CN104557630A - Method for preparing dimethyl sulfoxide - Google Patents
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- CN104557630A CN104557630A CN201310520907.6A CN201310520907A CN104557630A CN 104557630 A CN104557630 A CN 104557630A CN 201310520907 A CN201310520907 A CN 201310520907A CN 104557630 A CN104557630 A CN 104557630A
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Abstract
The invention provides a method for preparing dimethyl sulfoxide. The method comprises the following steps: contacting dimethyl sulfide and at least one peroxide with a catalyst bed filled with at least one titanium silicalite molecular sieve in a fixed bed reactor under an oxidation condition to obtain a reaction mixture containing dimethyl sulfoxide, wherein at least part of the titanium silicalite molecular sieve is a non-fresh titanium silicalite molecular sieve. Compared with a reaction that dimethyl sulfide is contacted with peroxide without existence of the titanium silicalite molecular sieve, the method has the advantages of improving the conversion rate of dimethyl sulfide, effective utilization rate of oxidant and selectivity of dimethyl sulfoxide. Compared with the reaction that dimethyl sulfide and peroxide are contacted with fresh titanium silicalite molecular sieve, the method has the advantages that a higher oxidant effective utilization rate can be obtained, and the conversion rate of dimethyl sulfide and selectivity of dimethyl sulfoxide can be more stable in a continuous reacting process. Furthermore, the method is mild in reacting condition and easy to control, and is suitable for devices with various production scales.
Description
Technical field
The present invention relates to a kind of preparation method of dimethyl sulfoxide (DMSO).
Background technology
Dimethyl sulfoxide (DMSO) (DMSO) is a kind of organic compounds containing sulfur, is colourless transparent liquid under normal temperature, has the characteristics such as high polarity, high-hygroscopicity, flammable and high boiling point be non-proton.Dimethyl sulfoxide (DMSO) is water-soluble, ethanol, acetone, EC, it is the inert solvent that polarity is strong, be widely used as solvent and reaction reagent, such as, as process solvent and the solvent that reels off raw silk from cocoons in acrylonitrile polymerization reaction, as synthetic and the solvent that reels off raw silk from cocoons of urethane, as the synthetic of polymeric amide, fluoroaluminate glasses, polyimide and polysulfones.Further, dimethyl sulfoxide (DMSO) has very high selective extraction method ability, can be used as the Extraction solvent that alkane is separated with aromatic hydrocarbon, such as: dimethyl sulfoxide (DMSO) can be used for the extracting of aromatic hydrocarbons or divinyl.Meanwhile, in medicine industry, dimethyl sulfoxide (DMSO) not only directly as raw material and the carrier of some drugs, and can also play the effects such as anti-inflammatory analgetic, diuresis and calmness, and therefore the active ingredient of Chang Zuowei analgesic drug product makes an addition in medicine.In addition, dimethyl sulfoxide (DMSO) also can be used as capacitor dielectric, frostproofer, brake solution and rare metal extracting agent etc.
At present, dimethyl sulfoxide (DMSO) generally adopts dimethyl thioether oxidation style to obtain, and according to the difference of oxygenant, can be divided into: nitric acid oxidation method, peroxide oxidation method and Ozonation.Wherein, the main drawback of nitric acid oxidation method is that equipment corrosion is serious, and reaction conditions is restive, can produce a large amount of oxynitride, cause environmental pollution in simultaneous reactions process; Ozone oxidation rule faces the not high problem of dimethyl thioether transformation efficiency.The reaction conditions of peroxide oxidation method is gentle, environmental pollution is little, can obtain the dimethyl sulfoxide (DMSO) that purity is higher.But in peroxide oxidation method, the price of oxygenant is higher, consumption is large, causes the cost of product high.
Therefore, when adopting peroxide oxidation method to prepare dimethyl sulfoxide (DMSO), reduce the consumption of oxygenant and the effective rate of utilization improving oxygenant is technical problem urgently to be resolved hurrily.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of the dimethyl sulfoxide (DMSO) using superoxide as oxygenant, the method can obtain the oxygenant effective rate of utilization of raising.
In employing HTS as in the various full scale plants of catalyzer, as in Ammoximation reaction, hydroxylating and epoxidation reaction device, usually after plant running for some time, the catalytic activity of catalyzer declines, need to carry out in device or ex-situ regeneration, even if when carry out regenerating also be difficult to obtain satisfied active time, need catalyzer to draw off from device (that is, more catalyst changeout).The catalyzer drawn off (namely, drawing off agent or spent catalyst) current treatment process normally piles up and buries, occupy valuable land resources and inventory space on the one hand, HTS production cost is higher on the other hand, directly passes into disuse and also result in great waste.
The present inventor finds in research process: when adopting peroxide oxidation legal system for dimethyl thioether, if these are drawn off agent (namely, the HTS drawn off) regenerate after as catalyzer, with employing fresh titanium si molecular sieves as catalyzer (namely, when oxidizing reaction starts, use fresh titanium si molecular sieves as catalyzer) compare, still higher dimethyl thioether transformation efficiency and dimethyl sulfoxide (DMSO) selectivity can be obtained, and higher oxygenant effective rate of utilization can be obtained, simultaneously in tandem reaction sequence dimethyl thioether transformation efficiency and dimethyl sulfoxide (DMSO) selectivity more stable.Complete the present invention on this basis.
The invention provides a kind of preparation method of dimethyl sulfoxide (DMSO), under the method is included in oxidation reaction condition, in fixed-bed reactor, dimethyl thioether is contacted with the beds being filled with at least one HTS with at least one superoxide, obtain the reaction mixture containing dimethyl sulfoxide (DMSO), wherein, at least part of described HTS is non-fresh HTS.
