CN103041825B - Preparation method of dimethyl sulfone as well as used catalyst and catalyst composition thereof - Google Patents
Preparation method of dimethyl sulfone as well as used catalyst and catalyst composition thereof Download PDFInfo
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Abstract
The invention belongs to the field of organic synthetic chemistry, and in particular relates to a preparation method of dimethyl sulfone as well as used catalyst and catalyst composition thereof. The general formula of the catalyst is aFe2O3.bMnO2.cTiO2.dRh203.eRuO2, wherein a, b and c are selected from 0 to 15 independently, and d and e are selected from 0.01 to 10 independently. The catalyst composition comprises the catalyst and photosensitizer with the mass ratio of 1:0.01 to 10. The catalyst/catalyst composition has efficient catalytic activity, oxygen is taken as single oxidant during a process of catalyzing dimethylsulfide or dimethyl sulfoxide to prepare dimethyl sulfone, and compared with a conventional nitric acid technique and a potassium permanganate method, the preparation method has the advantages that during preparation, any hazardous substances can not be caused, and pollution is not caused to the environment.
Description
Technical field
The invention belongs to synthetic organic chemical art, more specifically, relate to
onekind of the preparation method of dimethyl sulfone and the catalyst of use thereof and carbon monoxide-olefin polymeric.
Background technology
Dimethyl sulfone another name methyl sulfonyl methane (Methyl Sulfonyl Methane, MSM) is a kind of organic sulfur compound, is the necessary material of human collagen albumen synthesis, will cause health disorders once lack or disease occurs.It is industrially as organic synthesis high-temperature solvent and raw material simultaneously, GC stationary liquid, analytical reagent, food additives and medicine.The synthesis of dimethyl sulfone is formed through oxidation by dimethyl sulfide or dimethyl sulfoxide (DMSO).
According to research reports, dimethyl sulfone mainly contains several production method: being 1. oxidant with nitric acid, is that primary raw material synthesizes with dimethyl sulfoxide (DMSO).The method raw material availability is high, and nitric acid is cheap, but danger is comparatively large, and equipment is easily corroded, and has a large amount of waste gas waste water to pollute.2. take hydrogen peroxide as oxidant (CN1397548A), route and nitrate method are substantially identical.The method production process is pollution-free, and yield is high, and shortcoming is that hydrogen peroxide has certain danger, and not easily store transport, price is higher.3. permanganimetric method.This process recovery ratio is lower, and waste gas waste water is many, and product is not easily refined.CN1397533A uses transition metal complex catalyst in addition, only prepares dimethyl sulfone with air oxidant, but needs to add isopentyl aldehyde, considerably increases production cost.Also have CN102527408A to use self-control multimetal reforming catalyst, dimethyl sulfone can be prepared by the effective catalysis dimethyl sulphide of temperate condition again, but this catalyst use amount is large.
Summary of the invention
Primary technical problem to be solved by this invention is, in order to overcome the above-mentioned deficiency of prior art, provides a kind of
oneplant catalyst.The advantages such as this catalyst has efficiently, environmental protection, can reclaiming and repeat to apply mechanically, can take air or oxygen as single-oxidizer, and under relatively mild condition, catalytic oxidation dimethyl sulfide or dimethyl sulfoxide (DMSO) prepare dimethyl sulfone, and realizes zero-emission.
Secondary technical problem to be solved by this invention provides the preparation method of described catalyst.
Another technical problem to be solved by this invention provides a kind of carbon monoxide-olefin polymeric.
A technical problem more to be solved by this invention provides a kind of preparation method of carbon monoxide-olefin polymeric.
A technical problem more to be solved by this invention provides a kind of preparation method of dimethyl sulfone.
Above-mentioned technical problem to be solved by this invention is achieved by the following technical programs:
A kind of catalyst, its general formula is aFe
2o
3bMnO
2cTiO
2dRh
2o
3eRuO
2; Wherein a, b, c are independently selected from 0 ~ 15, d, e is independently selected from 0.01 ~ 10.
As a kind of preferred version, described a, b, c are independently selected from 0 ~ 5, d, e is independently selected from 0.05 ~ 3.
