CN111715292B - Preparation method and application of molybdenum catalyst - Google Patents
Preparation method and application of molybdenum catalyst Download PDFInfo
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- CN111715292B CN111715292B CN202010606590.8A CN202010606590A CN111715292B CN 111715292 B CN111715292 B CN 111715292B CN 202010606590 A CN202010606590 A CN 202010606590A CN 111715292 B CN111715292 B CN 111715292B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/72—Epoxidation
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/64—Molybdenum
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- 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
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a preparation method and application of a molybdenum catalyst, wherein pentaerythritol and ethylene oxide are reacted to prepare macromolecular alcohol; then, the macromolecular alcohol and ammonium dimolybdate react in the presence of a solvent to prepare a molybdenum catalyst solution. The molybdenum catalyst can be applied to styrene epoxidation reaction, the catalyst is in a homogeneous phase state under the reaction condition, the catalyst can be separated out from epoxidation reaction liquid by cooling after the reaction is finished, and the catalyst is obtained by simple separation. The method can effectively improve the conversion rate of styrene and peroxide, effectively reduce the content of byproducts, improve the selectivity of the product styrene oxide, facilitate the recovery of the catalyst, realize the recycling of the molybdenum catalyst, and is a green synthesis process.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a preparation method of a molybdenum catalyst and application of the molybdenum catalyst in epoxidation reaction.
Technical Field
Styrene oxide, also known as styrene oxide, is an important organic synthetic intermediate and epoxy resin diluent.
At present, the main process of the styrene oxide is a halogen alcohol method, but the method has serious environmental pollution, and the direct oxidation method is more and more concerned by people for finding an environment-friendly preparation method. The direct oxidation method mainly adopts crop oxidants such as hydrogen peroxide, TBHP and the like, but needs to add expensive metal catalysts in the reaction, but the currently adopted catalysts are mainly molybdenum catalysts and homogeneous catalysis systems, the selectivity of peroxides in the systems is low, unconverted peroxides increase the difficulty of aftertreatment, the catalysts cannot be effectively recovered after the reaction, the waste of resources is caused, particularly molybdenum resources increase the cost, and the method is not suitable for large-scale industrialization. .
In the patent US3806467A, for the first time, an olefin and H are proposed in the presence of a bis (tri-n-methylstannoxy) molybdic acid catalyst2O2A process for the preparation of epoxides by reaction, although the oxidation reaction shows good results for cyclohexene, the yield of styrene oxide is less than 3%.
V.R. Choudhary et al in US6933397A provide a process for the preparation of styrene oxide in the presence of a metal oxide-nanogold supported catalyst in the liquid phase using an organic hydroperoxide as the oxidant, when the catalyst support is Yb2O3In the case of the catalyst, the conversion of styrene is up to 81%, but the selectivity is low, up to 70%.
Disclosure of Invention
The invention aims to provide a preparation method of a molybdenum catalyst, the prepared catalyst has a good temperature control effect, the catalyst can be recycled, and the selectivity is high.
The invention also aims to provide the application of the molybdenum catalyst, which can be used in epoxidation reaction, particularly for preparing styrene oxide by directly oxidizing styrene, and has the advantages of high reaction conversion rate, high selectivity, recyclable catalyst and low cost.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a preparation method of a molybdenum catalyst comprises the following steps:
(1) pentaerythritol reacts with ethylene oxide to prepare macromolecular alcohol;
(2) and (2) reacting the macromolecular alcohol prepared in the step (1) with ammonium dimolybdate in the presence of a solvent to prepare the molybdenum catalyst.
In the invention, in the step (1), pentaerythritol and ethylene oxide react in the presence of an inorganic acid or an organic acid at a reaction temperature of 100-130 ℃ for 1-10 hours, preferably 110-120 ℃, for 2-5 hours, wherein the molar ratio of the ethylene oxide to the pentaerythritol is 8-40, preferably 20-32.
In the present invention, in the step (1), the inorganic acid or organic acid is added in an amount of 0.1 to 2wt.%, preferably 0.2 to 1.5 wt.%, for example 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.8 wt.%, 0.9 wt.%, 1.5 wt.%, 1.8 wt.%, 1.9 wt.% of the mass of pentaerythritol.