According to method of the present invention, with not under catalyzer (as HTS) exists by dimethyl thioether compared with superoxide contact reacts, the dimethyl thioether transformation efficiency of raising, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity can be obtained.With by dimethyl thioether and superoxide and fresh titanium si molecular sieves (namely, when oxidizing reaction starts, using fresh titanium si molecular sieves as catalyzer) contact reacts compares, higher oxygenant effective rate of utilization can be obtained according to method of the present invention, simultaneously in tandem reaction sequence, the transformation efficiency of dimethyl thioether and the selectivity of dimethyl sulfoxide (DMSO) more stable.
In addition, gentle according to method reaction conditions of the present invention, be easy to control, be applicable to various production-scale device.
In a preferred embodiment of the invention, the mol ratio of dimethyl thioether and described superoxide is preferably higher than 1 for being not less than 1(), method of the present invention also comprises isolates unreacted dimethyl thioether from described containing the mixture of dimethyl sulfoxide (DMSO), and is again sent in fixed-bed reactor by isolated dimethyl thioether.According to this preferred embodiment, the consumption of oxygenant is little, and keeping higher dimethyl thioether transformation efficiency and dimethyl sulfoxide (DMSO) optionally simultaneously, can obtain the effective rate of utilization of more hyperoxia agent, thus effectively can reduce production cost.
Embodiment
The invention provides a kind of preparation method of dimethyl sulfoxide (DMSO), under the method is included in oxidation reaction condition, in fixed-bed reactor, dimethyl thioether is contacted with the beds being filled with at least one HTS with at least one superoxide, obtain the reaction mixture containing dimethyl sulfoxide (DMSO), wherein, at least part of described HTS is non-fresh HTS.
Described HTS is the general name that titanium atom replaces a class zeolite of a part of Siliciumatom in lattice framework, can use chemical formula xTiO
2siO
2represent.The present invention is not particularly limited for the content of titanium atom in HTS, can be that the routine of this area is selected.Particularly, x can be 0.0001-0.05, is preferably 0.01-0.03, is more preferably 0.015-0.025.
Described HTS can for the common HTS with various topological framework, such as: described HTS can be selected from the HTS (as TS-1) of MFI structure, the HTS (as TS-2) of MEL structure, the HTS (as Ti-Beta) of BEA structure, the HTS (as Ti-MCM-22) of MWW structure, the HTS of hexagonal structure is (as Ti-MCM-41, Ti-SBA-15), the HTS (as Ti-MOR) of MOR structure, the HTS (as Ti-TUN) of TUN structure and the HTS (as Ti-ZSM-48) of other structure.
Preferably, described HTS is selected from the HTS of the HTS of MFI structure, the HTS of MEL structure and BEA structure.More preferably, described HTS is the HTS of MFI structure, as TS-1 molecular sieve.
From the optionally angle improving the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO) further, the crystal grain of described HTS is hollow structure, the radical length of the chamber portion of this hollow structure is 5-300 nanometer, and described HTS is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm.Herein, the HTS with this structure is called hollow HTS.Described hollow HTS can be commercially available (be such as purchased from the trade mark of Sinopec Hunan Jianchang Petrochemical Co., Ltd be the molecular sieve of HTS), also method can prepare disclosed in CN1132699C.
According to method of the present invention, at least part of described HTS is non-fresh HTS.That is, when reaction starts, at least part of HTS is non-fresh HTS.When at least part of HTS is non-fresh HTS, satisfied dimethyl thioether transformation efficiency and dimethyl sulfoxide (DMSO) can obtained optionally simultaneously, higher oxygenant effective rate of utilization can be obtained, and in tandem reaction sequence, the transformation efficiency of dimethyl thioether and the selectivity of dimethyl sulfoxide (DMSO) more stable.
Herein, fresh titanium si molecular sieves refers to that the HTS prepared (is generally except carrying out activation treatment before use and carries out roasting, to remove the material or group that remain in the preparation process of HTS), do not live through the HTS of other physical chemistry treating processes outward.Otherwise, except activation treatment, what also live through other physical and chemical process is then non-fresh titanium si molecular sieves, as used the HTS of rear inactivation or part inactivation as the catalyzer of reaction, even comprising the HTS that the active process such as hydrothermal aging make its active reduction.
Described non-fresh HTS can be the non-fresh HTS in various source, such as, can be one or more in HTS to be generated, regeneration HTS and the HTS of fresh titanium si molecular sieves being carried out the active process as hydrothermal aging etc. and obtaining.Although HTS to be generated also can be directly used in the present invention, if but directly use HTS to be generated, some impurity may be introduced, improve the separating difficulty of the mixture containing dimethyl sulfoxide (DMSO) finally obtained, therefore, described non-fresh HTS is preferably the HTS regenerating HTS and/or fresh titanium si molecular sieves is carried out the active process as hydrothermal aging etc. and obtains.
Described regeneration HTS can for carrying out regenerating under common various regeneration conditions by the HTS to be generated in various source and the HTS obtained.
According to method of the present invention, (namely what described non-fresh HTS was preferably reaction unit using HTS as catalyzer draws off agent, described HTS to be generated is for drawing off agent) and/or undertaken regenerating and the HTS obtained by drawing off agent, be more preferably and undertaken regenerating and the HTS obtained by drawing off agent.Described draw off agent can for draw off from the device of various use HTS draw off agent, such as can for draw off from oxidation reaction apparatus draw off agent.Described oxidizing reaction can be various oxidizing reaction, draw off such as agent can for Ammoximation reaction device draw off agent, hydroxylating device draw off agent and epoxidation reaction device draw off in agent one or more, be specifically as follows cyclohexanone oxamidinating reaction unit draw off agent, phenol hydroxylation reaction unit draw off agent and propylene ring oxidation reaction device draw off in agent one or more.
