 DEG C, obtained solution (I)；By 10.00 grams of ammonium heptamolybdates (four
Water) it is dissolved in 60.0 grams 30 DEG C of water, obtained solution (II)；5.50 grams of oxalic acid hydrate niobiums are dissolved in 10.0 grams of water formation solution
((III) prepares the sulfuric acid solution (IV) of 0.1 mol/L；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) is gradually added into sulfuric acid solution (IV) in 80 DEG C of whipping process so that the pH value of solution (I) is finally
2.0；1.65 grams of antimony oxide powder are subsequently added, are stirred 2 hours at 90 DEG C, then successively by solution (II) and solution (III)
It is added in solution (I), is eventually adding oxalic acid solution (V), obtains mixture paste.
The slurry is put into 120 DEG C of oven drying 8 hours, then in 650 DEG C of high-pure helium after 90 DEG C are stirred 2 hours
Atmosphere encloses middle roasting 3 hours, finally gives Mo1.00V0.31Nb0.18Sb0.20OxCatalyst.
The catalyst takes 60 ~ 80 mesh powder to be used for propane ammoxidation reaction after tabletting, screening, and reaction temperature is 430
DEG C, reaction pressure is that the mol ratio of propane, ammonia and air in normal pressure, unstripped gas is 1.0/1.3/10.0, and time of contact is
1.71 grams of minute/milliliters, acquired results are as shown in table 1.
【Embodiment 3】
In the water that 1.33 grams of ammonium metavanadates are dissolved in 60.0 grams 80 DEG C, obtained solution (I)；By 10.00 grams of ammonium heptamolybdates (four
Water) it is dissolved in 60.0 grams 30 DEG C of water, obtained solution (II)；4.58 grams of oxalic acid hydrate niobiums are dissolved in 10.0 grams of water formation solution
((III) prepares the hydrochloric acid solution (IV) of 0.1 mol/L；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) is gradually added into hydrochloric acid solution (IV) in 80 DEG C of whipping process so that the pH value of solution (I) is finally
4.5；1.90 grams of antimony oxide powder are subsequently added, are stirred 5 hours at 90 DEG C, then successively by solution (II) and solution (III)
It is added in solution (I), is eventually adding citric acid solution (V), obtains mixture paste.
The slurry is put into 120 DEG C of oven drying 10 hours, then in 550 DEG C of high-purity argon after 90 DEG C are stirred 5 hours
Atmosphere encloses middle roasting 4 hours, finally gives Mo1.00V0.20Nb0.15Sb0.23OxCatalyst.
The catalyst takes 60 ~ 80 mesh powder to be used for propane ammoxidation reaction after tabletting, screening, and reaction temperature is 420
DEG C, reaction pressure is that the mol ratio of propane, ammonia and air in normal pressure, unstripped gas is 1.0/1.1/10.0, and time of contact is
2.00 grams of minute/milliliters, acquired results are as shown in table 1.
【Embodiment 4】
In the water that 2.32 grams of ammonium metavanadates are dissolved in 60.0 grams 80 DEG C, obtained solution (I)；By 10.00 grams of ammonium heptamolybdates (four
Water) it is dissolved in 60.0 grams 30 DEG C of water, obtained solution (II)；6.70 grams of oxalic acid hydrate niobiums are dissolved in 10.0 grams of water formation solution
((III) prepares the salpeter solution (IV) of 0.1 mol/L；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) is gradually added into salpeter solution (IV) in 80 DEG C of whipping process so that the pH value of solution (I) is finally
4.5；2.07 grams of antimony oxide powder are subsequently added, are stirred 8 hours at 80 DEG C, then successively by solution (II) and solution (III)
It is added in solution (I), is eventually adding L-TARTARIC ACID solution (V), obtains mixture paste.
The slurry is put into 100 DEG C of oven drying 12 hours, then in 600 DEG C of High Purity Nitrogen after 80 DEG C are stirred 2 hours
Atmosphere encloses middle roasting 2 hours, finally gives Mo1.00V0.35Nb0.22Sb0.25OxCatalyst.
The catalyst takes 60 ~ 80 mesh powder to be used for propane ammoxidation reaction after tabletting, screening, and reaction temperature is 410
DEG C, reaction pressure is that the mol ratio of propane, ammonia and air in normal pressure, unstripped gas is 1.0/1.5/15.0, and time of contact is
1.91 grams of minute/milliliters, acquired results are as shown in table 1.
