CN108067303B - Preparation method and application of seven-core manganese substituted silicotungstic oxygen cluster catalyst - Google Patents
Preparation method and application of seven-core manganese substituted silicotungstic oxygen cluster catalyst Download PDFInfo
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- CN108067303B CN108067303B CN201711421253.6A CN201711421253A CN108067303B CN 108067303 B CN108067303 B CN 108067303B CN 201711421253 A CN201711421253 A CN 201711421253A CN 108067303 B CN108067303 B CN 108067303B
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1608—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes the ligands containing silicon
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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Abstract
The invention discloses a preparation method and application of a heptanuclear manganese substituted silicotungsten oxygen cluster catalyst. In the reaction process of synthesizing TBiTD by an oxygen method, the yield of the catalyst is up to 86%, the reaction process is simple, the purity of the obtained product is high, and the post-treatment is simple.
Description
Technical Field
The invention belongs to the technical field of catalyst material preparation, and relates to a preparation method and application of a heptanuclear manganese substituted silicotungstic oxygen cluster catalyst.
Technical Field
Polyoxometalates (abbreviated as POMs) are cluster compounds containing elements such as Mo, W, V, and the like, and research on catalysis is becoming more and more extensive, and research focus is on transition from structure to catalysis. At present, industrialization projects of preparing isopropanol by catalyzing propylene hydration through POMs, preparing methacrylic acid by oxidizing 2-methylacrolein through POMs in a gas phase, preparing acetic acid by oxidizing ethylene through POMs are realized in Japan in succession, and the important achievements have wide influence in the international chemical industry and bring huge economic benefits. The silicon-tungsten-oxygen cluster is a relatively common and important compound in the polymetallic oxygen cluster. Because the silicon-tungsten oxygen clusters have an electron-rich effect, and certain acidity and oxidizability are determined, the silicon-tungsten oxygen clusters show excellent catalytic characteristics in a plurality of organic synthesis reactions.
Meanwhile, the rubber vulcanization accelerator TiBTD (diisobutyl thiuram disulfide) is a novel, safe and environment-friendly thiuram accelerator, can be widely used for natural rubber, butadiene rubber, styrene butadiene rubber and the like, and is a green product for generating N-nitrosamine auxiliaries instead of accelerators TMTD, TETD, TMTM, TRA and the like. Most of the existing methods for synthesizing TiBTD are synthesized by a hydrogen peroxide method, but most of the oxygen method synthesis involves the use of sodium hydroxide and sulfuric acid, which undoubtedly causes corrosion to equipment. The oxygen method synthesis method does not need sulfuric acid and sodium hydroxide, is environment-friendly, and is key to selecting a proper catalyst. However, transition metal substituted silicon tungsten oxygen clusters have not been reported for this reaction catalysis.
Through searching, no published patent literature relevant to the application of the invention is found.
Disclosure of Invention
The invention aims to provide a preparation method for synthesizing a heptanuclear manganese substituted silicotungsten oxygen cluster catalyst for synthesizing a rubber vulcanization accelerator TiBTD by an oxygen method, so as to play a good catalysis role in the reaction of synthesizing the rubber vulcanization accelerator TiBTD and achieve the aim of synthesizing the rubber vulcanization accelerator TiBTD under the condition of a low dosage of the catalyst.
The design idea of the invention is as follows:
1. the catalytic active center Mn is connected with the silicon-tungsten-oxygen cluster through Mn-O bonds, and water molecules coordinated on manganese atoms are easy to separate in the reaction process, so that metal ions can play a role of a catalytic center;
2. obtaining a single crystal of the heptanuclear manganese substituted silicotungstic oxygen cluster catalyst by using a conventional method;
3. the seven-core manganese-substituted silicotungstic oxygen cluster single-component catalyst with a definite structure is applied to the reaction of synthesizing the rubber vulcanization accelerator TiBTD, so that the aim of synthesizing the compound by an oxygen method is fulfilled.
The crystal structure information of such catalysts is obtained by the following method:
the crystal of the heptanuclear manganese-substituted silicotungstic oxygen cluster catalyst is synthesized by a hydrothermal synthesis method, and the specific description experiment method is as follows:
sequentially adding sodium tungstate, water, manganese salt, sodium silicate and potassium chloride into a clean reaction kettle, regulating the pH value of the solution to 4-6 by using hydrochloric acid under vigorous stirring, stirring for 12-24 h, reacting for 5-7 days at 150-180 ℃, cooling to room temperature after the reaction is finished, and filtering to obtain black crystals. The yield is about 29-52%.
