CN104418776A - Method for preparing dimethyl sulfoxide - Google Patents
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Abstract
The invention provides a method for preparing dimethyl sulfoxide. The method comprises the steps as follows: dimethyl sulfide and at least one oxidant come into contact with at least one titanium-silicalite molecular sieve in a reaction region of a reactor under an oxidative reaction condition; and the titanium-silicalite molecular sieve moves along the radial direction of the reactor in the reaction region in the contact process. According to the method disclosed by the invention, high dimethyl sulfide conversion rate, effective utilization rate of the oxidant and dimethyl sulfoxide selectivity can be obtained; the problems such as temperature runaway which can be generated by a fixed bed reactor can be effectively avoided; meanwhile, the titanium-silicalite molecular sieve of which the activity cannot meet the requirements can be moved out of a reaction system to be regenerated under the condition that the device is not shut down.
Description
Technical field
The present invention relates to a kind of method preparing 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, the following several production technique of general employing.
1, methyl alcohol dithiocarbonic anhydride method: with methyl alcohol and dithiocarbonic anhydride for raw material, with γ-Al
2o
3as catalyzer, first synthesizing dimethyl thioether, then use nitrogen peroxide (or nitric acid) oxidation to obtain dimethyl sulfoxide (DMSO).
2, nitrogen peroxide method: with methyl alcohol and hydrogen sulfide for raw material, generate dimethyl thioether under gama-alumina effect; Sulfuric acid and Sodium Nitrite are reacted obtained nitrogen peroxide; The dimethyl thioether generated and nitrogen peroxide carry out oxidizing reaction at 60-80 DEG C and generate thick dimethyl sulfoxide (DMSO), also have direct oxygen to be oxidized, the thick dimethyl sulfoxide (DMSO) of same generation; Thick dimethyl sulfoxide (DMSO), through underpressure distillation, obtains refining dimethyl sulfoxide (DMSO).
3, dimethyl sulfate ester process: methyl-sulfate and sodium sulphite are reacted, obtained dimethyl thioether; Sulfuric acid and Sodium Nitrite react and generate nitrogen peroxide; Dimethyl thioether and nitrogen peroxide carry out oxidizing reaction, obtain thick dimethyl sulfoxide (DMSO), through neutralizing treatment, obtain refining dimethyl sulfoxide (DMSO) after distillation.
Adopt anonizing also can by dimethyl sulphide production dimethyl sulfoxide (DMSO), but the cost of anonizing be higher, is unsuitable for scale operation.
Summary of the invention
The present inventor finds in research process, when adopting oxidation style to prepare dimethyl sulfoxide (DMSO) by dimethyl thioether, if use HTS effectively can improve the effective rate of utilization of oxygenant and the selectivity of dimethyl sulfoxide (DMSO) as catalyzer, high dimethyl thioether transformation efficiency can also be obtained simultaneously.
Adopt HTS as catalyzer, when preparing dimethyl sulfoxide (DMSO) by oxidation style by dimethyl thioether, can carry out in fixed-bed reactor, but when carrying out contact reacts in fixed-bed reactor, in reaction process, easily occur that in beds, local temperature is too high, occurs the problem of temperature runaway; In addition, when regenerating after catalyst deactivation, need to stop work.
The present invention is intended to overcome above shortcomings when adopting fixed-bed reactor to prepare dimethyl sulfoxide (DMSO) by oxidation style by dimethyl thioether, there is provided a kind of method preparing dimethyl sulfoxide (DMSO), the method can avoid above shortcomings in fixed-bed reactor effectively.
The invention provides a kind of method preparing dimethyl sulfoxide (DMSO), under the method is included in oxidation reaction condition, dimethyl thioether is contacted with at least one HTS with at least one oxygenant in the reaction zone of reactor, in the process of described contact, described HTS moves in reaction zone along the radial direction of reactor.
High dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity can not only be obtained according to method of the present invention, and the problem such as the beds temperature runaway can effectively avoiding fixed-bed reactor to occur, under the condition simultaneously can also do not stopped work at device, the HTS that activity cannot meet the demands is shifted out reaction system and regenerate.