As the further preferred version of one, a is selected from 0 ~ 1, b and is selected from 0 ~ 2, c and is selected from 1 ~ 3, d and is selected from 0.05 ~ 0.5, e and is selected from 0.05 ~ 1.
As one most preferably scheme, a is selected from 0.05 ~ 1, b and is selected from 0.05 ~ 2, c and is selected from 1 ~ 2, d and is selected from 0.1 ~ 0.5, e and is selected from 0.1 ~ 0.5.
Prepare a method for above-mentioned catalyst, comprise the steps: the catalyst aFe by required preparation
2o
3bMnO
2cTiO
2dRh
2o
3eRuO
2molar ratio take di-iron trioxide, manganese dioxide, titanium oxide, rhodium oxide and ruthenium-oxide, roasting 0.5 ~ 24 hour at 50 ~ 500 DEG C after mixing, cooling obtains.
As a kind of preferred version, above-mentioned sintering temperature is 100 ~ 400 DEG C, and roasting time is 0.5 ~ 10 hour.
A kind of carbon monoxide-olefin polymeric, comprises above-mentioned catalyst and sensitising agent; The mass ratio of described catalyst and sensitising agent is 1:0.01 ~ 10.
Sensitising agent is the luminous energy of the certain wavelength of Absorbable rod, Light energy transfer to some on the insensitive reactant of light, improve the material of its reactivity.
As a kind of preferred version, described described catalyst and the mass ratio of sensitising agent are 1:0.1 ~ 5.
As one most preferably scheme, described described catalyst and the mass ratio of sensitising agent are 1:0.1 ~ 1.
As a kind of preferred version, described sensitising agent is selected from the mixing of one or more in transient metal complex, porphyrin substance, phthalocyanines material, chlorophyll, vitamin, purine, phenolphthalein, organic dyestuff, pigment, pigment and styrax ether material.
As one most preferably scheme, described sensitising agent is selected from phthalocyanine, fluorescein, eosin, acridine red, methylene blue, curcumin, benzophenone, 9,10-dintrile anthracenes, 1,2,4,5-four cyano benzene, 2,3, the mixing of one or more in the chloro-Isosorbide-5-Nitrae-benzoquinones of 5,6-tetra-, rose-red and haematoporphyrin.
A preparation method for carbon monoxide-olefin polymeric, comprises the steps: above-mentioned catalyst and sensitising agent to mix, grinds to form uniform powder.
Above-mentioned catalyst or the application of carbon monoxide-olefin polymeric in the synthesis of catalysis dimethyl sulfoxide (DMSO).
A kind of preparation method of dimethyl sulfone, comprise the steps: with dimethyl sulfide or dimethyl sulfoxide (DMSO) as raw material, after adding solvent, add catalysts, the illumination being 190 ~ 780nm through wavelength is penetrated, react under the air or oxygen atmosphere of 1 ~ 100atm, reaction temperature is 0 ~ 120 DEG C, and the reaction time is 1 ~ 48 hour; The weight ratio of its Raw, solvent and catalysts is 1:0 ~ 50:0.01 ~ 2; Described catalysts is above-mentioned catalyst or above-mentioned carbon monoxide-olefin polymeric.
As a kind of preferred version, the weight ratio of described raw material, solvent and catalysts is 1:5 ~ 10:0.01 ~ 0.5; Described reaction temperature is 50 ~ 100 DEG C; Described solvent is selected from one or more mixtures in carrene, 1,2-dichloroethanes, oxolane, ethyl acetate, methyl alcohol, ethanol, toluene, acetone, ether, Isosorbide-5-Nitrae-dioxane, acetonitrile, nitromethane, water.
As a kind of preferred version, described carbon monoxide-olefin polymeric forms support type or non-loading type catalysts composition.
As a kind of preferred version, carrying method can be chemical load, or physical load.
As a kind of preferred version, above-mentioned light-struck wavelength is 380 ~ 780nm.