【Embodiment 5】
In the water that 1.92 grams of ammonium metavanadates are dissolved in 60.0 grams 80 DEG C, obtained solution (I)；By 10.00 grams of ammonium heptamolybdates (four
Water) it is dissolved in 60.0 grams 30 DEG C of water, obtained solution (II)；4.57 grams of oxalic acid hydrate niobiums are dissolved in 10.0 grams of water formation solution
((III) prepares the salpeter solution (IV) of 0.1 mol/L；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) is gradually added into salpeter solution (IV) in 80 DEG C of whipping process so that the pH value of solution (I) is finally
5.0；2.07 grams of antimony oxide powder are subsequently added, are stirred 12 hours at 95 DEG C, then successively by solution (II) and solution
(III) it is added in solution (I), is eventually adding oxalic acid solution (V), obtains mixture paste.
The slurry is put into 110 DEG C of oven drying 10 hours, then in 650 DEG C of high-pure helium after 95 DEG C are stirred 4 hours
Atmosphere encloses middle roasting 3 hours, finally gives Mo1.00V0.29Nb0.15Sb0.25OxCatalyst.
The catalyst takes 60 ~ 80 mesh powder to be used for propane ammoxidation reaction after tabletting, screening, and reaction temperature is 450
DEG C, reaction pressure is that the mol ratio of propane, ammonia and air in normal pressure, unstripped gas is 1.0/1.5/14.3, and time of contact is
2.00 grams of minute/milliliters, acquired results are as shown in table 1.
【Embodiment 6】
In the water that 1.92 grams of ammonium metavanadates are dissolved in 60.0 grams 80 DEG C, obtained solution (I)；By 10.00 grams of ammonium heptamolybdates (four
Water) it is dissolved in 60.0 grams 30 DEG C of water, obtained solution (II)；6.10 grams of oxalic acid hydrate niobiums are dissolved in 10.0 grams of water formation solution
((III) prepares the salpeter solution (IV) of 0.1 mol/L；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) is gradually added into salpeter solution (IV) in 80 DEG C of whipping process so that the pH value of solution (I) is finally
3.5；1.49 grams of antimony oxide powder are subsequently added, are stirred 7 hours at 95 DEG C, then successively by solution (II) and solution (III)
It is added in solution (I), is eventually adding oxalic acid solution (V), obtains mixture paste.
The slurry is put into 150 DEG C of oven drying 5 hours, then in 650 DEG C of high-purity argon after 95 DEG C are stirred 2 hours
Atmosphere encloses middle roasting 2 hours, finally gives Mo1.00V0.29Nb0.20Sb0.18OxCatalyst.
The catalyst takes 60 ~ 80 mesh powder to be used for propane ammoxidation reaction after tabletting, screening, and reaction temperature is 430
DEG C, reaction pressure is that the mol ratio of propane, ammonia and air in normal pressure, unstripped gas is 1.0/1.2/10.0, and time of contact is
2.10 grams of minute/milliliters, acquired results are as shown in table 1.
【Comparative example 1】
As different from Example 1, nitric acid and oxalic acid solution are added without in catalyst preparation process, detailed process is：
In the water that 1.92 grams of ammonium metavanadates are dissolved in 60.0 grams 80 DEG C, obtained solution (I)；By 10.00 grams of ammonium heptamolybdates (four
Water) it is dissolved in 60.0 grams 30 DEG C of water, obtained solution (II)；1.08 grams of oxalic acid hydrate niobiums are dissolved in 10.0 grams of water formation solution
((Ⅲ)。
Solution (I) in 80 DEG C of whipping process, add 1.16 grams of antimony oxide powder, 90 DEG C stir 5 hours, then
Solution (II) and solution (III) are added in solution (I) successively, mixture paste is obtained.
The slurry is put into 120 DEG C of oven drying 5 hours, then in 600 DEG C of High Purity Nitrogen after 90 DEG C are stirred 2 hours
Atmosphere encloses middle roasting 2 hours, finally gives Mo1.00V0.29Nb0.03Sb0.14OxCatalyst.