In the present invention, the inorganic acid may be selected from one or more of sulfuric acid, phosphoric acid, hydrochloric acid, etc., and the organic acid may be selected from one or more of formic acid, acetic acid, butyric acid, etc.
In the present invention, the molecular weight of the macroalcohol prepared in step (1) is 400-2000, preferably 1000-1500.
In the present invention, in the step (2), the solvent is preferably a benzene solvent, which may be toluene, ethylbenzene, cumene, xylene, etc., preferably ethylbenzene, and is added in an amount of 30 to 100% by mass based on the mass of the macroalcohol.
In the invention, in the step (2), the reaction temperature of the macrogol and the ammonium dimolybdate is 100-.
In the invention, in the step (2), the mass ratio of the macroalcohol to the ammonium dimolybdate is 2: 1-8: 1.
the invention also provides an application of the molybdenum catalyst, and the molybdenum catalyst is used in a reaction for preparing styrene oxide by oxidizing styrene.
Preferably, the styrene oxide is directly oxidized to obtain the styrene oxide under the catalysis of the molybdenum catalyst, wherein the styrene oxide is used as a raw material, and peroxide is used as an oxidant.
In the present invention, the peroxide is preferably an organic peroxide, such as t-butyl hydroperoxide, ethylbenzene hydroperoxide, cumene hydroperoxide.
A process for the preparation of styrene oxide wherein a molybdenum catalyst is added in an amount of 0.1 to 1%, preferably 0.2 to 0.5% by weight of the peroxide.
A preparation method of styrene oxide, wherein the molar ratio of the added styrene to the added peroxide is 8: 1-2: 1, preferably 6: 1-3: 1
A process for preparing styrene oxide features that the reaction temp is 70-110 deg.C, preferably 80-100 deg.C, and the reaction time is 1-20 hr, preferably 2-5 hr.
In the invention, after the styrene epoxidation reaction is finished, the reaction liquid is cooled to 10-30 ℃, the catalyst is separated out from the system, and the catalyst solid is obtained by settling and decanting.
The catalyst solid obtained by decantation is continuously put into a new batch of reaction and circularly used, the catalyst can still be in a liquid state under the reaction condition and reacts with the reaction liquid in a homogeneous phase, and the catalyst can be repeatedly used, so that the use cost is reduced.
The molybdenum catalyst prepared by the invention is a temperature control type catalyst, is in a homogeneous state under the reaction condition (70-110 ℃), can be separated out at 10-30 ℃ after the temperature is reduced after the reaction is finished, and can be repeatedly used.
Compared with the prior art, the invention has the following advantages:
(1) pentaerythritol is used as an initiator, the macromolecular alcohol obtained by the reaction of the pentaerythritol and ethylene oxide is tetrafunctional alcohol, a molecular chain is in a star polymer form, and the pentaerythritol has good compatibility with a reaction system and shows excellent catalytic activity under a higher temperature condition in the reaction process; when the reaction system is cooled to 10-30 ℃, the catalyst is separated out from the system due to the drastic change of the solubility, and the separation proportion is high and the loss is small.
(2) The catalyst is in a homogeneous state under the reaction condition, so that the reaction efficiency is higher;
(3) after the reaction is finished, the catalyst can be separated by cooling, the recovery is easy, the obtained molybdenum catalyst can be reused, the recycling of molybdenum resources is realized, and the problem that the molybdenum catalyst cannot be recovered in the prior art is solved;
(4) the complexation of pentaerythritol and Mo is adopted, the activation of active site metal Mo and organic peroxide is more sufficient, so that higher catalytic activity is presented, the conversion rate of the oxidant is extremely high, the residual rate of the peroxide is very low, trace peroxide residue in a reaction system can be realized, the recovery operation of the oxidant is not needed, the process flow is simplified, the problem of coexistence of styrene and the oxidant in a separation process is avoided, the polymerization probability of styrene is greatly reduced, and the intrinsic safety level of a separation system is improved.
(5) The molybdenum catalyst of the invention effectively reduces the content of the by-product and improves the selectivity of the product epoxyphenylethane.
Detailed Description
And (3) molecular weight analysis: the solvent used was tetrahydrofuran, using gel chromatography GPC.
Molybdenum content: measurement was carried out by ICP-OES.
Water content: measured with a Mettler moisture meter.