The condition that HTS to be generated carries out regenerating is not particularly limited, appropriate selection can be carried out according to the source of HTS to be generated, such as: high-temperature roasting and/or solvent wash.
Fresh titanium si molecular sieves is carried out the active process such as hydrothermal aging thus the condition obtaining non-fresh HTS is also not particularly limited, can be conventional selection, such as: can by fresh titanium si molecular sieves under hydrothermal conditions (as at autogenous pressures, utilize steam treatment 0.5-72 hour 200-800 DEG C, preferably 600-800 DEG C, preferred 1-5 hour), thus obtain the non-fresh HTS of hydrothermal aging.
The activity of described non-fresh HTS is different according to its source.Usually, the activity of described non-fresh HTS can be the 5-95% of the activity of this HTS when fresh (that is, the activity of fresh titanium si molecular sieves).Preferably, the activity of described non-fresh HTS can be the 10-90% of the activity of this HTS when fresh, more preferably the 10-60% of the activity of this HTS when fresh, as 30-55%.When the activity of described non-fresh HTS is the 10-60% of the activity of this HTS when fresh, gratifying dimethyl thioether transformation efficiency and dimethyl sulfoxide (DMSO) selectivity can not only be obtained, and the oxygenant effective rate of utilization improved further can be obtained, in tandem reaction sequence dimethyl thioether transformation efficiency and dimethyl sulfoxide (DMSO) selectivity more stable.The activity of described fresh titanium si molecular sieves is generally more than 95%.
Described activity measures by the following method: the catalyzer respectively non-fresh HTS and fresh titanium si molecular sieves being used as cyclohexanone oxamidinating reaction, and the condition of this Ammoximation reaction is: HTS, 36 % by weight ammoniacal liquor (with NH
3meter), the hydrogen peroxide of 30 % by weight is (with H
2o
2meter), the trimethyl carbinol and pimelinketone by weight 1:7.5:10:7.5:10, at atmosheric pressure in 80 DEG C of reactions 2 hours.The transformation efficiency that to calculate with non-fresh HTS and fresh titanium si molecular sieves be respectively pimelinketone during catalyzer, and it can be used as the activity of non-fresh HTS and fresh titanium si molecular sieves, wherein, transformation efficiency=[molar weight of the pimelinketone of (molar weight of the molar weight-unreacted pimelinketone of the pimelinketone added)/add] × 100% of pimelinketone.
According to method of the present invention, as long as although containing non-fresh HTS in HTS, but with the total amount of described HTS for benchmark, the content of non-fresh HTS is preferably more than 5 % by weight, the effect better improving oxygenant effective rate of utilization can not only be obtained like this, and reaction process is more steadily easy to control, also can obtain gratifying dimethyl thioether transformation efficiency and dimethyl sulfoxide (DMSO) selectivity simultaneously.According to method of the present invention, even if all HTS be non-fresh HTS (namely, the content of non-fresh HTS is 100 % by weight) time, still can obtain gratifying dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity.Under the prerequisite obtaining high oxygenant effective rate of utilization, from improving the transformation efficiency of dimethyl thioether and the optionally angle of dimethyl sulfoxide (DMSO) further, with the total amount of described HTS for benchmark, the content of non-fresh HTS is more preferably 50-80 % by weight.
According to method of the present invention, described HTS is preferably shaping HTS.The carrier of described shaping HTS for conventional various heat-resistant inorganic oxides, as aluminum oxide and/or silicon oxide, can be preferably silicon oxide.Can adopt conventional various methods that HTS is shaping.Such as, after HTS can being mixed with support material, carry out shaping, and the forming composition obtained is carried out drying and optional roasting, thus obtain described shaping HTS.Described support material can be conventional selection, such as, can be selected from the precursor of inorganic heat-resistant inorganic oxide, the precursor of heat-resistant inorganic oxide, silicate and silicate.The precursor of described heat-resistant inorganic oxide can for forming the material of described heat-resistant inorganic oxide.Such as, when described heat-resistant inorganic oxide is aluminum oxide, described precursor can be various hydrated aluminum oxide; When described heat-resistant inorganic oxide is silicon oxide, described precursor can be selected from various silicon sol and organo-siloxane.The granular size of described shaping HTS is also not particularly limited, and can carry out appropriate selection according to concrete shape.Preferably, when described shaping HTS is spherical, the median size of described shaping HTS can be 2-5000 micron, is preferably 5-2000 micron, is more preferably 40-800 micron.Described particle diameter is the volume average particle size adopting laser particle analyzer to measure.
According to method of the present invention, the mol ratio of dimethyl thioether and described superoxide can be 1:0.1-2, is preferably 1:0.1-1.5.One of the present invention preferred embodiment in, the mol ratio of dimethyl thioether and described superoxide is for being not less than 1:1, can be such as 1:0.1-1, higher oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity can be obtained like this, reduce running cost further.Further preferably, the mol ratio of dimethyl thioether and described superoxide is 1:0.2-0.8, as 1:0.2-0.5.
Described superoxide refers to the compound containing-O-O-key in molecular structure, can be hydrogen peroxide and/or organo-peroxide, its specific examples can include but not limited to: hydrogen peroxide, tertbutyl peroxide, dicumyl peroxide, cyclohexyl hydroperoxide, Peracetic Acid and Perpropionic Acid.Preferably, described oxygenant is hydrogen peroxide, can reduce separation costs further like this.The hydrogen peroxide existed in a variety of manners that described hydrogen peroxide can be commonly used for this area.
