CN106423141A - Antimony-containing low-carbon alkane ammoxidation catalyst - Google Patents
Antimony-containing low-carbon alkane ammoxidation catalyst Download PDFInfo
- Publication number
- CN106423141A CN106423141A CN201510492924.2A CN201510492924A CN106423141A CN 106423141 A CN106423141 A CN 106423141A CN 201510492924 A CN201510492924 A CN 201510492924A CN 106423141 A CN106423141 A CN 106423141A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- preparation
- atmosphere
- roasting
- hours
- 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.)
- Pending
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
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to an antimony-containing low-carbon alkane ammoxidation catalyst, mainly aiming at solving the problem that catalysts in the prior art are low in yield and poor in selectivity. According to the invention, the antimony-containing low-carbon alkane ammoxidation catalyst comprises a mixture of the following formula according to an atomic ratio: Mo1.00VaNbbSbcOx with the range of a to be 0.1-1.0, the range of b to be 0.01-1.0 and the range of c to be 0.01-1; wherein x is the total number of oxygen atoms required for the valences of all elements in the catalyst. In this way, the above problem can be well solved. The antimony-containing low-carbon alkane ammoxidation catalyst can be used for the industrial production of unsaturated nitriles through low-carbon alkane ammoxidation.
Description
Technical field
The present invention relates to a kind of low-carbon alkanes ammoxidation catalyst containing antimony element.It is specially adapted to propane ammoxidation reaction synthesis propylene
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 source material of basic organic industry.Warp
After development for many years, acrylonitrile industrial production technology has reached its maturity and perfect.At present, the acrylonitrile in the whole world more than 95%
Commercial plant all adopts the Sohio method technique with propylene as raw material for the BP/Ineos company.
In recent years, with the development and utilization of a large amount of shale gas in home and abroad, between propane and propylene, define huge price difference.
The main production firm of global acrylonitrile, such as Ineos company and Asahi Kasei company all actively put into exploitation
Acrylonitrile (methacrylonitrile) synthesis technique of raw material, to reducing production cost, improves product competitiveness.2013 2 months,
Asahi Kasei company builds up the whole world 200,000 tons/year of acrylonitrile commercial plants with propane as raw material of first set in Thailand and successfully goes into operation.
At present, propane (iso-butane) ammoxidation synthesis of acrylonitrile (methacrylonitrile) catalyst mainly has Mo-V-Nb-Te (Sb) and Sb-V
Two big catalyst system and catalyzings.
([1] .Robert K.Grasselli.Advances and future trends in selective oxidation and such as Grasselli
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 furtherd investigate it is believed that this catalyst is by club shaped structure orthorhombic phase
(chemical formula is Mo to M17.8V1.95Nb0.86Te1.33Ox, or { TeO }1-x(Mo,V,Nb)10O28, { TeO } is to insert in skeleton duct
Component), slab construction standard six side phases M2 (chemical formula be Mo1.0V0.28/0.31Nb0.08Te0.27-0.39O4.24, or { TeO }2-x
(Mo,V,Nb)6O18) and trace monocline crystalline phase TeMo5O16Composition.Wherein M1 activates phase for propane, and M2 is propylene activity of conversion
Phase, when the two ratio is 3/2, acrylonitrile yield reaches as high as 62%, however, the preparation of simple M1 and M2 phase is complicated.
The propane mainly V in M1 phase5+On activated, but vanadium-oxygen system is sufficiently complex, oxide huge number, wherein
Common oxidation state has V2+, V3+, V4+And V5+.There are multiple coherent conditions in vanadium ion, such as in the solution：Positive vanadic acid root VO4 3-,
Pyrovanadium acid group V2O7 4-, metavanadic acid root (VO3 -)n, polyoxovanadate V10O28 6-With double vanadyl VO2 +Deng, and the gathering shape of vanadium ion
State is relevant with the acidity of solution.In addition, Anderson type heteropolyacid salt (NH4)6TeMo6O24·n H2O is for raising Mo-V
The performance of series catalysts has a major impact, but at the pH value of slurry, mixing temperature and subsequent thermal in its formation and preparation process
Reason process is closely related.Therefore, the Mo-V series catalysts structure that different researchers obtain, phase composition difference are larger, lead to catalyst
Performance difference is very big.