The catalyst takes 60 ~ 80 mesh powder to be used for propane ammoxidation reaction after tabletting, screening, and reaction temperature is 440
DEG C, reaction pressure is that the mol ratio of propane, ammonia and air in normal pressure, unstripped gas is 1.0/1.2/10.0, and time of contact is
1.91 grams of minute/milliliters, acquired results are as shown in table 1.
【Comparative example 2】
As different from Example 2, sulfuric acid and oxalic acid solution are added without in catalyst preparation process, detailed process is：
In the water that 2.06 grams of ammonium metavanadates are dissolved in 60.0 grams 80 DEG C, obtained solution (I)；By 10.00 grams of ammonium heptamolybdates (four
Water) it is dissolved in 60.0 grams 30 DEG C of water, obtained solution (II)；5.50 grams of oxalic acid hydrate niobiums are dissolved in 10.0 grams of water formation solution
((Ⅲ)。
Solution (I) in 80 DEG C of whipping process, add 1.65 grams of antimony oxide powder, 90 DEG C stir 2 hours, then
Solution (II) and solution (III) are added in solution (I) successively, mixture paste is obtained.
The slurry is put into 120 DEG C of oven drying 8 hours, then in 650 DEG C of high-pure helium after 90 DEG C are stirred 2 hours
Atmosphere encloses middle roasting 3 hours, finally gives Mo1.00V0.31Nb0.18Sb0.20OxCatalyst.
The catalyst takes 60 ~ 80 mesh powder to be used for propane ammoxidation reaction after tabletting, screening, and reaction temperature is 430
DEG C, reaction pressure is that the mol ratio of propane, ammonia and air in normal pressure, unstripped gas is 1.0/1.3/10.0, and time of contact is
1.71 grams of minute/milliliters, acquired results are as shown in table 1.
【Comparative example 3】
As different from Example 3, hydrochloric acid and citric acid solution are added without in catalyst preparation process, detailed process is：
In the water that 1.33 grams of ammonium metavanadates are dissolved in 60.0 grams 80 DEG C, obtained solution (I)；By 10.00 grams of ammonium heptamolybdates (four
Water) it is dissolved in 60.0 grams 30 DEG C of water, obtained solution (II)；4.58 grams of oxalic acid hydrate niobiums are dissolved in 10.0 grams of water formation solution
((Ⅲ)。
Solution (I) in 80 DEG C of whipping process, add 1.90 grams of antimony oxide powder, 90 DEG C stir 5 hours, then
Solution (II) and solution (III) are added in solution (I) successively, mixture paste is obtained.
The slurry is put into 120 DEG C of oven drying 10 hours, then in 550 DEG C of high-purity argon after 90 DEG C are stirred 5 hours
Atmosphere encloses middle roasting 4 hours, finally gives Mo1.00V0.20Nb0.15Sb0.23OxCatalyst.
The catalyst takes 60 ~ 80 mesh powder to be used for propane ammoxidation reaction after tabletting, screening, and reaction temperature is 420
DEG C, reaction pressure is that the mol ratio of propane, ammonia and air in normal pressure, unstripped gas is 1.0/1.1/10.0, and time of contact is
2.00 grams of minute/milliliters, acquired results are as shown in table 1.
【Comparative example 4】
As different from Example 1, only nitric acid is added to be not added with oxalic acid in catalyst preparation process, detailed process is：
In the water that 1.92 grams of ammonium metavanadates are dissolved in 60.0 grams 80 DEG C, obtained solution (I)；By 10.00 grams of ammonium heptamolybdates (four
Water) it is dissolved in 60.0 grams 30 DEG C of water, obtained solution (II)；1.08 grams of oxalic acid hydrate niobiums are dissolved in 10.0 grams of water formation solution
((III) prepares the salpeter solution (IV) of 0.1 mol/L.
Solution (I) is gradually added into salpeter solution (IV) in 80 DEG C of whipping process so that the pH value of solution (I) is finally
3.0；1.16 grams of antimony oxide powder are subsequently added, are stirred 5 hours at 90 DEG C, then successively by solution (II) and solution (III)
It is added in solution (I), obtains mixture paste.
The slurry is put into 120 DEG C of oven drying 5 hours, then in 600 DEG C of High Purity Nitrogen after 90 DEG C are stirred 2 hours
Atmosphere encloses middle roasting 2 hours, finally gives Mo1.00V0.29Nb0.03Sb0.14OxCatalyst.