From the angle improved further according to the security of method of the present invention, preferably use the hydrogen peroxide existed as an aqueous solution according to method of the present invention.According to method of the present invention, when described hydrogen peroxide provides as an aqueous solution, the concentration of described aqueous hydrogen peroxide solution can be the normal concentration of this area, such as: 20-80 % by weight.The aqueous solution that concentration meets the hydrogen peroxide of above-mentioned requirements can adopt ordinary method to prepare, and also can be commercially available, such as: can for can be commercially available the hydrogen peroxide of 30 % by weight, the hydrogen peroxide of 50 % by weight or 70 % by weight hydrogen peroxide.
According to method of the present invention, from the degree of mixing improved further in reaction system between each reactant, enhanced dispersion and more easily to the angle that the severe degree of reaction regulates, described contact is preferably carried out in the presence of at least one solvent.The kind of described solvent is not particularly limited.Usually, described solvent can be selected from water, C
1-C
6alcohol, C
3-C
8ketone and C
2-C
6nitrile.The specific examples of described solvent can include but not limited to: water, methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol, acetone, butanone and acetonitrile.Preferably, described solvent is selected from water and C
1-C
6alcohol.More preferably, described solvent is methyl alcohol and/or water.Water as solvent can be the water in various source, is hydrogen peroxide at described oxygenant, and when hydrogen peroxide provides as an aqueous solution, the water in aqueous hydrogen peroxide solution can use as solvent.
The consumption of described solvent is not particularly limited, and can be conventional selection.Usually, the mass ratio of solvent and dimethyl thioether can 0.1-1000:1, is preferably 1-800:1, is more preferably 50-500:1.
According to method of the present invention, the avtive spot contact reacts of dimethyl thioether and oxygenant and optional solvent formation mixture and HTS, thus generate dimethyl sulfoxide (DMSO).In a preferred embodiment, method of the present invention also comprises adds at least one alkaline matter in the mixture contacted with described HTS, the addition of described alkaline matter makes the pH value of this mixture be 5-9, can improve the effective rate of utilization of oxygenant, dimethyl thioether transformation efficiency and dimethyl sulfoxide (DMSO) selectivity so further.More preferably, the addition of described alkaline matter makes the pH value of this mixture be 5.5-8.5.
Herein, described alkaline matter refer to the pH value of its aqueous solution be greater than 7 material.The specific examples of described alkaline matter can include but not limited to: ammonia (that is, NH
3), amine, quaternary ammonium hydroxide and M
1(OH)
n(wherein, M
1for basic metal or alkaline-earth metal, n is and M
1the identical integer of valency).
As described alkaline matter, ammonia can be introduced with the form of liquefied ammonia, also can introduce as an aqueous solution, can also introduce with the form of gas.Concentration as the ammonia (that is, ammoniacal liquor) of aqueous solution form is not particularly limited, and can be conventional selection, such as 1-36 % by weight.
As described alkaline matter, amine refers to hydrogen partial on ammonia or is all replaced the material formed by alkyl, comprises primary amine, secondary amine and tertiary amine.Described amine is specifically as follows the material shown in formula I and/or C
3-C
11heterocyclic amine,
In formula I, R
1, R
2and R
3can be H or C separately
1-C
6alkyl (as C
1-C
6alkyl), and R
1, R
2and R
3be asynchronously H.Herein, C
1-C
6alkyl comprise C
1-C
6straight chained alkyl and C
3-C
6branched-chain alkyl, its specific examples can include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, neo-pentyl and n-hexyl.
The specific examples of amine can include but not limited to: methylamine, dimethylamine, Trimethylamine 99, ethamine, diethylamine, triethylamine, Tri N-Propyl Amine, di-n-propylamine, Tri-n-Propylamine, Isopropylamine, Diisopropylamine, n-butylamine, di-n-butyl amine, tri-n-butyl amine, sec-butylamine, diisobutyl amine, triisobutyl amine, tert-butylamine, n-amylamine, two n-amylamines, tri-n-amyl amine, neopentyl amine, isobutylcarbylamine, di-iso-amylamine, tri-isoamylamine, tertiary amylamine, normal hexyl Amine and n-octyl amine.
Described heterocyclic amine is compound finger ring having nitrogen-atoms and this nitrogen-atoms has lone-pair electron.Described heterocyclic amine can be such as one or more in substituted or unsubstituted pyrroles, substituted or unsubstituted Pyrrolidine, substituted or unsubstituted pyridine, substituted or unsubstituted hexahydropyridine, substituted or unsubstituted imidazoles, substituted or unsubstituted pyrazoles, substituted or unsubstituted quinoline, substituted or unsubstituted dihydroquinoline, substituted or unsubstituted tetrahydroquinoline, substituted or unsubstituted decahydroquinoline, substituted or unsubstituted isoquinoline 99.9 and substituted or unsubstituted pyrimidine.
As described alkaline matter, quaternary ammonium hydroxide is specifically as follows the material shown in formula II,
In formula II, R
4, R
5, R
6and R
7can be C separately
1-C
6alkyl (as C
1-C
6alkyl).Described C
1-C
6alkyl comprise C
1-C
6straight chained alkyl and C
3-C
6branched-chain alkyl, its specific examples can include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, neo-pentyl, isopentyl, tert-pentyl and n-hexyl.
The specific examples of described quaternary ammonium hydroxide can include but not limited to: Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH (comprising four n-propyl ammonium hydroxide and tetra isopropyl ammonium hydroxide), TBAH (comprising 4-n-butyl ammonium hydroxide, four sec-butyl ammonium hydroxide, four isobutyl-ammonium hydroxide and tetra-tert ammonium hydroxide) and four pentyl ammonium hydroxide.