Embodiment
The invention provides a kind of method preparing dimethyl sulfoxide (DMSO), under the method is included in oxidation reaction condition, dimethyl thioether is contacted with at least one HTS with at least one oxygenant in the reaction zone of reactor.
According to method of the present invention, in the process of described contact, described HTS as catalyzer moves in reaction zone along the radial direction of reactor, when can effectively avoid beds to fix in the reactor like this, be easy to the problem that in the reaction process occurred, in beds, local temperature is too high.
The top of HTS from reaction zone can be sent into, by oxygenant and dimethyl thioether respectively since the top of reaction zone or bottom are sent into, with in HTS dropping process with oxygenant and dimethyl thioether contact reacts.Under preferable case, by HTS and oxygenant respectively in the feeding reaction zone, top of reaction zone, by dimethyl thioether from the feeding reaction zone, bottom of reaction zone, in moving process, dimethyl thioether and oxygenant form mixture and with HTS contact reacts.The feeding position of described HTS, oxygenant and dimethyl thioether can be selected according to the concrete specification of reactor.
Can adopt conventional various can realize the state making HTS be in movement under react with dimethyl thioether and oxidising agent, thus obtain method or the device of dimethyl sulfoxide (DMSO), such as can in moving-burden bed reactor, dimethyl sulfoxide (DMSO) and dimethyl thioether and oxygenant are carried out contact reacts.
According to method of the present invention, HTS can move out reaction zone after the reaction, and the HTS moving out reaction zone can circulate in feeding reaction zone.When the activity of the HTS moving out reaction zone cannot meet service requirements, after the HTS moving out reaction zone can being regenerated, again send in reaction zone.The present invention is not particularly limited for the condition of regeneration, the ordinary method of this area can be adopted to carry out, such as: solvent soaking, high-temperature roasting.Described regeneration can be carried out in the revivifier outside reactor; Also breeding blanket can be set in reactor, the HTS moving out reaction zone be sent into after regenerating in breeding blanket, again send in reaction zone.
The HTS moving out reaction zone is sent into regenerate in breeding blanket or revivifier time, correspondingly can supplement in reaction zone and send into the active HTS that can meet the demands.The amount of the HTS of supplementing can be selected according to the activity of the HTS of supplementing, and is as the criterion can make the reacting balance in reaction zone.
According to method of the present invention, HTS, dimethyl thioether and the oxygenant translational speed in reaction zone can carry out appropriate selection according to the processing power of reaction zone.Usually, the weight hourly space velocity of dimethyl thioether in reaction zone can be 0.05-100h
-1, be preferably 0.1-20h
-1, be more preferably 1-10h
-1.HTS and the oxygenant translational speed in reaction zone can carry out appropriate selection according to the ratio between dimethyl thioether and HTS and oxygenant, wherein, the ratio between dimethyl thioether and HTS and the ratio between dimethyl thioether and oxygenant will be described hereinafter.
According to method of the present invention, 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 (as Ti-MOR) of MOR structure, the HTS (as Ti-TUN) of TUN structure, the HTS of two dimension hexagonal structure is (as Ti-MCM-41, and the HTS of other structure (as Ti-ZSM-48) etc. Ti-SBA-15).Described HTS is preferably selected from the HTS of the HTS of MFI structure, the HTS of MEL structure and BEA structure, is more preferably the HTS of MFI structure.
From the optionally angle improving the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO) further, described HTS is the HTS of MFI structure, and the crystal grain of this HTS is hollow structure, the radical length of the chamber portion of this hollow structure is 5-300nm, and described HTS is at 25 DEG C, P/P
0=0.10, adsorption time is the benzene adsorptive capacity that records under the condition of 1h is at least 70mg/g, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm.In the present invention, 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, the median size of described HTS can carry out appropriate selection according to concrete operational condition.Preferably, the median size of described HTS is in the scope of 0.1-1.5 μm, more preferably in the scope of 0.2-1.2 μm, preferred in the scope of 0.5-1 μm further.Described median size is the volume average particle size adopting laser mean particle size instrument to measure.