In a preferred embodiment, sodium tungstate: manganese nitrate: sodium silicate: the ratio of the amount of the potassium chloride is 0.5-0.9: 0.1-0.5: 0.1-0.4: 0.8-1.6.
Preferably, the solvent is water, and the mass-to-volume ratio (g/ml) of the sodium tungstate to the water is 0.16-0.3: 10 to 25.
The product was characterized by single crystal X-ray diffraction, powder X-ray diffraction and accurate information about the crystal structure was obtained from fig. 1, fig. 2 and the crystallographic data table 1. The specific results are as follows:
the molecular formula of the crystal is K10(H2O)26Mn7(H2O)9Si4W40O140,Wherein the cation part is Mn, K and water molecule form complex cation, and the anion is Si4W40O140 24-The anion, the three are connected and combined together through an oxygen atom covalent bond.
TABLE 1 Compound K10(H2O)26Mn7(H2O)9Si4W40O140Crystallographic data of
Formula | H70K10Mn7O175Si4W40 |
M r | 11111.87 |
Crystal system | Monoclinic |
Space group | C2/c |
Temperature | 296(2) K |
a (Å) | 33.962(3) |
b (Å) | 24.252(2) |
c (Å) | 24.268(2) |
α (deg) | 90.00 |
β (deg) | 92.752(2) |
γ (deg) | 90.00 |
V (Å3) | 19965(3) |
Z | 2 |
D calc.(g cm-3) | 2.374 |
F(000) | 5518 |
R 1[I>2σ(I)] | 0.1181 |
wR 2[I>2σ(I)] | 0.3262 |
R 1(all data) | 0.2095 |
wR 2(all data) | 0.3884 |
GOOF | 1.102 |
As can be seen from Table 1, the crystal data of this compound is monoclinic and the space group isC2/cThe chemical formula of the crystal is H70K10Mn7O175Si4W40The molecular weight is 11111.87, and the molecular weight can be well matched with the crystal structure.
The invention mainly synthesizes the seven-core manganese substituted silicon-tungsten oxygen cluster single-component catalyst which is applied to the reaction of synthesizing the rubber vulcanization accelerator TiBTD. The catalyst can realize the synthesis of the rubber vulcanization accelerator TiBTD by an oxygen method, and the yield is as high as 86%. The preparation method of the catalyst has simple reaction process.
The catalyst provided by the invention has the following characteristics:
1. the preparation method is simple, and the catalysts have definite molecular structures, thereby being beneficial to researching the catalytic reaction mechanism;
2. the catalyst has Mn active sites and can catalyze the reaction of synthesizing TiBTD.
Drawings
FIG. 1 Compound K10(H2O)26Mn7(H2O)9Si4W40O140Schematic representation of the crystal structure in different directions (hydrogen atoms and water solvent molecules are removed for structural clarity);
FIG. 2 Compound K10(H2O)26Mn7(H2O)9Si4W40O140RXRD characterization of (a), the upper gray line is the synthesized sample and the lower black line is the simulated sample.
Detailed Description
Example 1: compound K10(H2O)26Mn7(H2O)9Si4W40O140Preparation of
Adding sodium tungstate (0.5mmol), water (10 mL), manganese chloride (0.1mmol), sodium silicate (0.1mmol) and potassium chloride (0.8mmol) into a clean reaction kettle in sequence, adjusting the pH value of the solution to 4 by hydrochloric acid under vigorous stirring, stirring for 12h, reacting at 150 ℃ for 5 days, cooling to room temperature after the reaction is finished, and filtering to obtain black crystals. The yield was about 31%.
Example 2: compound K10(H2O)26Mn7(H2O)9Si4W40O140Preparation of
Adding sodium tungstate (0.6mmol), water (15 mL), manganese chloride (0.1mmol), sodium silicate (0.1mmol) and potassium chloride (0.8mmol) into a clean reaction kettle in sequence, adjusting the pH value of the solution to 4 by hydrochloric acid under vigorous stirring, stirring for 12h, reacting at 150 ℃ for 5 days, cooling to room temperature after the reaction is finished, and filtering to obtain black crystals. The yield was about 35%.