As described alkaline matter, M
1(OH)
nfor the oxyhydroxide of alkali-metal oxyhydroxide or alkaline-earth metal, such as, can be sodium hydroxide, potassium hydroxide, magnesium hydroxide, hydrated barta and calcium hydroxide.
According to method of the present invention, described alkaline matter can directly use, and uses after also described alkaline matter can being mixed with solution.By alkaline matter and dimethyl thioether, superoxide and optionally can contact with HTS after solvent, described mixing can be carried out outside reactor, also can carry out in reactor, be not particularly limited.
In a preferred embodiment, can also comprise according to method of the present invention and isolate unreacted dimethyl thioether from described containing the mixture of dimethyl sulfoxide (DMSO), and isolated dimethyl thioether is sent in fixed-bed reactor again.The effective rate of utilization of method superoxide of the present invention is high and the selectivity of product is good, and from reaction mixture, the purity of isolated unreacted dimethyl thioether is higher, directly can send in fixed-bed reactor recycle without the need to further purifying.This mol ratio being preferred embodiment particularly suitable for dimethyl thioether and described superoxide is for being not less than 1(as higher than 1) occasion.
Can adopt various method from reaction mixture, isolate unreacted dimethyl thioether, such as: the reaction mixture obtained can be carried out flash distillation, thus be separated by dimethyl thioether wherein.
According to method of the present invention, the weight hourly space velocity of dimethyl thioether can be 0.1-500h
-1, as 100-500h
-1.The temperature of described oxidizing reaction can be 0-100 DEG C, is preferably 20-80 DEG C.For the reaction of dimethyl thioether oxidation preparation dimethyl sulfoxide (DMSO), reduce the selectivity that temperature of reaction is conducive to improving dimethyl sulfoxide (DMSO).But, the reaction of dimethyl thioether oxidation preparation dimethyl sulfoxide (DMSO) is thermopositive reaction, when reacting at lower than the temperature of 50 DEG C, in order to avoid the temperature rise caused due to exothermic heat of reaction, the temperature of corresponding heat-eliminating medium should be lower, and the use of low-temperature cooling media will inevitably increase energy consumption.According to method of the present invention, even if carry out oxidizing reaction at 50-80 DEG C, also can obtain high dimethyl sulfoxide (DMSO) selectivity and high dimethyl thioether transformation efficiency, also avoid the demand for low-temperature cooling media simultaneously.In gauge pressure, the pressure of described oxidizing reaction can be 0-3MPa, is preferably 0.1-2.5MPa.
The invention will be further described for following embodiment, but therefore do not limit content of the present invention.
In following examples and comparative example, if not otherwise specified, used reagent is commercially available reagent.
In following examples and comparative example, the hydrogen peroxide of use is the hydrogen peroxide of 30 % by weight.
In following examples and comparative example, pressure is all in gauge pressure.
In following examples and comparative example, adopting and be purchased the median size measuring shaping HTS from the Mastersizer2000 type laser fineness gage of Malvern company of Britain, is volume average particle size.
In following examples and comparative example, fresh titanium silicalite TS-1 used is according to Zeolites, the 1992,12nd volume, prepared by the method described in 943-950 page, and its titanium oxide content is 2.5 % by weight.
In following examples, fresh hollow HTS used is prepared according to method disclosed in CN1132699C, by analysis, this HTS is MFI structure, there is hysteresis loop between the nitrogen absorption under low temperature of this HTS and desorption isotherm, crystal grain is hollow crystal grain and the radical length of chamber portion is 15-180 nanometer; This HTS sample at 25 DEG C, P/P
0=0.10, adsorption time is the benzene adsorptive capacity recorded under the condition of 1 hour is 78 milligrams/gram, and its titanium oxide content is 2.5 % by weight.
In following examples and comparative example, adopt vapor-phase chromatography to analyze the content of each composition in the reaction solution obtained, adopt following formula to calculate dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity on this basis respectively:
Dimethyl thioether transformation efficiency=[molar weight of the dimethyl thioether of (molar weight-unreacted dimethyl thioether molar weight of the dimethyl thioether added)/add] × 100%;
Oxygenant effective rate of utilization=[molar weight/(molar weight of the molar weight-unreacted oxygenant of the oxygenant added) of the dimethyl sulfoxide (DMSO) that reaction generates] × 100%;
Dimethyl sulfoxide (DMSO) selectivity=[molar weight/(molar weight of the molar weight-unreacted dimethyl thioether of the dimethyl thioether added) of the dimethyl sulfoxide (DMSO) that reaction generates] × 100%.
In following examples, following methods is adopted to determine the activity of shaping HTS (comprising fresh shaping HTS and the shaping HTS of non-fresh):
By shaping HTS, 36 % by weight ammoniacal liquor (with NH
3meter), the hydrogen peroxide of 30 % by weight is (with H
2o
2meter), the trimethyl carbinol and pimelinketone after=1:7.5:10:7.5:10 mixing at atmosheric pressure in 80 DEG C of stirring reactions after 2 hours, reactant is filtered, by vapor-phase chromatography, the liquid phase obtained is analyzed, adopt the transformation efficiency of following formulae discovery pimelinketone
The transformation efficiency of pimelinketone=[molar weight of the pimelinketone of (molar weight-unreacted pimelinketone molar weight of the pimelinketone added)/add] × 100%.
Embodiment 1-20 is for illustration of method of the present invention.