Described HTS can be the former powder of HTS, also can be shaping HTS.
In employing HTS as in the various full scale plants of catalyzer, as Ammoximation reaction, in 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, catalyzer is needed to draw off (namely from device, more catalyst changeout), and 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 pass into disuse and also result in great waste.The present inventor finds in research process, if these are drawn off agent (namely, the HTS drawn off) carry out contacting under oxidation reaction condition with oxygenant with dimethyl thioether after regeneration, still higher dimethyl thioether transformation efficiency and dimethyl sulfoxide (DMSO) selectivity can be obtained, and higher oxygenant effective rate of utilization can be obtained, in tandem reaction sequence dimethyl thioether transformation efficiency and dimethyl sulfoxide (DMSO) selectivity more stable.Therefore, according to method of the present invention, at least part of described HTS be preferably through regeneration the reaction unit using HTS as catalyzer draw off agent.Described draw off agent can for from various use HTS as the agent that draws off drawn off the reaction unit of catalyzer, such as can for draw off from oxidation reaction apparatus draw off agent.Particularly, draw off described in agent be Ammoximation reaction device draw off agent, hydroxylating device draw off agent and epoxidation reaction device draw off in agent one or more.More specifically, draw off described in agent can for 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.
Being not particularly limited drawing off the condition that agent carries out regenerating, appropriate selection can being carried out according to the source drawing off agent, such as: high-temperature roasting and/or solvent wash.
The activity drawing off agent through regeneration is different according to its source.Usually, the activity drawing off agent through regeneration 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 drawing off agent through regeneration can be the 10-90% of the activity of this HTS when fresh, more preferably through the 10-50% drawing off the activity of agent when fresh of regeneration.When the activity drawing off agent through regeneration is the 10-50% 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.The activity of described fresh titanium si molecular sieves is generally more than 90%, is generally more than 95%.
Described activity measures by the following method: will draw off through regeneration the catalyzer that agent and fresh titanium si molecular sieves are used as cyclohexanone oxamidinating reaction respectively, 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 reaction 2h.The transformation efficiency that to calculate with non-fresh HTS and fresh titanium si molecular sieves be respectively pimelinketone during catalyzer, thus determine the activity of fresh titanium si molecular sieves and non-fresh HTS, 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.
At least part of HTS be through regeneration reaction unit draw off agent time, with the total amount of described HTS for benchmark, the content that reaction unit through regeneration draws off agent 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 higher dimethyl thioether transformation efficiency and dimethyl sulfoxide (DMSO) selectivity simultaneously.According to method of the present invention, even if whole HTS is the reaction unit through regenerating draw off agent (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 that the reaction unit through regeneration draws off agent is more preferably 50-80 % by weight.
According to method of the present invention, the consumption of described HTS is as the criterion can realize catalysis.Usually, the weight ratio of dimethyl thioether and HTS can be 0.1-1000:1, is preferably 0.5-100:1, more preferably 10-50:1.
According to method of the present invention, the various compounds that dimethyl thioether oxidation can be formed dimethyl sulfoxide (DMSO) that described oxygenant can be commonly used for this area.Preferably, described oxygenant is selected from superoxide (that is, the compound containing-O-O-key in molecular structure).Described superoxide can be hydrogen peroxide and/or organo-peroxide, and 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.
When described oxygenant is superoxide, the superoxide existed in a variety of manners that described superoxide 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 superoxide existed as an aqueous solution according to method of the present invention.Such as: when described oxygenant is hydrogen peroxide, the hydrogen peroxide that preferred use exists as an aqueous solution.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.
The present invention is not particularly limited for the consumption of described oxygenant, can be conventional selection.Usually, the mol ratio of dimethyl thioether and described oxygenant can be 1:0.1-2, is preferably 1:0.2-1.5, is more preferably 1:0.2-1.
