CN103521216A - Nano bismuth molybdate catalyst and use thereof - Google Patents
Nano bismuth molybdate catalyst and use thereof Download PDFInfo
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- CN103521216A CN103521216A CN201210225850.2A CN201210225850A CN103521216A CN 103521216 A CN103521216 A CN 103521216A CN 201210225850 A CN201210225850 A CN 201210225850A CN 103521216 A CN103521216 A CN 103521216A
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- bismuth molybdate
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Abstract
The invention relates to a nano bismuth molybdate catalyst and use thereof, and is mainly used for solving the problems of small specific surfaces, low activity, and low adaptive weight space velocity of Mo-Bi series catalysts in the prior art. The nano bismuth molybdate catalyst comprises the following components in parts by weight: A, 10-50 parts of at least one carrier selected from SiO2, Al2O3, ZrO2 or TiO2, and B, 50-90 parts of nano bismuth molybdate supported on the carrier, wherein the particle diameter of nano bismuth molybdate is 20-200nm. By adopting the technical scheme of the nano bismuth molybdate catalyst and use thereof, the problem is better solved; the nano bismuth molybdate catalyst can be applied to industrial production of acraldehyde and acrylic acid by propylene oxidation.
Description
Technical field
The present invention relates to a kind of nano bismuth molybdate catalyst, and the application in propylene oxidation acrolein.
Background technology
The catalytic oxidation of propylene and amine are oxidized to undersaturated methacrylaldehyde, acrylic acid and acrylonitrile by industrialization widely, and it is an important elementary cell during petrochemical industry is produced.Wherein methacrylaldehyde itself is a kind of good biological extinguishing chemical, can be for aquatic products herbicide and slimicide; Methacrylaldehyde or important chemical intermediate, can be for the preparation of acrylic acid, D, L-Methionine, 1,3-PD and glutaraldehyde etc.
Propylene catalytic oxidation is that methacrylaldehyde catalyst is in the Cu of exploitation in 1948 the earliest by Shell
2o catalyst (U.S. Patent 2451485), until the beginning of the sixties, U.S. Sohio SOHIO company successfully develops Bi
9p
1mo
12o
52/ SiO
2(SiO
2content 50%) after catalyst, the oxidation of propylene and the industrialization of ammoxidation just make a breakthrough (U.S. Patent 2904580).Japan chemical drug company (Nippon Kayaku Co. Ltd.) finds in Mo-Bi-Fe catalyst system and catalyzing, to add divalence transition element simultaneously, as Co
2+and Ni
2+, (JP 43/002324, and JP 44/005855, and JP43/006264), this discovery extensively approved at present, and these type of new catalyst patents are delivered in succession in a large number subsequently to promote significantly propylene oxidation acrolein reaction selective and active.
Along with the research that deepens continuously to Mo-Bi catalyst system and catalyzing is found: there is one deck bismuth molybdate on polynary Mo-Bi catalyst granules surface, other element be distributed in catalyst particles plastochondria mutually in, and what play catalytic action is mainly surperficial bismuth molybdate.The Main Function that adds of divalence and trivalent transition metal has 2 points, and the firstth, (common bismuth molybdate is approximately 2 m to have improved the specific surface of catalyst
2/ g), more bismuth molybdate active sites is come out, second point is to adsorb, and transmits oxonium ion to bismuth molybdate, with bismuth molybdate, forms together synergy.But from the activity of catalyst own (reaction rate on unit specific surface), the active molybdate far above other of bismuth molybdate (particularly α and β phase), the bismuth molybdate of therefore preparing high-ratio surface can improve activity and the mass space velocity of current catalyst greatly.
Summary of the invention
One of technical problem to be solved by this invention is that in present technology, at propylene oxidation, to prepare the Mo-Bi catalyst activity existing in acrolein reaction on the low side, and the problem that mass space velocity is low, provides a kind of new nano bismuth molybdate catalyst.This catalyst is prepared acrolein reaction for propylene oxidation, has propylene conversion high, the advantage that mass space velocity is high.Two of the technical problem of solution required for the present invention is to provide a kind of new nano bismuth molybdate catalyst applications.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of nano bismuth molybdate catalyst, comprises following component in parts by weight:
A:10-50 part be selected from SiO
2, Al
2o
3, ZrO
2or TiO
2in at least one carrier; With its year thereon
The nano bismuth molybdate of B:50-90 part;
Wherein the grain diameter of nano bismuth molybdate is 20-200nm, preferential 35-100nm.