Peroxide content: titration was performed using a Mettler potentiometric titrator.
Gas phase analysis conditions: performing online Agilent chromatography determination by adopting an Agilent HP-5ms chromatographic column, wherein the temperature of a vaporization chamber is 300 ℃, and the temperature of a detector is 300 ℃; temperature programming is carried out for 2min at 50 ℃; at 100 ℃ for 1 min; 10 deg.C/min to 300 deg.C, 10 min.
Example 1
The preparation method of the molybdenum catalyst comprises the following steps:
firstly, 100g of pentaerythritol and 0.36g of formic acid were charged into a reaction vessel, the reaction vessel was purged with nitrogen, heated to 100 ℃, 258g of ethylene oxide was charged into the vessel over 1 hour, the reaction was continued for 5 hours, and the ethylene oxide was removed under reduced pressure to obtain a macroalcohol, and Mn ═ 481 by GPC analysis.
And adding 100g of the obtained macromolecular alcohol, 50g of ammonium dimolybdate and 30g of ethylbenzene into another reaction kettle, reacting for 60 hours at the temperature of 100 ℃, cooling to room temperature after the reaction is finished, and filtering to remove possible residual solid matters to obtain the molybdenum catalyst, wherein the serial number of the molybdenum catalyst is Mo-1.
The preparation of other catalysts is the same as the above method, and the specific feeding amount and conditions are controlled as the following table.
TABLE 1
Note: the above time is aging time, excluding feeding time, and the feeding time is 1 h.
TABLE 2 Synthesis conditions of molybdenum catalysts
Examples 2 to 5
The epoxidation evaluation was carried out separately for the four catalysts prepared in example 1:
the evaluation method is described by taking the evaluation of the catalyst Mo-1 as an example:
adding 565.8g of styrene, 5.6g of hydroquinone and 0.2g of catalyst Mo-1 into an epoxidation reaction kettle, heating to the reaction temperature of 110 ℃ after nitrogen replacement is finished, adding 295.8g of tert-butyl hydroperoxide (with the concentration of 55%) into the system for 1h, continuing to react for 1h after the addition is finished, and then cooling to 30 ℃. The conversion of t-butyl hydroperoxide was analyzed to be 99.2% and the selectivity to styrene oxide 98.3%.
The other catalysts were evaluated in the same manner as described above, and the specific amounts and conditions were controlled as shown in the following table.
Comparative example 1
Preparing molybdenum glycol: adding 100g of ethylene glycol, 50g of ammonium dimolybdate and 30g of ethylbenzene into a reaction kettle, reacting for 60 hours at 100 ℃, cooling to room temperature after the reaction is finished, and filtering to remove possible residual solid matters to obtain the molybdenum catalyst, wherein the serial number of the molybdenum catalyst is Mo-D. Then, styrene epoxidation reaction was carried out in the same manner as in example 2, and the specific reaction conditions were as shown in Table 3.
TABLE 3 epoxidation reaction
Note: the above time is the aging time after the feeding is finished, and the feeding time is unified to 1 h.
Examples 8 to 11
The evaluation above shows that all solids are precipitated after the reaction is cooled, and the solid matters can be obtained by simple sedimentation and decantation, and the solid matters are uniformly and simply dried (dried for 4h at 100 ℃) to obtain 0.16g, 0.24g, 0.54g and 0.88g of the solid matters in examples 2 to 5. The four solids are numbered Mo-1 ', Mo-2', Mo-3 'and Mo-4', respectively.
The solids obtained above were subjected to ICP tests and found to contain a high amount of molybdenum, with the results given in the following table:
| solid number | Mo-1’ | Mo-2’ | Mo-3’ | Mo-4’ |
| Content of molybdenum% | 13.22 | 6.10 | 9.87 | 8.24 |
Therefore, the evaluation of the epoxidation catalytic effect of the above solid was continued, and the evaluation was carried out by using a glass reaction apparatus in order to observe the state of the solid.
Adding 565.8g of styrene, 5.6g of hydroquinone and 0.16g of solid Mo-1' into a glass reaction kettle, heating to the reaction temperature of 110 ℃ after nitrogen replacement is finished, adding 295.8g of tert-butyl hydroperoxide (with the concentration of 55%) into the system for 1h, continuing to react for 1h after the addition is finished, and then cooling to 30 ℃.