According to method of the present invention, from enhanced dispersion and more easily to the angle that the severe degree of reaction regulates, dimethyl thioether preferably carries out in the presence of at least one solvent with described oxygenant and contacting of described HTS.The kind of described solvent is not particularly limited.Usually, described solvent can be selected from water, C
1-C
8alcohol, C
3-C
8ketone, C
2-C
8nitrile and C
2-C
8carboxylic acid, be preferably water, C
1-C
6alcohol, C
3-C
6ketone and C
2-C
7nitrile.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, acetonitrile, propionitrile, benzyl cyanide and acetic acid.Preferably, described solvent is selected from water, acetone, methyl alcohol, benzyl cyanide and the trimethyl carbinol.More preferably, described solvent selected from methanol and/or water.From the further angle improving the environment friendly of method of the present invention, described solvent is water.
The present invention is not particularly limited for the consumption of solvent, can be conventional selection.Usually, the weight ratio of dimethyl thioether and solvent can be 1:0.5-100, is preferably 1:1-25.
According to method of the present invention, the conventional various methods in this area can be adopted to send in described reaction zone by described solvent, carry out in the presence of solvent with described oxygenant and contacting of HTS to make dimethyl thioether.Such as: can solvent be sent into described reaction zone from the top of reaction zone, also can send into described reaction zone from the bottom of reaction zone, can also send into described reaction zone from the middle part of reaction zone.When being sent into described reaction zone from the bottom of reaction zone by described solvent, described solvent is preferably admitted in described reaction zone with described oxygenant at same position, described solvent and oxygenant is sent in described reaction zone more particularly by same opening for feed.
According to method of the present invention, dimethyl thioether and oxygenant formed mixture in the reaction region with the avtive spot contact reacts of HTS, thus generate dimethyl sulfoxide (DMSO).Preferably, the pH value of the mixture contacted with described HTS is made to be 5-9.The pH value of the mixture contacted with HTS refers to the pH value measured when pressure is 1 standard atmospheric pressure and temperature is 25 DEG C according to the liquid mixture of the proportions of each non-Solid raw materials sending into reaction zone.Make pH value be that the mixture of 5-9 contacts with HTS, the effective rate of utilization of oxygenant, dimethyl thioether transformation efficiency and dimethyl sulfoxide (DMSO) selectivity can be improved.Further, by being that the mixture of 5-9 contacts with HTS by pH value, even if operate continuously for a long time, high oxygenant effective rate of utilization, dimethyl thioether transformation efficiency and dimethyl sulfoxide (DMSO) selectivity can still be obtained.From the optionally angle improving the effective rate of utilization of oxygenant and the transformation efficiency of dimethyl thioether and dimethyl sulfoxide (DMSO) further, the pH value of described liquid phase mixture is 5.5-8.5.
According to method of the present invention, by conventional various methods the pH value of described liquid phase mixture can be adjusted to and be within previously described scope.Particularly, can by adding the pH value that at least one basic cpd regulates described liquid phase mixture in reaction zone.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
6the specific examples of alkyl 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
6the specific examples of alkyl 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 add in described liquid phase mixture, adds in described liquid phase mixture after also described alkaline matter can being mixed with solution.
According to method of the present invention, described alkaline matter is preferably ammonia.Adopt ammonia as alkaline matter, can regulate the pH value of described liquid phase mixture on the one hand, ammonia is easy to removing on the other hand, increases burden to follow-up separation and purification process.Meanwhile, adopt ammonia can also obtain higher oxygenant effective rate of utilization and dimethyl sulfoxide (DMSO) selectivity as alkaline matter, and in reaction process, the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfoxide (DMSO) is more stable.
The addition manner of described alkaline matter is not particularly limited.Such as, the aqueous solution of the alkaline matter of predetermined amount and oxygenant can be sent into reaction zone from the same position of reactor, thus the pH value of the liquid phase mixture contacted with HTS is in the reaction region within scope mentioned above.