Additionally, Te plays a significant role in Mo-V-Nb-Te catalyst, but due to relatively low (the metal Te fusing point of its fusing point
449 DEG C), this catalyst in heat treatment and course of reaction, due to the distillation of Te lead to catalyst stability reduce.For understanding
Determine this problem, generally stablize Te, avoid using Te or periodically add Te element using other auxiliary elements.
Patent CN 1220258 discloses a kind of Mo-V catalyst containing Te, finds the prolongation with the response time, and catalyst is lived
Property and acrylonitrile yield be gradually lowered, and pass through timing in reactor add containing Mo, Te activator, to improve catalyst
Stability, but this method brings many adverse effects for the continuous production of industrialized unit.
Patent CN 1344584, CN 1360971, CN 1419473, CN 1302227 disclose a kind of Mo-V-Nb-Te (Sb)
The preparation method of catalyst, it can be found that this preparation technology is complex, it is former that such as CN 1344584 employs a kind of special Nb
Material processing method, CN 1302227 reports a kind of method carrying out oxidation processes to raw mixture solution or slurry, these
The introducing of complex process, needs precise control each step process parameter to ensure the repeatability of catalyst performance, and this is multiple elements design oxygen
The amplification of compound catalyst produces and brings many difficulties.Additionally, by above-mentioned patent it has also been discovered that, Mo-V-Nb-Sb urges
Agent acrylonitrile yield substantially will be less than Mo-V-Nb-Te catalyst.
Patent CN 101616732 adopts hydrothermal synthesis method to prepare Mo-V-Nb-Sb catalyst series, and Te be impregnated in
In Mo-V-Nb-Sb catalyst series, although catalyst acrylonitrile yield is higher, this complicated process of preparation, influence factor is many
Many, the particularly Hydrothermal Synthesiss time is longer, and this brings many unfavorable factors for the amplification production of catalyst.
In summary it can be seen, the state-variable affecting its performance in Mo-V-Nb-Te (Sb) catalyst preparation process is more, and existing
The lengthy and tedious complexity of preparation technology, in production process, control parameter is numerous, and this amplifies steady production band for multicomponent composite oxide catalyst
Many difficulties are carried out.Additionally, still have in prior art that acrylonitrile yield is low, the asking of poor selectivity and poor catalyst stability
Topic.
Content of the invention
One of the technical problem to be solved is that catalyst yield present in prior art is low, poor selectivity, and stable
Property difference problem, provide a kind of low-carbon alkanes ammoxidation catalyst containing antimony element, it is high that this catalyst has high income, a selectivity,
And the feature of good stability.
The two of the technical problem to be solved are the preparation methoies of the described catalyst of one of above-mentioned technical problem.
The three of the technical problem to be solved are that the described catalyst of one of above-mentioned technical problem synthesizes in low-carbon alkanes ammoxidation
Application in unsaturated nitrile.
For solving one of above-mentioned technical problem, technical scheme is as follows：
Low-carbon alkanes ammoxidation catalyst containing antimony element, includes the mixture of general formula according to atomic ratio：
Mo1.00VaNbbSbcOx；
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 to meet the oxygen atom sum needed for each element quantivalence in catalyst.
In order to solve the two of above-mentioned technical problem, technical scheme is as follows：The preparation side of catalyst described in claim 1
Method, comprises the following steps：
1) corresponding to aequum Mo, V, Nb, Sb raw material is mixed to form slurry；
2), after mixed slurry is dried, preroast and final roasting are carried out successively；
Wherein pre-calcination temperature is less than sintering temperature.
In technique scheme, pre-calcination temperature is preferably 150～400 DEG C.
In technique scheme, pre-firing times are preferably 1～5 hour.
In technique scheme, one of the preferred oxidative of preroast atmosphere, reducibility gas or their mixture.More excellent
Select oxidizing gas.
In technique scheme, preroast process can be carried out for one section or more than one section, wherein preferably one section.When preroast is adopted
During with one section, more preferably 250～350 DEG C of the temperature of preroast, pre-firing times are preferably 1.0～2.5 hours.
In technique scheme, final calcination temperature is preferably 550～650 DEG C.
In technique scheme, final roasting time is preferably 0.5～5 hour.