The evaluation of other solid materials was carried out in the same manner as described above, and the specific amounts of the materials and conditions were controlled as shown in the following table.
Note: the above time is the aging time after the feeding is finished, and the feeding time is unified to 1 h.
As shown in the above examples, the catalyst of the present invention is in a homogeneous phase state under reaction conditions, and the catalyst is separated out after the reaction is completed and the temperature is reduced, so that the catalyst can be recycled after simple separation, and the effect is excellent.
Claims (19)
1. The preparation method of the molybdenum catalyst is characterized by comprising the following steps:
(1) pentaerythritol reacts with ethylene oxide to prepare macromolecular alcohol;
(2) reacting the macromolecular alcohol prepared in the step (1) with ammonium dimolybdate in the presence of a solvent to prepare a molybdenum catalyst solution;
in the step (1), the reaction temperature is 100-130 ℃, and the reaction time is 1-10 h;
in the step (1), pentaerythritol reacts with ethylene oxide in the presence of an inorganic acid or an organic acid, wherein the molar ratio of the ethylene oxide to the pentaerythritol is 8-40;
in the step (1), the addition amount of the inorganic acid or the organic acid is 0.1 to 2 weight percent of the mass of the pentaerythritol;
in the step (2), the mass ratio of the macrogol to the ammonium dimolybdate is 2: 1-8: 1;
in the step (2), the reaction temperature of the macromolecular alcohol and the ammonium dimolybdate is 100-200 ℃, and the reaction time is 5-60 h.
2. The preparation method of the molybdenum catalyst according to claim 1, wherein in the step (1), the reaction temperature is 110-120 ℃ and the reaction time is 2-5 h.
3. The method for preparing a molybdenum catalyst according to claim 1, wherein the molar ratio of the ethylene oxide to the pentaerythritol is 20 to 32.
4. The method for preparing a molybdenum catalyst according to claim 1, wherein the inorganic acid or the organic acid is added in an amount of 0.2 to 1.5 wt.% based on the mass of pentaerythritol in the step (1).
5. The method for preparing a molybdenum catalyst as claimed in claim 1, wherein the molecular weight of the macroalcohol prepared in step (1) is 400-2000.
6. The method for preparing a molybdenum catalyst as claimed in claim 5, wherein the molecular weight of the macroalcohol prepared in step (1) is 1000-1500.
7. The method for preparing a molybdenum catalyst as claimed in claim 1, wherein the reaction temperature of the macrogol and the ammonium dimolybdate in the step (2) is 120-150 ℃ and the reaction time is 10-30 h.
8. The method for preparing a molybdenum catalyst according to claim 1, wherein in the step (2), the solvent is selected from benzene solvents, and is added in an amount of 30-100% by mass of the macrogol.
9. The method for preparing a molybdenum catalyst according to claim 8, wherein the solvent in the step (2) is toluene, ethylbenzene, cumene or xylene.
10. Use of a molybdenum catalyst prepared by the process of any one of claims 1 to 9 in a reaction for the oxidation of styrene to styrene oxide.
11. The use of claim 10, wherein the styrene oxide is prepared by directly oxidizing styrene as a raw material and peroxide as an oxidant under the catalysis of the molybdenum catalyst prepared by the method of any one of claims 1 to 9.
12. The use according to claim 11, wherein the reaction temperature is 70-110 ℃ and the reaction time is 1-20 h.
13. The use according to claim 12, wherein the reaction temperature is 80-100 ℃ and the reaction time is 2-5 h.
14. Use according to claim 11, the peroxide being an organic peroxide.
15. Use according to claim 14, the organic peroxide being selected from tert-butyl hydroperoxide, ethylbenzene hydroperoxide or cumene hydroperoxide.
16. The use according to claim 11, wherein the molar ratio of the addition of styrene to peroxide is 8:1 to 2: 1.
17. The use according to claim 16, wherein the styrene and peroxide are added in a molar ratio of 6:1 to 3: 1.
18. Use according to claim 11, wherein the molybdenum catalyst is added in an amount of 0.1 to 1% by weight of the peroxide.
19. Use according to claim 18, wherein the molybdenum catalyst is added in an amount of 0.2 to 0.5% by weight of the peroxide.
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