Method according to the present invention is not particularly limited for the condition of oxidizing reaction, as long as be enough to make oxidized dose of dimethyl thioether be oxidized to generate dimethyl sulfoxide (DMSO).Usually, temperature can be 20-200 DEG C, is preferably 30-180 DEG C, is more preferably 30-120 DEG C; In gauge pressure, the pressure in reactor can be 0-3MPa, is preferably 0.1-2.5MPa.
According to method of the present invention, the logistics containing dimethyl sulfoxide (DMSO) that contact reacts obtains can adopt the conventional method (as rectifying) in this area to be separated, and to obtain dimethyl sulfoxide (DMSO), no longer describes in detail herein.
The present invention is described in detail below in conjunction with embodiment.
In following examples and comparative example, hollow HTS used is prepared according to method disclosed in Chinese patent CN1132699C, by analysis, this HTS is MFI structure, there is hysteresis loop between the adsorption isothermal line of 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 15-180nm; This HTS sample at 25 DEG C, P/P
0=0.10, adsorption time is the benzene adsorptive capacity recorded under the condition of 1h is 78mg/g, and its titanium oxide content is 2.5 % by weight, and median size is 0.6 μm.
In following examples and comparative example, titanium-silicon molecular sieve TS-1 used is by Journal of NaturalGas Chemistry, 2001, in 10 (4): 295-307 the 296th page of 9-24 capable described by method prepare, its titanium oxide content is 2.5 % by weight, and median size is 0.8 μm.
Adopt the Mastersizer2000 type laser particle distribution instrument be purchased from Malvern company of Britain to measure median size in following examples and comparative example, wherein, median size is volume average particle size.
In following examples and comparative example, pressure is gauge pressure.
In following examples and comparative example, the composition containing the logistics of unreacted dimethyl thioether adopting gas chromatography determination to obtain from the top of reaction zone and the composition containing the logistics of dimethyl sulfoxide (DMSO) obtained from the bottom of reaction zone, undertaken quantitatively, adopting the effective rate of utilization of the following transformation efficiency of formulae discovery dimethyl thioether, the selectivity of dimethyl sulfoxide (DMSO) and hydrogen peroxide by correcting normalization method:
X
thioether=[(m
o thioether-m
thioether)/m
o thioether] × 100% (formula III)
In formula III, X
thioetherrepresent the transformation efficiency of dimethyl thioether;
M
o thioetherrepresent the quality of the dimethyl thioether added;
M
thioetherrepresent the quality of unreacted dimethyl thioether.
S
sulfoxide=[n
sulfoxide/ (n
o thioether-n
thioether)] × 100% (formula IV)
In formula IV, S
sulfoxiderepresent the selectivity of dimethyl sulfoxide (DMSO);
N
o thioetherrepresent the molar weight of the dimethyl thioether added;
N
thioetherrepresent the molar weight of unreacted dimethyl thioether;
N
sulfoxiderepresent the molar weight of the dimethyl sulfoxide (DMSO) obtained.
U
oxygenant=[n
sulfoxide/ (n
o oxygenant-n
oxygenant)] × 100% (formula V)
In formula V, U
oxygenantrepresent the effective rate of utilization of oxygenant;
N
o oxygenantrepresent the molar weight of the oxygenant added;
N
oxygenantrepresent the molar weight of unreacted oxygenant;
N
sulfoxiderepresent the molar weight of the dimethyl sulfoxide (DMSO) obtained.
Embodiment 1-10 is for illustration of method of the present invention.
Embodiment 1
Using dimethyl thioether, oxygenant, ammoniacal liquor, in the methyl alcohol and hollow HTS HTS difference continuous feeding moving-burden bed reactor of solvent, carry out contact reacts.Wherein, the bottom of dimethyl thioether from reactor is sent into, the mixture of oxygenant and solvent, ammoniacal liquor (concentration is 25 % by weight) and HTS are sent into reactor from being arranged in the liquid phase feeding mouth of reactor head, auxiliary agent opening for feed and solid phase opening for feed respectively.Wherein, oxygenant is the hydrogen peroxide of 27.5 % by weight, dimethyl thioether with in the mol ratio of the oxygenant of hydrogen peroxide for 1:1, the weight ratio of dimethyl thioether and solvent is 1:5, dimethyl thioether is 10:1 with the feed weight ratio of HTS, and the weight hourly space velocity of dimethyl thioether in reactor is 1.0h
-1, the temperature in reactor is 60 DEG C, in the pressure of gauge pressure for 0.2MPa, regulates the input speed of ammoniacal liquor to make the pH value of the liquid phase mixture in reaction zone be 7.2.In operational process, from reactor bottom export HTS for recycling.