Example 3: compound K10(H2O)26Mn7(H2O)9Si4W40O140Preparation of
Adding sodium tungstate (0.7mmol), water (20 mL), manganese nitrate (0.5mmol), sodium silicate (0.1mmol) and potassium chloride (0.8mmol) into a clean reaction kettle in sequence, adjusting the pH value of the solution to 6 by hydrochloric acid under vigorous stirring, stirring for 24h, reacting at 160 ℃ for 7 days, cooling to room temperature after the reaction is finished, and filtering to obtain black crystals. The yield was about 43%.
Example 4: compound K10(H2O)26Mn7(H2O)9Si4W40O140Preparation of
Adding sodium tungstate (0.9mmol), water (20 mL), manganese nitrate (0.5mmol), sodium silicate (0.4mmol) and potassium chloride (1.4 mmol) into a clean reaction kettle in sequence, adjusting the pH value of the solution to 5 by hydrochloric acid under vigorous stirring, stirring for 24h, reacting at 180 ℃ for 7 days, cooling to room temperature after the reaction is finished, and filtering to obtain black crystals. The yield was about 49%.
Example 5: compound K10(H2O)26Mn7(H2O)9Si4W40O140Preparation of
Adding sodium tungstate (0.8mmol), water (10 mL), manganese nitrate (0.3mmol), sodium silicate (0.2mmol) and potassium chloride (1.6 mmol) into a clean reaction kettle in sequence, adjusting the pH value of the solution to 6 by hydrochloric acid under vigorous stirring, stirring for 18h, reacting at 170 ℃ for 7 days, cooling to room temperature after the reaction is finished, and filtering to obtain black crystals. The yield was about 46%.
Example 6: compound K10(H2O)26Mn7(H2O)9Si4W40O140Preparation of
Adding sodium tungstate (0.5mmol), water (10 mL), manganese acetate (0.1mmol), sodium silicate (0.2mmol) and potassium chloride (1.0 mmol) into a clean reaction kettle in sequence, adjusting the pH value of the solution to 5 by using hydrochloric acid under vigorous stirring, stirring for 12h, reacting at 180 ℃ for 5 days, cooling to room temperature after the reaction is finished, and filtering to obtain black crystals. The yield was about 40%.
Example 7: compound K10(H2O)26Mn7(H2O)9Si4W40O140Preparation of
Adding sodium tungstate (0.7mmol), water (15 mL), manganese nitrate (0.2mmol), sodium silicate (0.2mmol) and potassium chloride (1.5 mmol) into a clean reaction kettle in sequence, adjusting the pH value of the solution to 6 by hydrochloric acid under vigorous stirring, stirring for 12h, reacting at 180 ℃ for 5 days, cooling to room temperature after the reaction is finished, and filtering to obtain black crystals. The yield was about 51%.
Example 8: compound K10(H2O)26Mn7(H2O)9Si4W40O140Preparation of
Adding sodium tungstate (0.6mmol), water (10 mL), manganese nitrate (0.3mmol), sodium silicate (0.2mmol) and potassium chloride (1.5 mmol) into a clean reaction kettle in sequence, adjusting the pH value of the solution to 4 by hydrochloric acid under vigorous stirring, stirring for 16h, reacting at 180 ℃ for 5 days, cooling to room temperature after the reaction is finished, and filtering to obtain black crystals. The yield was about 45%.
Example 9: compound K10(H2O)26Mn7(H2O)9Si4W40O140Preparation of
Adding sodium tungstate (0.5mmol), water (20 mL), manganese nitrate (0.1mmol), sodium silicate (0.1mmol) and potassium chloride (0.8mmol) into a clean reaction kettle in sequence, adjusting the pH value of the solution to 4 by hydrochloric acid under vigorous stirring, stirring for 12h, reacting at 150 ℃ for 5 days, cooling to room temperature after the reaction is finished, and filtering to obtain black crystals. The yield was about 37%.