In technique scheme, final calcination atmosphere is preferably noble gases.
In technique scheme, reducibility gas are preferably ammonia.
In technique scheme, described oxidizing gas are preferably air, oxygen or their mixture
In technique scheme, noble gases are preferably at least one in helium, nitrogen or argon.
As most preferred technical scheme, preroast atmosphere is oxidizing gas, and preroast is divided into one section, and final calcination atmosphere is
Noble gases, now have best conversion of propane and acrylonitrile selectivity.
For solving the three of above-mentioned technical problem, technical scheme is as follows：
Catalyst described in the technical scheme of one of above-mentioned technical problem synthesizes the application in unsaturated nitrile in low-carbon alkanes ammoxidation, its
Middle low-carbon alkanes are preferably C3～C4, described application preferably propane ammoxidation synthesis of acrylonitrile and iso-butane ammoxidation synthesizing methyl third
Alkene nitrile.
In technique scheme, the oxidant used by ammoxidation preferably is selected from the mixture of molecular oxygen or molecule-containing keto.Such as but not limited to
Pure oxygen, oxygen-enriched and air, but it is preferably air from cost meter.
In technique scheme, the mol ratio for ammonia and propane in the unstripped gas of propane ammoxidation is preferably between 0.8～2.0,
It is well 1.0～1.5；Mol ratio for air in the unstripped gas of propane ammoxidation and propane is preferably 8.0～16.0, preferably
10.0～15.0.Reaction temperature is preferably 370～460 DEG C, preferably 390～450 DEG C.
Mo raw material in catalyst is preferably corresponding oxide or its ammonium salt, preferably ammonium heptamolybdate；V raw material is preferably corresponding
Oxide or its ammonium salt, preferably ammonium metavanadate；Sb raw material is preferably corresponding oxide, preferably antimony oxide；Nb raw material is
It is well corresponding oxide, hydroxide, nitrate or oxalates, preferably niobium oxalate.
The roasting process of catalyst is divided into preroast and final firing stage by the present invention, and in oxidation, reduction or noble gases
Carry out in atmosphere.Preroast process can carry out (all using one section of roasting in embodiment), catalyst for one section or more than one section
Presoma was decomposed and redox reaction in this stage, adjusted the chemical valence state of various elements compound.This method of roasting work
Skill is simple, and repeatability, stability are preferable, and needed raw material is easy to get, and the low-carbon alkanes ammoxidation that can prepare function admirable is urged
Agent.
Catalyst of the present invention internal diameter be 8 millimeters fixed bed reactors in evaluated, loaded catalyst be 3.0 grams.
The conversion ratio of propane, the selectivity of acrylonitrile and be defined as follows time of contact：
When the catalyst of the present invention is used for propane ammoxidation reaction synthesis of acrylonitrile, conversion of propane is up to 69.1%, and acrylonitrile selects
Property, up to 52.3%, achieves preferable technique effect.
Below by specific embodiment, the invention will be further elaborated, but the present invention is not limited by the following examples.
Specific embodiment
【Embodiment 1】
19.2 grams of ammonium metavanadates are dissolved in 600.0 grams 80 DEG C of water, obtained solution (I)；100.0 grams of ammonium heptamolybdates (are tied containing four
Brilliant water, referred to as four water, similarly hereinafter) be dissolved in 600.0 grams 30 DEG C of water, obtained solution (II)；10.8 grams of oxalic acid hydrate niobiums are dissolved in
100.0 grams of water form solution (III), prepare the salpeter solution (IV) of 0.1 mol/L；25.0 grams of oxalic acid (two water) are dissolved in 50.0 grams of water
Middle formation solution (V)；Wherein oxalic acid molecule and molybdenum atom mol ratio are 0.35.
Solution (I), in 80 DEG C of whipping process, is gradually added into salpeter solution (IV) so that the pH value of solution (I) is finally 3.0；Subsequently
Add 11.6 grams of antimony oxide powder, stir 5 hours at 90 DEG C, subsequently successively solution (II) and solution (III) are added to solution
(I), in, it is eventually adding oxalic acid solution (V), obtains mixture paste.This slurry, after 90 DEG C of stirrings 2 hours, puts into 120 DEG C
Oven drying 5 hours, obtains Mo1.00V0.29Nb0.06Sb0.14OxCatalyst precursor.