Reaction is started the reaction mixture that rear 0.5h and 100h obtain and carries out gas chromatographic analysis, and calculate 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 1.
Embodiment 2
The method identical with embodiment 1 is adopted to prepare dimethyl sulfoxide (DMSO), unlike, use the titanium-silicon molecular sieve TS-1 of equivalent to replace hollow HTS HTS.Reaction is started the reaction mixture that rear 0.5h and 100h obtain and carries out gas chromatographic analysis, and calculate 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 1.
Embodiment 3
The method identical with embodiment 1 is adopted to prepare dimethyl sulfoxide (DMSO), unlike, in reactor, do not send into ammoniacal liquor.Reaction is started the reaction mixture that rear 0.5h and 100h obtain and carries out gas chromatographic analysis, and calculate 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 1.
Embodiment 4
The method identical with embodiment 1 is adopted to prepare dimethyl sulfoxide (DMSO), unlike, not the pH value using ammoniacal liquor regulator solution phase mixture, but use the pH value of the aqueous solution (concentration is 2.5 % by weight) the regulator solution phase mixture of NaOH.Reaction is started the reaction mixture that rear 0.5h and 100h obtain and carries out gas chromatographic analysis, and calculate 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 1.
Comparative example 1
Be seated in fixed-bed reactor by hollow HTS HTS, form beds, wherein, the quantity of beds is 1 layer.Dimethyl thioether, oxygenant and solvent are mixed according to the ratio identical with embodiment 1, and the liquid phase mixture obtained is sent into the beds contact reacts in fixed-bed reactor and containing HTS.Wherein, in dimethyl thioether, the weight hourly space velocity of liquid phase mixture in fixed-bed reactor is identical with embodiment 1, and the temperature and pressure in fixed-bed reactor is also identical with the temperature and pressure in the moving-burden bed reactor of embodiment 1.
Reaction is started the reaction mixture that rear 0.5h and 100h obtain and carries out gas chromatographic analysis, and calculate 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 1.
Comparative example 2
The method identical with embodiment 1 is adopted to prepare dimethyl sulfoxide (DMSO), unlike, in reactor, do not send into HTS.Reaction is started the reaction mixture that rear 0.5h and 100h obtain and carries out gas chromatographic analysis, and calculate 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 1.
Embodiment 5-8 adopts following methods to measure the activity of HTS.
By 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 after 80 DEG C of stirring reaction 2h, reactant is filtered, by gas-chromatography, liquid phase is analyzed, adopt the transformation efficiency of following formulae discovery pimelinketone and it can be used as the activity of HTS
The transformation efficiency of pimelinketone=[molar weight of the pimelinketone of (molar weight of the molar weight-unreacted pimelinketone of the pimelinketone added)/add] × 100%.
Embodiment 5
The method identical with embodiment 1 is adopted to prepare dimethyl sulfoxide (DMSO), unlike, the HTS used obtains for being carried out regenerating by the titanium-silicon molecular sieve TS-1 drawn off from cyclohexanone oxamidinating reaction process, its activity is 50%, activity when fresh is 95%, median size is 0.6 μm, and regeneration condition is: at 550 DEG C in air atmosphere roasting 4h.Reaction is started the reaction mixture that rear 0.5h and 100h obtain and carries out gas chromatographic analysis, and calculate 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 1.