The catalyst takes 60 ~ 80 mesh powder to be used for propane ammoxidation reaction after tabletting, screening, and reaction temperature is 440
DEG C, reaction pressure is that the mol ratio of propane, ammonia and air in normal pressure, unstripped gas is 1.0/1.2/10.0, and time of contact is
1.91 grams of minute/milliliters, acquired results are as shown in table 1.
【Comparative example 5】
As different from Example 1, nitric acid is not added with catalyst preparation process and only adds oxalic acid, detailed process is：
In the water that 1.92 grams of ammonium metavanadates are dissolved in 60.0 grams 80 DEG C, obtained solution (I)；By 10.00 grams of ammonium heptamolybdates (four
Water) it is dissolved in 60.0 grams 30 DEG C of water, obtained solution (II)；1.08 grams of oxalic acid hydrate niobiums are dissolved in 10.0 grams of water formation solution
((III), 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
For 0.35.
Solution (I) in 80 DEG C of whipping process, add 1.16 grams of antimony oxide powder, 90 DEG C stir 5 hours, then
Solution (II) and solution (III) are added in solution (I) successively, oxalic acid solution (V) is eventually adding, obtains mixture paste.
The slurry is put into 120 DEG C of oven drying 5 hours, then in 600 DEG C of High Purity Nitrogen after 90 DEG C are stirred 2 hours
Atmosphere encloses middle roasting 2 hours, finally gives Mo1.00V0.29Nb0.03Sb0.14OxCatalyst.
The catalyst takes 60 ~ 80 mesh powder to be used for propane ammoxidation reaction after tabletting, screening, and reaction temperature is 440
DEG C, reaction pressure is that the mol ratio of propane, ammonia and air in normal pressure, unstripped gas is 1.0/1.2/10.0, and time of contact is
1.91 grams of minute/milliliters, acquired results are as shown in table 1.
Table 1
| Catalyst is constituted | Prepare committed step | |
| Embodiment 1 | Mo1.00V0.29Nb0.03Sb0.14Ox | Nitric acid adjusts pH=3.0, and oxalic acid is reducing agent |
| Embodiment 2 | Mo1.00V0.31Nb0.18Sb0.20Ox | Sulfuric acid adjusts pH=2.0, and oxalic acid is reducing agent |
| Embodiment 3 | Mo1.00V0.20Nb0.15Sb0.23Ox | Hydrochloric acid adjusts pH=4.5, and citric acid is reducing agent |
| Embodiment 4 | Mo1.00V0.35Nb0.22Sb0.25Ox | Nitric acid adjusts pH=4.5, and tartaric acid is reducing agent |
| Embodiment 5 | Mo1.00V0.29Nb0.15Sb0.25Ox | Nitric acid adjusts pH=6.0, and oxalic acid is reducing agent |
| Embodiment 6 | Mo1.00V0.29Nb0.20Sb0.18Ox | Nitric acid adjusts pH=3.5, and oxalic acid is reducing agent |
| Comparative example 1 | Mo1.00V0.29Nb0.06Sb0.14Ox | PH, no oxalic acid are adjusted without nitric acid |
| Comparative example 2 | Mo1.00V0.31Nb0.18Sb0.20Ox | PH, no oxalic acid are adjusted without sulfuric acid |
| Comparative example 3 | Mo1.00V0.20Nb0.15Sb0.23Ox | Without hydrochloric acid adjusts pH, no citric acid |
| Comparative example 4 | Mo1.00V0.29Nb0.06Sb0.14Ox | Nitric acid adjusts pH=3.0, no oxalic acid |
| Comparative example 5 | Mo1.00V0.29Nb0.06Sb0.14Ox | PH is adjusted without nitric acid, oxalic acid is reducing agent |
Table 1（It is continuous）
| Key reaction condition | Conversion of propane (%) | Acrylonitrile selectivity (%) | |
| Embodiment 1 | 440 DEG C, normal pressure, C3H8/NH3/Air=1.0/1.2/10.0 | 43.9 | 31.4 |
| Embodiment 2 | 430 DEG C, normal pressure, C3H8/NH3/Air=1.0/1.3/12.0 | 40.6 | 29.4 |
| Embodiment 3 | 420 DEG C, normal pressure, C3H8/NH3/Air=1.0/1.1/14.3 | 41.8 | 30.2 |
| Embodiment 4 | 410 DEG C, normal pressure, C3H8/NH3/Air=1.0/1.5/15.0 | 40.6 | 28.8 |
| Embodiment 5 | 450 DEG C, normal pressure, C3H8/NH3/Air=1.0/1.5/14.3 | 45.2 | 30.5 |
| Embodiment 6 | 430 DEG C, normal pressure, C3H8/NH3/Air=1.0/1.2/10.0 | 42.4 | 29.0 |