Compared with prior art, the present invention has following effect of optimization:
(1) catalyst/carbon monoxide-olefin polymeric of the present invention has high-efficiency catalytic activity, prepare in the process of dimethyl sulfone at catalysis dimethyl sulphide or dimethyl sulfoxide (DMSO), using oxygen as single-oxidizer, contrast traditional nitrate method, permanganimetric method, in preparation process, do not produce any harmful substance, pollution can not be made to environment;
(2) preparation method of dimethyl sulfone disclosed by the invention contrasts peroxide passivation, and condition is gentleer, easy and simple to handle, and without dangerous, cost is low, and efficiency is high;
(3) the recyclable repetition of catalyst/carbon monoxide-olefin polymeric of the present invention is applied mechanically.
Detailed description of the invention
Explain the present invention further below in conjunction with specific embodiment, but embodiment is not limited in any way to the present invention.
Embodiment 1
Take 16g di-iron trioxide, 17.4g manganese dioxide, 24g titanium oxide, 2.5g rhodium oxide and 1.3g ruthenium-oxide, put into 100 DEG C, baking oven activation 10 hours after mixing, after cooling, grinding is even obtains Fe
2o
32MnO
23TiO
20.1Rh
2o
30.1RuO
2.
Embodiment 2
Take 8.7g manganese dioxide, 8g titanium oxide, 1.3g rhodium oxide and 0.6g ruthenium-oxide, put into Muffle furnace 250 DEG C activation 5 hours after mixing, after cooling, grinding is even obtains MnO
2tiO
20.05Rh
2o
30.05RuO
2.
Embodiment 3
Take 1.3g rhodium oxide, 1.3g ruthenium-oxide, put into Muffle furnace 300 DEG C activation 3 hours after mixing, after cooling, grinding is even obtains 0.5Rh
2o
3ruO
2.
Embodiment 4
Take 25.4g rhodium oxide, 0.01g ruthenium-oxide, put into Muffle furnace 300 DEG C activation 3 hours after mixing, after cooling, grinding is even obtains 10Rh
2o
30.01RuO
2.
Embodiment 5
Take 79.9g di-iron trioxide, 1.3g rhodium oxide and 0.7g ruthenium-oxide, put into 120 DEG C, baking oven activation 9 hours after mixing, after cooling, grinding is even obtains 5Fe
2o
30.05Rh
2o
30.05RuO
2.
Embodiment 6
Take 43.5g manganese dioxide, 40g titanium oxide, 1.3g rhodium oxide and 0.7g ruthenium-oxide, put into Muffle furnace 250 DEG C activation 5 hours after mixing, after cooling, grinding is even obtains 5MnO
25TiO
20.05Rh
2o
30.05RuO
2.
Embodiment 7
Take 79.9g di-iron trioxide, 43.5g manganese dioxide, 40g titanium oxide, 1.3g rhodium oxide and 0.7g ruthenium-oxide, put into 150 DEG C, baking oven activation 7 hours after mixing, after cooling, grinding is even obtains 5Fe
2o
35MnO
25TiO
20.05Rh
2o
30.05RuO
2.
Embodiment 8
Take 240g di-iron trioxide, 130g manganese dioxide, 120g titanium oxide, 0.25g rhodium oxide and 0.14g ruthenium-oxide, put into 150 DEG C, baking oven activation 7 hours after mixing, after cooling, grinding is even obtains 15Fe
2o
315MnO
215TiO
20.01Rh
2o
30.01RuO
2.
Embodiment 9
Take 16g di-iron trioxide, 17.4g manganese dioxide, 24g titanium oxide, 2.5g rhodium oxide and 1.3g ruthenium-oxide, after mixing, put into 100 DEG C, baking oven activation 10 hours, obtained 61.2g catalyst Fe
2o
32MnO
23TiO
20.1Rh
2o
30.1RuO
2, mix with 0.6g fluorescein after cooling, then grind into powder obtains composite catalyst A.
Embodiment 10
Take 8.7g manganese dioxide, 8g titanium oxide, 1.3g rhodium oxide and 0.6g ruthenium-oxide, after mixing, put into Muffle furnace 250 DEG C activation 5 hours, obtained 18.6g catalyst MnO
2tiO
20.05Rh
2o
30.05RuO
2, after cooling, obtain composite catalyst B with the rose-red grind into powder again that mixes of 18.6g.