Weigh in 10.0 grams of catalyst precursors loading roasters and be ready for roasting.First, air air speed be 500h-1Gas
In atmosphere, catalyst precursor keeps 300 DEG C of preroasts 2 hours；Subsequently in nitrogen air speed 500h-1630 DEG C of roastings are kept in atmosphere
2 hours.
After catalyst roasting, through tabletting and screening, take 60～80 mesh powder for propane ammoxidation reaction, reaction temperature is 440 DEG C,
Reaction pressure is normal pressure, and in unstripped gas, the mol ratio of propane, ammonia and air is 1.0/1.5/12.0, is 1.91 grams time of contact
Minute/milliliter, acquired results are as shown in table 1.By Data Comparison it is found that catalyst precursor is in air and ammonia atmosphere
Middle after two sections of preroast, conversion of propane and acrylonitrile selectivity highest.
【Embodiment 2】
Weigh in embodiment 1 and be ready for roasting in 10.0 grams of catalyst precursors loading roasters.First, in oxygen air speed it is
300h-1Atmosphere in, catalyst precursor keeps 300 DEG C of preroasts 2 hours；Subsequently in nitrogen air speed 500h-1Keep in atmosphere
630 DEG C of roastings 2 hours.
After catalyst roasting, through tabletting and screening, take 60～80 mesh powder for propane ammoxidation reaction, reaction condition and enforcement
Example 1 is identical, and acquired results are as shown in table 1.
【Embodiment 3】
Weigh in embodiment 1 and be ready for roasting in 10.0 grams of catalyst precursors loading roasters.First, in ammonia air speed it is
200h-1Atmosphere in, catalyst precursor keeps 300 DEG C of preroasts 2 hours；Subsequently in helium air speed 500h-1Keep in atmosphere
630 DEG C of roastings 2 hours.
After catalyst roasting, through tabletting and screening, take 60～80 mesh powder for propane ammoxidation reaction, reaction condition and enforcement
Example 1 is identical, and acquired results are as shown in table 1.
【Embodiment 4】
Weigh in embodiment 1 and be ready for roasting in 10.0 grams of catalyst precursors loading roasters.First, rub in air and ammonia
Your ratio is 14.3, and air speed is 500h-1In atmosphere, catalyst precursor keeps 300 DEG C of preroasts 2 hours；Subsequently in argon air speed
500h-1630 DEG C of roastings 2 hours are kept in atmosphere.
After catalyst roasting, through tabletting and screening, take 60～80 mesh powder for propane ammoxidation reaction, reaction condition and enforcement
Example 1 is identical, and acquired results are as shown in table 1.
【Embodiment 5】
Weigh in embodiment 1 and be ready for roasting in 10.0 grams of catalyst precursors loading roasters.First, in air air speed it is
500h-1In atmosphere, catalyst precursor keeps 320 DEG C of preroasts 1.5 hours；Subsequently in nitrogen air speed 500h-1Keep in atmosphere
600 DEG C of roastings 2.5 hours.
After catalyst roasting, through tabletting and screening, take 60～80 mesh powder for propane ammoxidation reaction, reaction condition and enforcement
Example 1 is identical, and acquired results are as shown in table 1.
【Embodiment 6】
Weigh in embodiment 1 and be ready for roasting in 10.0 grams of catalyst precursors loading roasters.First, in air air speed it is
500h-1In atmosphere, catalyst precursor keeps 350 DEG C of preroasts 3 hours；Subsequently in nitrogen air speed 500h-1Keep in atmosphere
600 DEG C of roastings 3 hours.
After catalyst roasting, through tabletting and screening, take 60～80 mesh powder for propane ammoxidation reaction, reaction condition and enforcement
Example 1 is identical, and acquired results are as shown in table 1.
【Comparative example 1】
Weigh in embodiment 1 and prepare to carry out roasting in air atmosphere in 10.0 grams of catalyst precursors loading roasters.First, exist
Air air speed is 500h-1In atmosphere, catalyst precursor keeps 300 DEG C of preroasts 2 hours；In air air speed it is still subsequently
500h-1630 DEG C of roastings 2 hours are kept in atmosphere.