In technique scheme, the grain diameter preferable range of nano bismuth molybdate is 35-100nm.The specific area preferable range of catalyst is 10-50m
2/ g; The phase preferred version of catalyst is α phase, β phase or its mixture.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of nano bismuth molybdate catalyst is prepared acrolein reaction for propylene oxidation.
Nano bismuth molybdate catalyst, prepares acrolein reaction for propylene oxidation, and take propylene, air, water is raw material, and its mol ratio is 1:6-8:1.5-2, and reaction temperature is 350-380 ℃, and reaction pressure is normal pressure, and mass space velocity is 800-2000 hour
-1.
The preparation method of above-mentioned nano bismuth molybdate catalyst, comprises the following steps:
(a) by least one in P-123, Berol 226, F-127 (non-ionic surface active agent), be dissolved in n-hexane, normal octane, hexadecane or its mixed solvent, make solution I;
(b) bismuth nitrate and ammonium molybdate are dissolved in respectively to HNO
3in, be then diluted with water to finite concentration, make solution II and III;
(c) solution II of aequum is added in solution I, form microemulsion A, needed solution III is added in solution I, form microemulsion B, then microemulsion A is slowly added in microemulsion B to vigorous stirring;
(d) finally will obtain adding acetone in mixed liquor, until all Precipitations leach precipitation, continue with acetone washing, dry, roasting;
(e) to the SiO that is selected from that adds aequum in the powder obtaining
2, ZrO
2, Al
2o
3or TiO
2in at least one carrier, in kneader, mediate 20-60 minute, take out extrusion, by 350-600 ℃ of roasting, obtain required catalyst after dry.
Wherein, the concentration range 10-30% of solution I, solution II and III concentration range are 5-30%, the addition of II and III solution accounts for the 10-30% of solution I quality.
Nano bismuth molybdate catalyst is prepared to methacrylaldehyde for propylene oxidation, and take propylene, air, water is raw material, and mol ratio is 1:7.3:1.7, and reaction temperature is 375 ℃, and reaction pressure is normal pressure, and mass space velocity is 1000 hours
-1, its propylene conversion can reach 99.1%, methacrylaldehyde and acrylic acid selectively can reach 95.1%, and product methacrylaldehyde and acrylic acid yield can reach 94.2%, have obtained good technique effect.
Below by embodiment, the present invention is further elaborated.
The specific embodiment
[comparative example 1]
Take 123 grams of four water ammonium molybdates, 48.5 grams of bismuth nitrates, solvent is in 500ml deionized water, in 80 degree, dry, through 350 degree roastings, after 4 hours, pulverize, add in kneader and mediate, add Ludox (40% wt), mediate after 40 minutes, take out and put into banded extruder extrusion molding, obtain the cylinder of φ 6x6mm, after dry, high-temperature roasting obtains catalyst finished product, and sintering temperature is 400-550 ℃.This catalyst formed and preparation condition is listed in table 1,350 ℃, normal pressure, reaction velocity 1200 hours
-1under condition, check and rate, its reaction result is listed in table 2.
The reactor using is fixed bed reactors, 25.4 millimeters of internal diameters, 750 millimeters of reactor length.Catalyst filling amount is 150 grams.Product absorbs with 0 ℃ of diluted acid, uses gas chromatographic analysis product.And calculate Carbon balance, when Carbon balance is valid data during at (95～105) %.
Propylene conversion, product yield and be optionally defined as:
[embodiment 1]
50g P-123 is dissolved in 450g n-hexane, makes solution I, and be evenly divided into two parts; Bismuth nitrate and ammonium molybdate are dissolved in respectively to HNO
3in, be then diluted with water to finite concentration 10%, make solution II and III; 27.5g solution II is added in a copy of it solution I, form microemulsion A, 27.5g solution III is added in another part of solution I, form microemulsion B, then microemulsion A is slowly added in microemulsion B to vigorous stirring; Finally will obtain adding acetone in mixed liquor, until all Precipitations leach precipitation, continue with acetone washing, dry, 350 degree roastings, then add SiO in the powder obtaining
2, in kneader, mediate 60 minutes, take out extrusion, obtain the cylinder of φ 6x6mm, after being dried, by 450 ℃ of roastings, obtain catalyst finished product.This catalyst forms and preparation condition is listed in table 1,350 ℃, normal pressure, reaction velocity 1200 hours
-1under condition, check and rate, it the results are shown in table 2.