Embodiment 11
Take 1.6g di-iron trioxide, 1.7g manganese dioxide, 2.4g titanium oxide, 0.25g rhodium oxide and 0.13g ruthenium-oxide, after mixing, put into 100 DEG C, baking oven activation 10 hours, obtained 6.1g catalyst Fe
2o
32MnO
23TiO
20.1Rh
2o
30.1RuO
2, mix with 30.5g rhodamine 6G after cooling, then grind into powder obtains composite catalyst C.
Embodiment 12
Take 1.6g di-iron trioxide, 1.7g manganese dioxide, 2.4g titanium oxide, 0.25g rhodium oxide and 0.13g ruthenium-oxide, after mixing, put into 100 DEG C, baking oven activation 10 hours, obtained 6.1g catalyst Fe
2o
32MnO
23TiO
20.1Rh
2o
30.1RuO
2, mix with 61g eosin after cooling, then grind into powder obtains composite catalyst D.
Embodiment 13
Take 16g di-iron trioxide, 17.4g manganese dioxide, 24g titanium oxide, 2.5g rhodium oxide and 1.3g ruthenium-oxide, after mixing, put into Muffle furnace 300 DEG C activation 10 hours, obtained Fe
2o
32MnO
23TiO
20.1Rh
2o
30.1RuO
2, cool for subsequent use.Get 10g active carbon, boil 30 minutes with 5% sodium hydroxide solution, be filtered dry, be washed till neutrality, then boil 1 hour with 5% nitric acid, be filtered dry, be washed till neutral rear 110 DEG C of oven dry.The active carbon of oven dry is joined in the ethanolic solution containing 2g fluorescein.Stir 12 hours, suction filtration, dry at 100 DEG C.Dried active carbon is mixed with metal oxide, obtained loaded catalyst after grinding evenly.
Embodiment 14
Take 200g dimethyl sulfide, add 500g acetonitrile as solvents, add Fe prepared by 20g embodiment 1
2o
32MnO
23TiO
20.1Rh
2o
30.1RuO
2, regulate oxygen pressure 1.5atm, 80 DEG C are stirred 12 hours.Filtering catalyst, separates out 273g dimethyl sulfone after solvent distillation, productive rate 90%.
Embodiment 15
Take 200g dimethyl sulfide, add 500g acetonitrile as solvents, add MnO prepared by 10g embodiment 2
2tiO
20.05Rh
2o
30.05RuO
2, regulate oxygen pressure 1.2atm, 80 DEG C are stirred 12 hours.Filtering catalyst, separates out 266g dimethyl sulfone after solvent distillation, productive rate 88%.
Embodiment 16
Take 200g dimethyl sulfide, add 1kg toluene and make solvent, add 0.5Rh prepared by 10g embodiment 3
2o
3ruO
2, regulate oxygen pressure 1.1atm, 110 DEG C are stirred 15 hours.Distillation fraction solvent post crystallization separates out 249g dimethyl sulfone, productive rate 82%.
Embodiment 17
Take 200g dimethyl sulfide, add 1 kg methanol as solvent, add 10Rh prepared by 10g embodiment 4
2o
30.01RuO
2, regulate 1.5atm oxygen atmosphere, 70 DEG C are stirred 24 hours.Distillation fraction solvent post crystallization separates out 227g dimethyl sulfone, productive rate 75%.
Embodiment 18
Take 200g dimethyl sulfide, add 1 kg methanol as solvent, add 5Fe prepared by 5g embodiment 5
2o
30.05Rh
2o
30.05RuO
2, regulate 1.5atm oxygen atmosphere, 100 DEG C are stirred 24 hours.Distillation fraction solvent post crystallization separates out 242g dimethyl sulfone, productive rate 80%.
Embodiment 19
Take 200g dimethyl sulfide, add 1kg toluene and make solvent, add 5MnO prepared by 8g embodiment 6
25TiO
20.05Rh
2o
30.05RuO
2, regulate oxygen pressure 1.1atm, 110 DEG C are stirred 15 hours.Distillation fraction solvent post crystallization separates out 240g dimethyl sulfone, productive rate 79%.