After catalyst roasting, through tabletting and screening, take 60～80 mesh powder for propane ammoxidation reaction, reaction condition and enforcement
Example 1 is identical, and acquired results are as shown in table 1.
【Comparative example 2】
Weigh in embodiment 1 and prepare to carry out roasting in nitrogen atmosphere in 10.0 grams of catalyst precursors loading roasters.First, exist
Nitrogen air speed is 500h-1In atmosphere, catalyst precursor keeps 300 DEG C of preroasts 2 hours；In nitrogen air speed it is still subsequently
500h-1630 DEG C of roastings 2 hours are kept in atmosphere.
After catalyst roasting, through tabletting and screening, take 60～80 mesh powder for propane ammoxidation reaction, reaction condition and enforcement
Example 1 is identical, and acquired results are as shown in table 1.
【Comparative example 3】
Weigh in embodiment 1 and prepare to carry out roasting in ammonia atmosphere in 10.0 grams of catalyst precursors loading roasters.First, exist
Ammonia air speed is 500h-1In atmosphere, catalyst precursor keeps 300 DEG C of preroasts 2 hours；In ammonia air speed it is still subsequently
500h-1630 DEG C of roastings 2 hours are kept in atmosphere.
After catalyst roasting, through tabletting and screening, take 60～80 mesh powder for propane ammoxidation reaction, reaction condition and enforcement
Example 1 is identical, and acquired results are as shown in table 1.
【Comparative example 4】
Weigh and prepare in 10.0 grams of catalyst precursors loading roasters in embodiment 1 to be roasted in air and ammonia mixing atmosphere
Burn.First, it is 14.3 in air and ammonia mol ratio, air speed is 500h-1In atmosphere, catalyst precursor keeps 300 DEG C of prebakes
Burn 2 hours；Subsequently still air and ammonia mol ratio be 14.3 air speeds be 500h-1630 DEG C of roastings 2 hours are kept in atmosphere.
After catalyst roasting, through tabletting and screening, take 60～80 mesh powder for propane ammoxidation reaction, reaction condition and enforcement
Example 1 is identical, and acquired results are as shown in table 1.
【Embodiment 7】
23.2 grams of ammonium metavanadates are dissolved in 600.0 grams 80 DEG C of water, obtained solution (I)；By 100.00 grams of ammonium heptamolybdates (four water)
It is dissolved in 600.0 grams 30 DEG C of water, obtained solution (II)；18.6 grams of oxalic acid hydrate niobiums are dissolved in 100.0 grams of water and form solution (III),
Prepare the salpeter solution (IV) of 0.1 mol/L；25.0 grams of oxalic acid (two water) are dissolved in 50.0 grams of water and form solution (V)；Its medium-height grass
Acid molecule and molybdenum atom mol ratio are 0.35.
Solution (I), in 80 DEG C of whipping process, is gradually added into salpeter solution (IV) so that the pH value of solution (I) is finally 3.0；Subsequently
Add 20.7 grams of antimony oxide powder, stir 5 hours at 90 DEG C, subsequently successively solution (II) and solution (III) are added to solution
(I), in, it is eventually adding oxalic acid solution (V), obtains mixture paste.This slurry, after 90 DEG C of stirrings 2 hours, puts into 120 DEG C
Oven drying 5 hours, obtains Mo1.00V0.35Nb0.10Sb0.25OxCatalyst precursor.
Weigh in 10.0 grams of catalyst precursors loading roasters and be ready for roasting.First, air air speed be 500h-1Gas
In atmosphere, catalyst precursor keeps 330 DEG C of preroasts 1.5 hours；Subsequently in nitrogen air speed 500h-1620 DEG C of roastings are kept in atmosphere
Burn 2 hours.
After catalyst roasting, through tabletting and screening, take 60～80 mesh powder for propane ammoxidation reaction, reaction temperature is 440 DEG C,
Reaction pressure is normal pressure, and in unstripped gas, the mol ratio of propane, ammonia and air is 1.0/1.5/12.0, is 1.91 grams time of contact
Minute/milliliter, acquired results are as shown in table 1.