Test example: application of heptanuclear manganese substituted silicotungstic oxygen cluster catalyst to TiBTD synthesis reaction
Example (c): adding 100-105 mmol of diisobutylamine, 100-110 mmol of carbon disulfide, 30-50 mg of catalyst and 30-50 mL of isopropanol into a clean 100 mL high-pressure reaction kettle, introducing oxygen to 3-5 atm, reacting at 50-60 ℃ for 3-5 h, pouring the mixture into a 250 mL reaction kettle while the mixture is hot after the reaction is finished, cooling, precipitating a large amount of solid, drying to obtain a compound, weighing, calculating and obtaining the yield, wherein the yield is up to 86%.
The experimental examples show that the designed and synthesized seven-core manganese-substituted silicotungsten oxygen cluster catalyst can realize the synthesis of the rubber vulcanization accelerator TBiTD under the action of oxygen, and the yield is as high as 86%.
Claims (3)
1. A preparation method of a seven-core manganese substituted silicotungstic oxygen cluster catalyst is characterized by comprising the following steps: the method comprises the following steps: sequentially adding sodium tungstate, water, manganese salt, sodium silicate and potassium chloride into a clean reaction kettle, adjusting the pH value of the solution to 4-6 by using hydrochloric acid under vigorous stirring, stirring for 12-24 h, reacting for 5-7 days at 170-180 ℃, cooling to room temperature after the reaction is finished, and filtering to obtain black crystals; sodium tungstate: manganese nitrate: sodium silicate: the ratio of the amount of potassium chloride is 0.5-0.9: 0.1-0.5: 0.1-0.4: 0.8-1.6; the molecular formula of the seven-core manganese substituted silicotungstic oxygen cluster catalyst is as follows: k10(H2O)26Mn7(H2O)9Si4W40O140。
2. The method of claim 1, wherein the method comprises: the used solvent is water, and the mass volume ratio g/mL of the sodium tungstate to the water is 0.16-0.3: 10 to 25.
3. The application of the heptanuclear manganese-substituted silicotungstic oxide cluster catalyst obtained by the preparation method of claim 1 in the reaction of synthesizing a rubber vulcanization accelerator TiBTD.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1861617A (en) * | 2005-05-12 | 2006-11-15 | 青岛科技大学 | Process of preparing 2-thio benzothiazole transition metal cluster compound |
CN1879896A (en) * | 2006-04-29 | 2006-12-20 | 中国科学院长春应用化学研究所 | Paramagnetic metal manganese doped multi-complex as magnetic resonance imaging contrast agent |
KR20130109830A (en) * | 2012-03-28 | 2013-10-08 | 삼성전자주식회사 | Adsorbent for carbon dioxide, method of preparing the same, and capture module for carbon dioxide |
CN106622372A (en) * | 2016-12-17 | 2017-05-10 | 聊城大学 | Barium-silicon tungsten oxygen cluster catalyst, preparation method and application thereof |
CN107297210A (en) * | 2017-07-16 | 2017-10-27 | 聊城市技师学院(聊城高级工程职业学校) | Four poly- nickel replace the preparation method of silicon tungsten oxygen cluster catalyst |
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US7820868B2 (en) * | 2007-01-19 | 2010-10-26 | Exxonmobil Chemical Patents Inc. | Transition metal substituted polyoxometalates and process for their preparation |
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1861617A (en) * | 2005-05-12 | 2006-11-15 | 青岛科技大学 | Process of preparing 2-thio benzothiazole transition metal cluster compound |
CN1879896A (en) * | 2006-04-29 | 2006-12-20 | 中国科学院长春应用化学研究所 | Paramagnetic metal manganese doped multi-complex as magnetic resonance imaging contrast agent |
KR20130109830A (en) * | 2012-03-28 | 2013-10-08 | 삼성전자주식회사 | Adsorbent for carbon dioxide, method of preparing the same, and capture module for carbon dioxide |
CN106622372A (en) * | 2016-12-17 | 2017-05-10 | 聊城大学 | Barium-silicon tungsten oxygen cluster catalyst, preparation method and application thereof |
CN107297210A (en) * | 2017-07-16 | 2017-10-27 | 聊城市技师学院(聊城高级工程职业学校) | Four poly- nickel replace the preparation method of silicon tungsten oxygen cluster catalyst |
Non-Patent Citations (1)
Title |
---|
"橡胶硫化促进剂的催化氧化合成工艺";樊云峰等;《化学工程师》;19931231;第6卷;第37-39页 * |
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