Embodiment 6
The method identical with embodiment 1 is adopted to prepare dimethyl sulfoxide (DMSO), unlike, the hollow HTS HTS drawn off from propylene ring oxidation reaction process carries out regenerating obtaining by the HTS used, its activity is 12%, activity when fresh is 96%, median size is 0.5 μm, and regeneration condition is: at 570 DEG C in air atmosphere roasting 4h.Reaction is started the reaction mixture that rear 0.5h and 100h obtain and carries out gas chromatographic analysis, and calculate 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 1.
Embodiment 7
The method identical with embodiment 1 is adopted to prepare dimethyl sulfoxide (DMSO), unlike, the hollow HTS HTS drawn off from phenol hydroxylation reaction unit carries out regenerating obtaining by the HTS used, its activity is 30%, activity when fresh is 96%, median size is 0.6 μm, and regeneration condition is: at 570 DEG C in air atmosphere roasting 4h.Reaction is started the reaction mixture that rear 0.5h and 100h obtain and carries out gas chromatographic analysis, and calculate 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 1.
Embodiment 8
Adopting the method identical with embodiment 6 to prepare dimethyl sulfoxide (DMSO), be the hollow HTS HTS that draws off and fresh hollow HTS HTS is mixture that 2:1 is mixed to get unlike, the HTS of the use in the present embodiment by weight.Reaction is started the reaction mixture that rear 0.5h and 100h obtain and carries out gas chromatographic analysis, and calculate 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 1.
Table 1
Embodiment 9
Using dimethyl thioether, oxygenant, ammoniacal liquor (concentration is 25 % by weight), send into continuously respectively in moving-burden bed reactor as the methyl alcohol of solvent and hollow HTS HTS, contact reacts.Wherein, the bottom of dimethyl thioether from reactor is sent into, the mixture of oxygenant and solvent, ammoniacal liquor and hollow HTS HTS are sent into reactor from being arranged in the liquid phase feeding mouth of reactor head, auxiliary agent opening for feed and solid phase opening for feed respectively.Wherein, oxygenant is the hydrogen peroxide of 50 % by weight, dimethyl thioether with in the mol ratio of the oxygenant of hydrogen peroxide for 1:0.5, the weight ratio of dimethyl thioether and solvent is 1:10, dimethyl thioether is 20:1 with the feed weight ratio of HTS, and the weight hourly space velocity of dimethyl thioether in reactor is 2.0h
-1, the temperature in reactor is 45 DEG C, in the pressure of gauge pressure for 0.15MPa, regulates the input speed of ammoniacal liquor to make the pH value of the liquid phase mixture in reaction zone be 8.5.
When being reacted to 100h, while export HTS from reactor, in reactor, send into fresh hollow HTS HTS, to change the HTS of 50 % by weight; At 500 DEG C of roasting 3h in the HTS feeding revivifier more swapped out, obtain regenerating HTS; After this, every 50h, while export HTS from reactor, in reactor, send into regeneration HTS, to change the HTS of 50 % by weight.
Reaction is started the reaction mixture that rear 0.5h and 400h obtain and carries out gas chromatographic analysis, and calculate 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 2.
Embodiment 10
Using dimethyl thioether, oxygenant, ammoniacal liquor (concentration is 25 % by weight), send into continuously respectively in moving-burden bed reactor as the water of solvent and hollow HTS HTS, contact reacts.Wherein, the bottom of dimethyl thioether from reactor is sent into, the mixture of oxygenant and solvent, ammoniacal liquor and hollow HTS HTS are sent into reactor from being arranged in the liquid phase feeding mouth of reactor head, auxiliary agent opening for feed and solid phase opening for feed respectively.Wherein, oxygenant is the hydrogen peroxide of 50 % by weight, dimethyl thioether with in the mol ratio of the oxygenant of hydrogen peroxide for 1:0.2, the weight ratio of dimethyl thioether and solvent (comprising the water in hydrogen peroxide) is 1:15, dimethyl thioether is 50:1 with the feed weight ratio of HTS, and the weight hourly space velocity of dimethyl thioether in reactor is 10h
-1, the temperature in reactor is 110 DEG C, in the pressure of gauge pressure for 2.0MPa, regulates the input speed of ammoniacal liquor to make the pH value of the liquid phase mixture in reaction zone be 5.9.