Embodiment 1
The catalyzer C1 used in the present embodiment is for being undertaken regenerating by the shaping titanium-silicon molecular sieve TS-1 drawn off from cyclohexanone oxamidinating reaction unit (median size is 55 μm) and obtain, and wherein, regeneration condition is: at 550 DEG C in air atmosphere roasting 4h.With the total amount of shaping titanium-silicon molecular sieve TS-1 for benchmark, the content of titanium-silicon molecular sieve TS-1 is 85 % by weight, and the content of silicon oxide is 15 % by weight; Activity after regeneration is its activity when fresh of 50%(is 95%).
Be seated in by catalyzer C1 (loadings is 15mL, and reactor aspect ratio is 15) in stainless steel fixed-bed micro-reactor, form beds, wherein, the quantity of beds is 1 layer.
By dimethyl thioether, hydrogen peroxide and methanol mixed, form liquid mixture.In liquid mixture, add ammoniacal liquor (concentration is 25 % by weight), the pH value of liquid mixture is adjusted to 6.5.Then, described liquid mixture is sent in fixed-bed micro-reactor with beds contact reacts.Wherein, the mol ratio of dimethyl thioether and hydrogen peroxide is 1:1, and the weight ratio of dimethyl thioether and methyl alcohol is 1:5, and the weight hourly space velocity of liquid mixture is 100h
-1.Temperature in beds is 50 DEG C, and the pressure in reactor is 0.5MPa.
The reaction mixture exported from reactor is carried out flash distillation, dimethyl thioether is wherein steamed, be then reused for preparation liquid phase mixture as reaction raw materials.
Reaction is started latter 0.5 hour and the 200 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity.Result is listed in Table 1.
Comparative example 1
The method identical with embodiment 1 is adopted to prepare dimethyl sulfoxide (DMSO), unlike, there is no loading catalyst in reactor.Reaction is started latter 0.5 hour and the 200 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity.Result is listed in Table 1.
Comparative example 2
Adopt the method identical with embodiment 1 to prepare dimethyl sulfoxide (DMSO), the catalyzer D1 unlike, use is fresh shaping titanium-silicon molecular sieve TS-1 (that is, drawing off agent used fresh dose in formation embodiment 1).Reaction is started latter 0.5 hour and the 200 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity.Result is listed in Table 1.
Embodiment 2
The method identical with embodiment 1 is adopted to prepare dimethyl sulfoxide (DMSO), unlike, in liquid mixture, do not add ammoniacal liquor (pH value of liquid mixture is 5.8).Reaction is started latter 0.5 hour and the 200 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity.Result is listed in Table 1.
Embodiment 3
The method identical with embodiment 1 is adopted to prepare dimethyl sulfoxide (DMSO), unlike, the catalyzer C2 of use is for being undertaken regenerating by the shaping hollow HTS drawn off from cyclohexanone oxamidinating reaction process (median size is 55 μm) and obtain.With the total amount of shaping hollow HTS for benchmark, the content of hollow HTS is 84 % by weight, and the content of silicon oxide is 16 % by weight; Activity after regeneration is its activity when fresh of 47%(is 96%).
Reaction is started latter 0.5 hour and the 200 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity.Result is listed in Table 1.
Comparative example 3
Adopt the method identical with embodiment 3 to prepare dimethyl sulfoxide (DMSO), the catalyzer D2 unlike, use is fresh shaping hollow HTS (that is, drawing off agent used fresh dose in formation embodiment 3).Reaction is started latter 0.5 hour and the 200 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity.Result is listed in Table 1.
Table 1
Embodiment 1 and comparative example 2, embodiment 3 are compared can find out with comparative example 3, what adopt the reaction unit through regenerating draws off the catalyzer of agent as dimethyl thioether oxidizing reaction, can under the condition obtaining higher dimethyl thioether transformation efficiency, obtain higher oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity, simultaneously in tandem reaction sequence, the activity stability of catalyzer is better.
Embodiment 4
The method identical with embodiment 3 is adopted to prepare dimethyl sulfoxide (DMSO), unlike, the catalyzer C3 of use is for being undertaken regenerating by the shaping hollow HTS drawn off from cyclohexanone oxamidinating reaction process (median size is 65 μm) and obtain.With the total amount of shaping hollow HTS for benchmark, the content of hollow HTS is 90 % by weight, and the content of silicon oxide is 10 % by weight; Activity after regeneration is its activity when fresh of 30%(is 96%).
Reaction to be proceeded to 0.5 hour and the 200 little liquid phase mixtures obtained constantly are analyzed respectively, and calculate dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity, the result obtained is listed in table 2.
Embodiment 5
The method identical with embodiment 3 is adopted to prepare dimethyl sulfoxide (DMSO), unlike, the catalyzer C4 of use is for being undertaken regenerating by the shaping hollow HTS drawn off from cyclohexanone oxamidinating reaction process (median size is 40 μm) and obtain.With the total amount of shaping hollow HTS for benchmark, the content of hollow HTS is 92 % by weight, and the content of silicon oxide is 8 % by weight; Activity after regeneration is its activity when fresh of 65%(is 96%).
Reaction to be proceeded to 0.5 hour and the 200 little liquid phase mixtures obtained constantly are analyzed respectively, and calculate dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity, the result obtained is listed in table 2.
Embodiment 6
The method identical with embodiment 3 is adopted to prepare dimethyl sulfoxide (DMSO), unlike, the catalyzer C5 of use is for being undertaken regenerating by the shaping hollow HTS drawn off from cyclohexanone oxamidinating reaction process (median size is 5 μm) and obtain.With the total amount of shaping hollow HTS for benchmark, the content of hollow HTS is 95 % by weight, and the content of silicon oxide is 5 % by weight; Activity after regeneration is its activity when fresh of 54%(is 96%).Reaction to be proceeded to 0.5 hour and the 200 little liquid phase mixtures obtained constantly are analyzed respectively, and calculate dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity, the result obtained is listed in table 2.