Embodiment 20
Take 200g dimethyl sulfide, add 1kg ethanol as solvent, add 5Fe prepared by 20g embodiment 7
2o
35MnO
25TiO
20.05Rh
2o
30.05RuO
2, regulate oxygen pressure 1.5atm, 100 DEG C are stirred 20 hours.Distillation fraction solvent post crystallization separates out 230g dimethyl sulfone, productive rate 76%.
Embodiment 21
Take 200g dimethyl sulfide, add 1kg ethanol as solvent, add 15Fe prepared by 20g embodiment 8
2o
315MnO
215TiO
20.01Rh
2o
30.01RuO
2, regulate oxygen pressure 1.5atm, 100 DEG C are stirred 20 hours.Distillation fraction solvent post crystallization separates out 227g dimethyl sulfone, productive rate 75%.
Embodiment 22
Take 300g dimethyl sulfide, add 1.5kg methanol as solvent, add composite catalyst A prepared by 10g embodiment 9, regulate 1.5atm oxygen atmosphere.In ultra violet lamp situation, 70 DEG C are stirred 24 hours.Distillation fraction solvent post crystallization separates out 317g dimethyl sulfone, productive rate 70%.
Embodiment 23
Take 200g dimethyl sulfide, add 1kg ethanol as solvent, add composite catalyst B prepared by 10g embodiment 10, regulate 2atm oxygen atmosphere, under fluorescent lamp irradiates, 80 DEG C are stirred 12 hours.Filtering catalyst, distillation fraction solvent post crystallization separates out 272g dimethyl sulfone, productive rate 90%.
Embodiment 24
Take 200g dimethyl sulfide, add 1kg ethanol as solvent, add composite catalyst C prepared by 10g embodiment 11, regulate 2atm oxygen atmosphere, under incandescent lamp irradiates, 90 DEG C are stirred 12 hours.Filtering catalyst, distillation fraction solvent post crystallization separates out 282g dimethyl sulfone, productive rate 93%.
Embodiment 25
Take 200g dimethyl sulfide, add 1kg ethanol as solvent, add composite catalyst D prepared by 10g embodiment 12, regulate 2atm oxygen atmosphere, under incandescent lamp irradiates, 90 DEG C are stirred 12 hours.Filtering catalyst, distillation fraction solvent post crystallization separates out 279g dimethyl sulfone, productive rate 92%.
Embodiment 26
Take 200g dimethyl sulfoxide (DMSO), add 1.5kg acetone as solvent, add supported catalyst prepared by 15g embodiment 13, regulate oxygen pressure 1.5atm.Under fluorescent lamp irradiates, 60 DEG C are stirred 24 hours.Filtering catalyst, obtains 287g dimethyl sulfone after solvent distillation, productive rate 95%.
Embodiment 27
Take 200g dimethyl sulfoxide (DMSO), add 2L ethanol as solvent, add composite catalyst A prepared by 20g embodiment 4, under air atmosphere, under fluorescent lamp irradiates, 30 DEG C are stirred 48 hours.Filtering catalyst, solvent distillation post crystallization separates out 164g dimethyl sulfone, productive rate 68%.
Embodiment 28
Take 200g dimethyl sulfoxide (DMSO), add 1.5kg methanol as solvent, add composite catalyst B prepared by 10g embodiment 5, regulate oxygen pressure to 0.2MPa.Under fluorescent lamp irradiates, 70 DEG C are stirred 12 hours.Filtering catalyst, distillation fraction solvent post crystallization obtains 238g dimethyl sulfone, productive rate 99%.
Embodiment 29
Repeated to apply mechanically by the catalyst that embodiment 28 is filtered, method is with embodiment 28, and result is as follows:
Embodiment 30
Repeated to apply mechanically by the catalyst that embodiment 14 is filtered, method is with embodiment 14, and result is as follows:
Claims (2)
1. for the preparation of a catalyst for dimethyl sulfone, it is characterized in that, the general formula of described catalyst is aFe
2o
3bMnO
2cTiO
2dRh
2o
3eRuO
2; Wherein a, b, c are independently selected from 0 ~ 15, d, e is independently selected from 0.01 ~ 10; A, b are 0 time different.