| Comparative example 1 | Be the same as Example 1 | 28.6 | 15.3 |
| Comparative example 2 | Be the same as Example 2 | 25.8 | 11.3 |
| Comparative example 3 | Be the same as Example 3 | 24.3 | 9.7 |
| Comparative example 4 | Be the same as Example 1 | 33.8 | 10.4 |
| Comparative example 5 | Be the same as Example 1 | 18.3 | 12.5 |
Claims (5)
1. unsaturated nitrile catalyst preparation method, the active constituent of the catalyst is according to atomic ratio measuring formula：
Mo1.00VaNbbSbcOx
A span is 0.1~1.0；
B span is 0.01~1.0；
C span is 0.01~1.0；
X is the oxygen atom sum needed for meeting each element chemical valence in catalyst；
Comprise the following steps：
1）Solution (I) is made by the corresponding salt of aequum V is soluble in water；
2）Solution (II) is made by the corresponding salt of aequum Mo is soluble in water；
3）Solution (III) is made by the corresponding salt of aequum Nb is soluble in water；
4）It is 1.5 ~ 5.0 with the pH value of inorganic acid-conditioning solution (I), antimony oxide powder is added to mixing in solution (I)
Uniformly, stirred at least 2 hours at 80 ~ 100 DEG C, sequentially add solution (II) and solution (III), be eventually adding reducing agent and obtain
Mixture paste, wherein reducing agent are with Mo atomic molars ratio>0 and below 0.42, mixture paste is in 80 ~ 100 DEG C of stirrings
At least 2 hours, obtained thick slurry was calcined 0.5 ~ 8 hour in temperature is 400 ~ 800 DEG C of inert atmosphere, so that
To catalyst；
Inert atmosphere is at least one of helium, nitrogen or argon gas.
2. unsaturated nitrile catalyst preparation method according to claim 1, it is characterised in that inorganic acid be sulfuric acid, nitric acid with
At least one of and hydrochloric acid.
3. unsaturated nitrile catalyst preparation method according to claim 1, it is characterised in that reducing agent is oxalic acid, citric acid
At least one of and tartaric acid.
4. unsaturated nitrile catalyst preparation method according to claim 1, it is characterised in that sintering temperature is 500 ~ 700
℃。
5. unsaturated nitrile catalyst preparation method according to claim 1, it is characterised in that roasting time is 2 ~ 4 hours.
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| CN1302227A (en) * | 1998-08-28 | 2001-07-04 | 旭化成株式会社 | Method for producing oxide catalyst for use in producing acrylonitrile or methacrylonitrile from propane or isobutane |
| CN101616732A (en) * | 2007-02-16 | 2009-12-30 | 伊内奥斯美国公司 | Utilize the propane of mixed metal oxide catalyst and the method for ammoxidation of iso-butane |
| CN101884918A (en) * | 2009-05-13 | 2010-11-17 | 中国石油化工股份有限公司 | Method for preparing antimony-containing catalyst used for ammoxidation of alkane |
| CN101992107A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司 | Method for preparing catalyst for alkane ammonia oxidation reaction |
| JP2012077039A (en) * | 2010-10-04 | 2012-04-19 | Asahi Kasei Chemicals Corp | Method for producing unsaturated acid or unsaturated nitrile |
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|---|---|---|---|---|
| CN1302227A (en) * | 1998-08-28 | 2001-07-04 | 旭化成株式会社 | Method for producing oxide catalyst for use in producing acrylonitrile or methacrylonitrile from propane or isobutane |
| CN101616732A (en) * | 2007-02-16 | 2009-12-30 | 伊内奥斯美国公司 | Utilize the propane of mixed metal oxide catalyst and the method for ammoxidation of iso-butane |
| CN101884918A (en) * | 2009-05-13 | 2010-11-17 | 中国石油化工股份有限公司 | Method for preparing antimony-containing catalyst used for ammoxidation of alkane |
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