Table 2
Embodiment 7
The method identical with embodiment 3 is adopted to prepare dimethyl sulfoxide (DMSO), unlike, the mol ratio of dimethyl thioether and hydrogen peroxide is 2:1.Reaction to be proceeded to 0.5 hour and the 200 little liquid phase mixtures obtained constantly are analyzed respectively, and calculate dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity, the result obtained is listed in table 3.
Embodiment 8
The method identical with embodiment 3 is adopted to prepare dimethyl sulfoxide (DMSO), unlike, the mol ratio of dimethyl thioether and hydrogen peroxide is 4:1.Reaction to be proceeded to 0.5 hour and the 200 little liquid phase mixtures obtained constantly are analyzed respectively, and calculate dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity, the result obtained is listed in table 3.
Embodiment 9
The method identical with embodiment 3 is adopted to prepare dimethyl sulfoxide (DMSO), unlike, the mol ratio of dimethyl thioether and hydrogen peroxide is 5:4.Reaction to be proceeded to 0.5 hour and the 200 little liquid phase mixtures obtained constantly are analyzed respectively, and calculate dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity, the result obtained is listed in table 3.
Embodiment 10
The method identical with embodiment 3 is adopted to prepare dimethyl sulfoxide (DMSO), unlike, the mol ratio of dimethyl thioether and hydrogen peroxide is 1:2.Reaction to be proceeded to 0.5 hour and the 200 little liquid phase mixtures obtained constantly are analyzed respectively, and calculate dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity, the result obtained is listed in table 3.
Table 3
Embodiment 3-9 and embodiment 10 are compared and can find out, make dimethyl thioether and the mol ratio as the superoxide of oxygenant for being not less than 1:1, while obtaining higher dimethyl thioether transformation efficiency, the dimethyl sulfoxide (DMSO) selectivity of higher oxygenant effective rate of utilization can also be obtained.
Embodiment 11
The catalyzer C6 used in the present embodiment is for being undertaken regenerating by the shaping hollow HTS drawn off from propylene ring oxidation reaction process (median size is 150 μm) and obtain, and wherein, regeneration condition is: at 570 DEG C in air atmosphere roasting 4h.With the total amount of shaping hollow HTS for benchmark, the content of hollow HTS is 80 % by weight, and the content of silicon oxide is 20 % by weight; Activity after regeneration is its activity when fresh of 48%(is 96%).
Be seated in by catalyzer C6 (loadings is 15mL, and reactor aspect ratio is 15) in stainless steel fixed-bed micro-reactor, form beds, wherein, the quantity of beds is 1 layer.
By dimethyl thioether, Peracetic Acid and methanol mixed, form liquid mixture (pH value is 4.3).In liquid mixture, add ammoniacal liquor (concentration is 25 % by weight), the pH value of liquid mixture is adjusted to 5.5.Then, described liquid mixture is sent in fixed-bed micro-reactor with beds contact reacts.Wherein, the mol ratio of dimethyl thioether and Peracetic Acid is 3:1, and the weight ratio of dimethyl thioether and methyl alcohol is 1:8, and the weight hourly space velocity of liquid mixture is 200h
-1.Temperature in beds is 60 DEG C, and the pressure in reactor is 0.2MPa.
The reaction mixture exported from reactor is carried out flash distillation, dimethyl thioether is wherein steamed, be then reused for preparation liquid phase mixture as reaction raw materials.Reaction is started latter 0.5 hour and the 200 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity.Result is listed in table 4.
Comparative example 4
Adopt the method identical with embodiment 11 to prepare dimethyl sulfoxide (DMSO), the catalyzer unlike, use is corresponding fresh dose of catalyzer C6.Reaction is started latter 0.5 hour and the 200 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO).Result is listed in table 4.
Embodiment 12
The method identical with embodiment 11 is adopted to prepare dimethyl sulfoxide (DMSO), unlike, catalyzer is the mixture be mixed to get corresponding with catalyzer C6 for catalyzer C6 fresh dose by weight 3:1.
Reaction is started latter 0.5 hour and the 200 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity.Result is listed in table 4.
Embodiment 13
The method identical with embodiment 11 is adopted to prepare dimethyl sulfoxide (DMSO), unlike, catalyzer is the mixture be mixed to get corresponding with catalyzer C6 for catalyzer C6 fresh dose by weight 1:1.
Reaction is started latter 0.5 hour and the 200 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity.Result is listed in table 4.
Embodiment 14
The method identical with embodiment 11 is adopted to prepare dimethyl sulfoxide (DMSO), unlike, catalyzer is the mixture be mixed to get corresponding with catalyzer C6 for catalyzer C6 fresh dose by weight 1:2.
Reaction is started latter 0.5 hour and the 200 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity.Result is listed in table 4.
Embodiment 15
The method identical with embodiment 11 is adopted to prepare dimethyl sulfoxide (DMSO), unlike, the temperature in beds is 80 DEG C.Reaction is started latter 0.5 hour and the 200 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity.Result is listed in table 4.
Comparative example 5
Adopt the method identical with embodiment 15 to prepare dimethyl sulfoxide (DMSO), the catalyzer unlike, use is corresponding fresh dose of catalyzer C6.Reaction is started latter 0.5 hour and the 200 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity.Result is listed in table 4.
Embodiment 16
The method identical with embodiment 15 is adopted to prepare dimethyl sulfoxide (DMSO), unlike, the water of methyl alcohol equivalent replaces.Reaction is started latter 0.5 hour and the 200 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity.Result is listed in table 4.