2. catalyst according to claim 1, it is characterized in that, a, b, c are independently selected from 0 ~ 5, d, e is independently selected from 0.05 ~ 3; A, b are 0 time different.
3. catalyst according to claim 2, is characterized in that, a is selected from 0 ~ 1, b and is selected from 0 ~ 2, c and is selected from 1 ~ 3, d and is selected from 0.05 ~ 0.5, f and is selected from 0.05 ~ 1; A, b are 0 time different.
4. the preparation method of catalyst described in claim 1,2 or 3, it is characterized in that, comprise the steps: to take di-iron trioxide, manganese dioxide, titanium oxide, rhodium oxide and ruthenium-oxide in proportion, roasting 0.5 ~ 24 hour at 50 ~ 500 DEG C after mixing, cooling obtains.
5. for the preparation of a carbon monoxide-olefin polymeric for dimethyl sulfone, it is characterized in that, described carbon monoxide-olefin polymeric comprises catalyst and sensitising agent described in claim 1,2 or 3; The mass ratio of described catalyst and sensitising agent is 1:0.01 ~ 10; Described sensitising agent is selected from the mixing of one or more in transient metal complex, porphyrin substance, phthalocyanines material, chlorophyll, purine, phenolphthalein, organic dyestuff, pigment, pigment and styrax ether material, wherein said organic dyestuff is rhodamine 6G, fluorescein, eosin, acridine red, methylene blue, rose-red; Described pigment is benzophenone, 9,10-dintrile anthracene, 1,2,4,5-four cyano benzene, the chloro-Isosorbide-5-Nitrae-benzoquinones of 2,3,5,6-tetra-; Described pigment is curcumin.
6. the preparation method of carbon monoxide-olefin polymeric described in claim 5, comprises the steps: catalyst described in claim 1,2 or 3 and sensitising agent to mix, grinds to form uniform powder.
7. the preparation method of a dimethyl sulfone, it is characterized in that, comprise the steps: with dimethyl sulfide or dimethyl sulfoxide (DMSO) as raw material, after adding solvent, add catalysts, the illumination being 190 ~ 780nm through wavelength is penetrated, and reacts under the air or oxygen atmosphere of 1 ~ 100atm, reaction temperature is 30 ~ 120 DEG C, and the reaction time is 1 ~ 48 hour; The weight ratio of its Raw, solvent and catalysts is 1:2.5 ~ 50:0.01 ~ 2; Described catalysts is carbon monoxide-olefin polymeric described in catalyst described in claim 1,2 or 3 or claim 5 or 6.
8. preparation method according to claim 7, is characterized in that, the weight ratio of described raw material, solvent and catalysts is 1:5 ~ 10:0.01 ~ 0.5; Described reaction temperature is 50 ~ 100 DEG C; Described solvent is selected from one or more mixtures in carrene, 1,2-dichloroethanes, oxolane, ethyl acetate, methyl alcohol, ethanol, toluene, acetone, ether, Isosorbide-5-Nitrae-dioxane, acetonitrile, nitromethane, water.
9. the preparation method according to claim 7 or 8, is characterized in that, described carbon monoxide-olefin polymeric is support type or non-loading type catalysts composition.
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| CN104557625B (en) * | 2013-10-29 | 2017-01-25 | 中国石油化工股份有限公司 | Method for preparing dimethyl sulfone |
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| US6960693B2 (en) * | 2000-11-29 | 2005-11-01 | China Petroleum & Chemical Corporation | Oxidation reaction process catalyzed by phase-transfer catalyst controlling reaction |
| CN1226285C (en) * | 2003-12-15 | 2005-11-09 | 华南理工大学 | Method for preparing sulfone by catalytic oxidation of thioether |
| TWI381883B (en) * | 2006-03-10 | 2013-01-11 | Nippon Catalytic Chem Ind | Catalyst for wastewater treatment and method for wastewater treatment using said catalyst |
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