【Embodiment 8】
Weigh in embodiment 7 and be ready for roasting in 10.0 grams of catalyst precursors loading roasters.First, in oxygen air speed it is
300h-1Atmosphere in, catalyst precursor keeps 330 DEG C of preroasts 1.5 hours；Subsequently in nitrogen air speed 500h-1Protect in atmosphere
Hold 630 DEG C of roastings 2 hours.
After catalyst roasting, through tabletting and screening, take 60～80 mesh powder for propane ammoxidation reaction, reaction condition and enforcement
Example 7 is identical, and acquired results are as shown in table 1.
【Embodiment 9】
Weigh in embodiment 7 and be ready for roasting in 10.0 grams of catalyst precursors loading roasters.First, rub in air and ammonia
Your ratio is 14.3, and air speed is 500h-1In atmosphere, catalyst precursor keeps 330 DEG C of preroasts 1.5 hours；Subsequently empty in argon
Fast 500h-1620 DEG C of roastings 2 hours are kept in atmosphere.
After catalyst roasting, through tabletting and screening, take 60～80 mesh powder for propane ammoxidation reaction, reaction condition and enforcement
Example 7 is identical, and acquired results are as shown in table 1.
【Comparative example 5】
Weigh in embodiment 7 and prepare to carry out roasting in air atmosphere in 10.0 grams of catalyst precursors loading roasters.First, exist
Air air speed is 500h-1In atmosphere, catalyst precursor keeps 330 DEG C of preroasts 1.5 hours；In air air speed it is still subsequently
500h-1620 DEG C of roastings 2 hours are kept in atmosphere.
After catalyst roasting, through tabletting and screening, take 60～80 mesh powder for propane ammoxidation reaction, reaction condition and enforcement
Example 7 is identical, and acquired results are as shown in table 1.
【Comparative example 6】
Weigh in embodiment 7 and prepare to carry out roasting in nitrogen atmosphere in 10.0 grams of catalyst precursors loading roasters.First, exist
Nitrogen air speed is 500h-1In atmosphere, catalyst precursor keeps 330 DEG C of preroasts 1.5 hours；In nitrogen air speed it is still subsequently
500h-1620 DEG C of roastings 2 hours are kept in atmosphere.
After catalyst roasting, through tabletting and screening, take 60～80 mesh powder for propane ammoxidation reaction, reaction condition and enforcement
Example 7 is identical, and acquired results are as shown in table 1.
【Comparative example 7】
Weigh in embodiment 7 and prepare to carry out roasting in ammonia atmosphere in 10.0 grams of catalyst precursors loading roasters.First, exist
Ammonia air speed is 500h-1In atmosphere, catalyst precursor keeps 330 DEG C of preroasts 1.5 hours；In ammonia air speed it is still subsequently
500h-1620 DEG C of roastings 2 hours are kept in atmosphere.
After catalyst roasting, through tabletting and screening, take 60～80 mesh powder for propane ammoxidation reaction, reaction condition and enforcement
Example 7 is identical, and acquired results are as shown in table 1.
Table 1
Claims (10)
1. contain the low-carbon alkanes ammoxidation catalyst of antimony element, include the mixture of general formula according to atomic ratio：
Mo1.00VaNbbSbcOx；
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 to meet the oxygen atom sum needed for each element quantivalence in catalyst.
2. the preparation method of catalyst described in claim 1, comprises the following steps：
1) corresponding to aequum Mo, V, Nb, Sb raw material is mixed to form slurry；
2), after mixed slurry is dried, preroast and final roasting are carried out successively；
Wherein pre-calcination temperature is less than sintering temperature.
3. preparation method according to claim 2, is characterized in that pre-calcination temperature is 150～400 DEG C.
4. preparation method according to claim 2, is characterized in that pre-firing times are 1～5 hour.
5. preparation method according to claim 2, is characterized in that preroast atmosphere is selected from oxidisability, reducibility gas
One of or their mixture.
6. preparation method according to claim 2, is characterized in that final calcination temperature is 550～650 DEG C.
7. preparation method according to claim 2, is characterized in that final roasting time is 0.5～5 hour.
8. preparation method according to claim 2, is characterized in that final calcination atmosphere is noble gases.
9. preparation method according to claim 8, it is characterized in that noble gases be helium, in nitrogen or argon extremely
Few one kind.