Embodiment 17
The method identical with embodiment 15 is adopted to prepare dimethyl sulfoxide (DMSO), unlike, the acetonitrile of methyl alcohol equivalent replaces.Reaction is started latter 0.5 hour and the 200 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity.Result is listed in table 4.
Embodiment 18
The method identical with embodiment 15 is adopted to prepare dimethyl sulfoxide (DMSO), unlike, the acetone of methyl alcohol equivalent replaces.Reaction is started latter 0.5 hour and the 200 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity.Result is listed in table 4.
Table 4
Embodiment 19
The catalyzer C7 used in the present embodiment is for by fresh shaping hollow HTS (activity is 95%, and volume average particle size is 120 μm), at autogenous pressures, within 3 hours, obtain in 800 DEG C by steam treatment, its activity is 50%.With the total amount of shaping hollow HTS for benchmark, the content of hollow HTS is 91 % by weight, the content 9 % by weight of silicon oxide.
Be seated in by catalyzer C7 (loadings is 15mL, and reactor aspect ratio is 15) in stainless steel fixed-bed micro-reactor, form beds, wherein, the quantity of beds is 1 layer.
By dimethyl thioether, Perpropionic Acid and methanol mixed, form liquid mixture.In liquid mixture, add ammoniacal liquor (concentration is 30 % by weight), the pH value of liquid mixture is adjusted to 5.0.Then, described liquid mixture is sent in fixed-bed micro-reactor with beds contact reacts.Wherein, the mol ratio of dimethyl thioether and Perpropionic Acid is 1:0.4, and the weight ratio of dimethyl thioether and methyl alcohol is 1:10, and the weight hourly space velocity of liquid mixture is 300h
-1.Temperature in beds is 50 DEG C, and the pressure in reactor is 0.5MPa.
The reaction mixture exported from reactor is carried out flash distillation, dimethyl thioether is wherein steamed, be then reused for preparation liquid phase mixture as reaction raw materials.Reaction is started latter 0.5 hour and the 200 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity.Result is listed in table 5.
Embodiment 20
The method identical with embodiment 19 is adopted to prepare dimethyl sulfoxide (DMSO), unlike, use pyridine to replace ammoniacal liquor, the pH value of liquid mixture is adjusted to 6.Reaction is started latter 0.5 hour and the 200 little reaction mixtures obtained constantly carry out gas chromatographic analysis, and calculates dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity.Result is listed in table 5.
Table 5
Claims (14)
1. the preparation method of a dimethyl sulfoxide (DMSO), under the method is included in oxidation reaction condition, in fixed-bed reactor, dimethyl thioether is contacted with the beds being filled with at least one HTS with at least one superoxide, obtain the reaction mixture containing dimethyl sulfoxide (DMSO), wherein, at least part of described HTS is non-fresh HTS.
2. method according to claim 1, wherein, the mol ratio of dimethyl thioether and described superoxide is 1:0.1-2.
3. method according to claim 2, wherein, the mol ratio of dimethyl thioether and described superoxide is for being not less than 1:1.
4. according to the method in claim 1-3 described in any one, wherein, the method also comprises isolates unreacted dimethyl thioether from described reaction mixture, and is again sent in fixed-bed reactor by isolated dimethyl thioether.
5. according to the method in claim 1-3 described in any one, wherein, described superoxide is selected from hydrogen peroxide, tertbutyl peroxide, dicumyl peroxide, cyclohexyl hydroperoxide, Peracetic Acid and Perpropionic Acid.
6. method according to claim 1, wherein, described contact is carried out under at least one solvent exists, and the mass ratio of described solvent and dimethyl thioether is 0.1-1000:1.
7. method according to claim 6, wherein, described solvent is selected from water, C
1-C
6alcohol, C
3-C
8ketone and C
2-C
6nitrile.
8. according to the method in claim 1-3,6 and 7 described in any one, wherein, the method also comprises in the mixture of beds contact described in Xiang Yuyu adds at least one alkaline matter, and the addition of described alkaline matter makes the pH value of this mixture be 5-9.
9. method according to claim 1, wherein, with the total amount of described HTS for benchmark, the content of described non-fresh HTS is 5-100 % by weight.
10. the method according to claim 1 or 9, wherein, described non-fresh HTS be through regeneration the reaction unit using HTS as catalyzer draw off agent.
11. methods according to claim 10, wherein, described in draw off agent be Ammoximation reaction device draw off agent, hydroxylating device draw off agent and epoxidation reaction device draw off in agent one or more.
12. methods according to claim 1 or 9, wherein, the activity of described non-fresh HTS is the 10-60% of the activity of this HTS when fresh.
13. methods according to claim 1 or 9, wherein, described HTS is the HTS with MFI structure.
14. methods according to claim 1, wherein, the weight hourly space velocity of dimethyl thioether is 0.1-500h
-1, described oxidation reaction condition comprises: temperature is 0-100 DEG C; In gauge pressure, pressure is 0-3MPa.
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| CN106631930A (en) * | 2015-10-29 | 2017-05-10 | 中国石油化工股份有限公司 | Thioether oxidation method |
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| CN106631932B (en) * | 2015-10-29 | 2019-04-16 | 中国石油化工股份有限公司 | A kind of sulfide oxidation method |
| CN106631931B (en) * | 2015-10-29 | 2019-04-16 | 中国石油化工股份有限公司 | A kind of sulfide oxidation method |
| CN106631930B (en) * | 2015-10-29 | 2019-04-16 | 中国石油化工股份有限公司 | A kind of sulfide oxidation method |
| CN107235871A (en) * | 2016-03-29 | 2017-10-10 | 中国石油化工股份有限公司 | A kind of sulfide oxidation method |
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