[embodiment 2-10]
Each step by embodiment 1 makes catalyst, just changes catalyst preparation condition, and concrete outcome is listed in table 1, and under identical appreciation condition, reaction result is listed in table 2.
[embodiment 11-20]
The catalyst of preparing according to the experiment condition of embodiment 4, the appraisal result under different condition is listed in table 3.
Table 1 catalyst forms and preparation condition
Table 2 evaluating catalyst result 1
| ? | Acrolein+acrylic acid yield (%) | Acrolein+acrylic acid selective (%) | Propylene conversion (%) |
| Comparative example 1 | 65.6 | 81.6 | 80.4 |
| Comparative example 2 | 85.6 | 89.1 | 96.1 |
| Embodiment 1 | 88.6 | 94.9 | 93.4 |
| Embodiment 2 | 87.2 | 91.8 | 97.5 |
| Embodiment 3 | 85.1 | 94.3 | 90.2 |
| Embodiment 4 | 94.2 | 95.1 | 99.1 |
| Embodiment 5 | 91.4 | 92.9 | 98.4 |
| Embodiment 6 | 84.0 | 91.8 | 91.5 |
| Embodiment 7 | 89.8 | 94.3 | 95.2 |
| Embodiment 8 | 90.2 | 95.7 | 94.3 |
| Embodiment 9 | 90.4 | 92.2 | 98.1 |
| Embodiment 10 | 89.9 | 91.2 | 98.6 |
Evaluating catalyst result 2 under table 3 differential responses condition
| ? | Propylene: air: water | Reaction temperature (℃) | Reaction pressure | Air speed (hour -1) | Acrolein+acrylic acid yield (%) |
| Embodiment 11 | 1：7.3：1.7 | 350 | 0.1Mpa | 800 | 89.1 |
| Embodiment 12 | 1：7.3：1.7 | 375 | 0.1Mpa | 1000 | 94.2 |
| Embodiment 13 | 1：7.3：1.7 | 370 | 0.1Mpa | 1000 | 90.4 |
| Embodiment 14 | 1：7.3：1.7 | 380 | 0.1Mpa | 1000 | 92.5 |
| Embodiment 15 | 1：7.3：1.7 | 375 | 0.11Mpa | 1200 | 86.1 |
| Embodiment 16 | 1：7.3：1.7 | 375 | 0.12Mpa | 1200 | 87.9 |
| Embodiment 17 | 1：7.3：1.7 | 375 | 0.13Mpa | 1500 | 84.4 |
| Embodiment 18 | 1：7.3：1.7 | 370 | 0.12Mpa | 1500 | 83.5 |
| Embodiment 19 | 1：7.3：1.7 | 370 | 0.11Mpa | 2000 | 81.7 |
| Embodiment 20 | 1：7.3：1.7 | 375 | 0.12Mpa | 2000 | 82.5 |
Claims (4)
1. a nano bismuth molybdate catalyst, comprises following component in parts by weight:
A:10-50 part be selected from SiO
2, Al
2o
3, ZrO
2or TiO
2in at least one carrier; With its year thereon
The nano bismuth molybdate of B:50-90 part;
Wherein the grain diameter of nano bismuth molybdate is 20-200nm.
2. according to the nano bismuth molybdate catalyst described in claim 1, the grain diameter that it is characterized in that nano bismuth molybdate is 35-100nm.
3. according to the nano bismuth molybdate catalyst described in claim 1, it is characterized in that the specific surface 10-50m of catalyst
2/ g, its phase is α phase, β phase or its mixture.
4. the nano bismuth molybdate catalyst described in claim 1 is prepared acrolein reaction for propylene oxidation.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107715865A (en) * | 2017-09-22 | 2018-02-23 | 浙江海洋大学 | A kind of Bi2MoO6The preparation method of/mussel shell composite micro-nano rice catalysis material |
-
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Non-Patent Citations (2)
| Title |
|---|
| 宏存茂: "《丙烯在钼酸铋催化剂上的选择氧化动力学研究》", 《北京大学学报(自然科学版）》 * |
| 徐美珍等: "《丙烯在a-钼酸铋催化剂上的氧化反应动力学>", 《石油化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107715865A (en) * | 2017-09-22 | 2018-02-23 | 浙江海洋大学 | A kind of Bi2MoO6The preparation method of/mussel shell composite micro-nano rice catalysis material |
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