10. the catalyst described in claim 1 synthesizes the application in unsaturated nitrile in low-carbon alkanes ammoxidation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510492924.2A CN106423141A (en) | 2015-08-12 | 2015-08-12 | Antimony-containing low-carbon alkane ammoxidation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510492924.2A CN106423141A (en) | 2015-08-12 | 2015-08-12 | Antimony-containing low-carbon alkane ammoxidation catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106423141A true CN106423141A (en) | 2017-02-22 |
Family
ID=58093346
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510492924.2A Pending CN106423141A (en) | 2015-08-12 | 2015-08-12 | Antimony-containing low-carbon alkane ammoxidation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106423141A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5049692A (en) * | 1987-11-25 | 1991-09-17 | Mitsubishi Kasei Corporation | Catalytic conversion of alkanes to nitriles, and a catalyst therefor |
| CN1069723A (en) * | 1991-08-08 | 1993-03-10 | 三菱化成株式会社 | The production method of nitrile |
| 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 |
| CN104549224A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Unsaturated nitrile catalyst and preparation method thereof |
| CN104549373A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Low-carbon alkane ammoxidation catalyst |
-
2015
- 2015-08-12 CN CN201510492924.2A patent/CN106423141A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5049692A (en) * | 1987-11-25 | 1991-09-17 | Mitsubishi Kasei Corporation | Catalytic conversion of alkanes to nitriles, and a catalyst therefor |
| CN1069723A (en) * | 1991-08-08 | 1993-03-10 | 三菱化成株式会社 | The production method of nitrile |
| 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 |
| CN104549224A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Unsaturated nitrile catalyst and preparation method thereof |
| CN104549373A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Low-carbon alkane ammoxidation catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 王尚弟等: "《催化剂工程导论》", 31 August 2001, 化学工业出版社 * |
| 白崎高保: "《催化剂制造》", 31 August 1981, 石油工业出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102451702B (en) | Acrylic acid catalyst prepared by acrolein oxidation and preparation method thereof | |
| CN102066001A (en) | Catalyst for producing acrolein and acrylic acid through glycerin dehydration and production method of same | |
| CN104549373B (en) | Low-carbon alkanes ammoxidation catalyst | |
| CN100566829C (en) | Catalyst for preparing acrylonitrile by ammonia oxidizing method | |
| CN103418402A (en) | Catalyst for preparing acrylic acid by acrolein oxidation and preparation method thereof | |
| CN101778669B (en) | Method of preparing improved catalyst for production of acrylic acid | |
| CN107282036A (en) | Low-carbon alkanes ammoxidation catalyst | |
| CN104549224B (en) | Unsaturated nitrile catalyst and preparation method thereof | |
| CN105312067B (en) | Low-carbon alkanes ammoxidation catalyst | |
| CN112844400A (en) | Bi-based polyacid catalyst and application thereof in preparation of 2-methylacrolein by oxidation of 2-methyl propylene | |
| CN106423141A (en) | Antimony-containing low-carbon alkane ammoxidation catalyst | |
| CN102295581A (en) | Method for preparing 3,4-dichlorobenzonitrile by ammonia oxidation | |
| CN111068711A (en) | Acrylic acid catalyst and application thereof | |
| CN106423222A (en) | Low carbon alkane ammoxidation catalyst | |
| CN107282058A (en) | Composite oxide catalysts | |
| CN109305910A (en) | Methacrylaldehyde acrylic acid | |
| CN104549261B (en) | The catalyst of alkane unsaturated nitrile | |
| CN106881098A (en) | Composite oxide catalysts and its production and use | |
| CN107282076A (en) | Alkane ammoxidation catalyst | |
| CN115090308B (en) | Metal-doped sodium super-ionic catalyst and preparation method and application thereof | |
| CN109305904A (en) | For prepared by acrolein oxidation acrylic acid | |
| CN109304155B (en) | Catalyst for acrylic acid synthesis | |
| CN115518646B (en) | Catalyst for low-carbon alkane oxidation/ammoxidation and preparation method thereof | |
| CN112547062B (en) | Catalyst for preparing acrylic acid from acrolein and preparation method and application thereof | |
| CN109305905B (en) | Method for synthesizing acrylic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170222 |
|
| RJ01 | Rejection of invention patent application after publication |