When being reacted to 100h, while export HTS from reactor, in reactor, send into fresh hollow HTS HTS, to change the HTS of 50 % by weight; At 500 DEG C of roasting 3h in the HTS feeding revivifier more swapped out, obtain regenerating HTS; After this, every 50h, while export HTS from reactor, in reactor, send into regeneration HTS, to change the HTS of 50 % by weight.
Reaction is started the reaction mixture that rear 0.5h and 400h obtain and carries out gas chromatographic analysis, and calculate 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 2.
Table 2
Claims (14)
1. prepare the method for dimethyl sulfoxide (DMSO) for one kind, under the method is included in oxidation reaction condition, dimethyl thioether is contacted with at least one HTS with at least one oxygenant in the reaction zone of reactor, in the process of described contact, described HTS moves in reaction zone along the radial direction of reactor.
2. method according to claim 1, wherein, sends into the HTS circulation moving out reaction zone at least partly in reaction zone.
3. method according to claim 1, wherein, at least part of described HTS be through regeneration the reaction unit using HTS as catalyzer draw off agent.
4. method according to claim 3, 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.
5. method according to claim 1, wherein, the mol ratio of dimethyl thioether and oxygenant is 1:0.1-2, and the weight ratio of dimethyl thioether and HTS is 0.1-1000:1.
6. according to the method in claim 1-5 described in any one, wherein, the median size of described HTS is in the scope of 0.1-1.5 μm.
7. according to the method in claim 1-5 described in any one, wherein, described HTS is the HTS with MFI structure.
8. method according to claim 7, wherein, the crystal grain of described HTS is hollow structure, and the radical length of the chamber portion of this hollow structure is 5-300nm, and described HTS is at 25 DEG C, P/P
0=0.10, adsorption time is the benzene adsorptive capacity that records under the condition of 1h is at least 70mg/g, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm.
9. method according to claim 1 or 5, wherein, described oxygenant is superoxide.
10. method according to claim 9, wherein, described oxygenant is hydrogen peroxide.
11. methods according to claim 1, wherein, described contact is carried out under at least one solvent exists, and the weight ratio of dimethyl thioether and described solvent is 1:0.5-100.
12. methods according to claim 1 or 11, wherein, the pH value of the mixture contacted with described HTS is 5-9.
13. methods according to claim 1, wherein, the weight hourly space velocity of dimethyl thioether in reaction zone is 0.05-100h
-1, described oxidation reaction condition comprises: temperature is 20-200 DEG C; In gauge pressure, the pressure in reactor is 0-3MPa.
14. methods according to claim 1 or 13, wherein, described reactor is moving-burden bed reactor.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3996295A (en) * | 1974-07-04 | 1976-12-07 | Produits Chimiques Ugine Kuhlmann | Preparation of dimethylsulfoxide by liquid phase reaction of dimethysulfide and hydrogen peroxide |
| CN1301599A (en) * | 1999-12-24 | 2001-07-04 | 中国石油化工集团公司 | Titanium-silicon molecular sieve and its preparing method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3996295A (en) * | 1974-07-04 | 1976-12-07 | Produits Chimiques Ugine Kuhlmann | Preparation of dimethylsulfoxide by liquid phase reaction of dimethysulfide and hydrogen peroxide |
| CN1301599A (en) * | 1999-12-24 | 2001-07-04 | 中国石油化工集团公司 | Titanium-silicon molecular sieve and its preparing method |
Non-Patent Citations (2)
| Title |
|---|
| RAVINDER S. REDDY等: "Sulfoxidation of Thioethers using Titanium Silicate Molecular Sieve Catalysts", 《J . CHEM. SOC., CHEM. COMMUN.》, no. 2, 31 December 1992 (1992-12-31), pages 84 - 85 * |
| 朱斌 等: "表面富钛TS-1分子筛的表征与评价", 《石油学报(石油化工)》, 31 October 2009 (2009-10-31), pages 112 - 115 * |
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