CN105439920A - A method of co-producing dimethyl sulfoxide and acetone - Google Patents
A method of co-producing dimethyl sulfoxide and acetone Download PDFInfo
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- CN105439920A CN105439920A CN201410424650.9A CN201410424650A CN105439920A CN 105439920 A CN105439920 A CN 105439920A CN 201410424650 A CN201410424650 A CN 201410424650A CN 105439920 A CN105439920 A CN 105439920A
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Abstract
A method of co-producing dimethyl sulfoxide and acetone is disclosed. The method includes bringing dimethyl sulfide and isopropanol into contact with a titanium silicalite molecular sieve in the presence of oxygen to obtain a mixture containing dimethyl sulfoxide and acetone. By the method, a high dimethyl sulfide conversion ratio and high dimethyl sulfoxide selectivity can be achieved and the acetone can be produced as a by-product. Raw materials used in the method are environmental friendly, and environment pollutants produced by the method is less, so that the method is beneficial to environment protection. The method can be free of solvents, the raw materials can be directly used without the need of preparing into solutions, and effective throughput of a device is not reduced. The method is simple and convenient in process, easy to operate and suitable for large-scale application.
Description
Technical field
The present invention relates to a kind of method of production dimethyl sulfoxide (DMSO) simultaneously and acetone.
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.
Dimethyl sulfoxide (DMSO) generally adopts dimethyl thioether oxidation style to prepare, and according to the difference of used oxygenant and mode of oxidizing, generally includes nitric acid oxidation method, peroxide oxidation method, Ozonation, anonizing and nitrogen peroxide oxidation style.
The deficiency that nitric acid oxidation method exists is that reaction is wayward, and equipment corrosion is serious, and environmental pollution is heavier simultaneously.There is the problem of dimethyl thioether low conversion rate in ozone oxidation rule.Anonizing is unsuitable for extensive enforcement.There is the problem of environmental pollution in nitrogen peroxide oxidation rule.
The reaction conditions of peroxide oxidation method is gentle, and equipment and process route is simple, and product does not need alkali to neutralize, and substantially pollution-free to environment.But, as oxygenant the most frequently used in peroxide oxidation method, hydrogen peroxide provides with the form of hydrogen peroxide usually, and its commodity concentration is generally between 20-50 % by weight, in reaction system, inevitably introduce large water gaging like this, reduce effective treatment capacity of device.In actual mechanical process, hydrogen peroxide (hydrogen peroxide) is generally existing use and now makes, thus be generally all equipped with hydrogen peroxide (hydrogen peroxide) productive unit using hydrogen peroxide (hydrogen peroxide) as the production equipment of oxygenant, add construction cost and the running cost of device.In addition, hydrogen peroxide may decompose in reaction process, thus reduces the effective rate of utilization of hydrogen peroxide, further increases the running cost of device.
Summary of the invention
The invention provides a kind of method preparing dimethyl sulfoxide (DMSO) newly, the method is safety and environmental protection not only, and higher dimethyl thioether transformation efficiency and dimethyl sulfoxide (DMSO) selectivity can be obtained, simultaneously can also by-product acetone, the method is without the need to introducing a large amount of solvent in addition, can obtain higher effective treatment capacity.
The invention provides a kind of method of production dimethyl sulfoxide (DMSO) simultaneously and acetone, the method comprises in the presence of oxygen, is contacted by dimethyl thioether with Virahol with HTS, obtains the mixture containing dimethyl sulfoxide (DMSO) and acetone.
Adopt method of the present invention, higher dimethyl thioether transformation efficiency and higher dimethyl sulfoxide (DMSO) selectivity can be obtained, simultaneously can also by-product acetone.
The raw material environmental protection that method according to the present invention uses, the environmental pollutant of generation are few, are more conducive to environment protection.Meanwhile, can not use solvent according to method of the present invention, various raw material can directly use simultaneously, and first need not be mixed with solution, can not affect effective treatment capacity of device.
Method technical process of the present invention is easy, and easy handling is suitable for extensive enforcement.
Embodiment
The invention provides a kind of method of production dimethyl sulfoxide (DMSO) simultaneously and acetone, the method comprises in the presence of oxygen, is contacted by dimethyl thioether with Virahol with HTS, obtains the mixture containing dimethyl sulfoxide (DMSO) and acetone.
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 for being 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, one or more in the HTS (as Ti-TUN) of TUN structure and the HTS (as Ti-ZSM-48) of other structure.
Preferably, described HTS be selected from the HTS of the HTS of MFI structure, the HTS of MEL structure and BEA structure one or more.More preferably, described HTS is the HTS of MFI structure, as TS-1 molecular sieve.
From the angle improving dimethyl thioether transformation efficiency and selectivity of product further, at least part of 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 5-300 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.
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 in the presence of oxygen with Virahol with dimethyl thioether after regeneration, still higher dimethyl thioether transformation efficiency and selectivity of product can be obtained, simultaneously in long-time continuous operational process, demonstrate better activity stability.Therefore, according to method of the present invention, at least part of described HTS be preferably through regeneration the reaction unit (except dimethyl thioether oxidation 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, the 30-50% of the activity more preferably when fresh.When the activity drawing off agent through regeneration is the 30-50% of the activity of this HTS when fresh, gratifying dimethyl thioether transformation efficiency and selectivity of product can not only be obtained, and in long-time continuous operational process, demonstrate better activity stability.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 1:7.5:10:7.5:10 in mass ratio, at atmosheric pressure in 80 DEG C of reaction 2h.Calculate to draw off through regeneration the transformation efficiency that agent and fresh titanium si molecular sieves are pimelinketone during catalyzer respectively, and using it as the activity drawing off agent and fresh titanium si molecular sieves through regeneration, 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.
Be that when drawing off agent through the reaction unit of regeneration, with the total amount of described HTS for benchmark, the content that the reaction unit through regeneration draws off agent is preferably more than 5 % by weight at least part of HTS.According to method of the present invention, even if whole HTS is the reaction unit through regenerating draw off agent (namely, the content drawing off agent through the reaction unit of regeneration is 100 % by weight) time, still can obtain gratifying dimethyl thioether transformation efficiency and selectivity of product.
According to method of the present invention, dimethyl thioether and Virahol and HTS contact carry out in fixed-bed reactor time, in the preferred embodiment of the present invention, be filled with hollow HTS and titanium-silicon molecular sieve TS-1 in described fixed-bed reactor, hollow HTS and the filling order of titanium-silicon molecular sieve TS-1 make successively to contact with described titanium-silicon molecular sieve TS-1 with described hollow HTS with the liquid mixture of Virahol containing dimethyl thioether.That is, with the flow direction of the liquid mixture containing dimethyl thioether and Virahol in fixed-bed reactor for benchmark, described hollow HTS is positioned at the upstream of described titanium-silicon molecular sieve TS-1.Can by hollow HTS and titanium-silicon molecular sieve TS-1 layering are seated in fixed-bed reactor, thus realize making successively to contact with titanium-silicon molecular sieve TS-1 with this si molecular sieves hollow with the liquid mixture of Virahol containing dimethyl thioether.According to this preferred embodiment, higher selectivity of product can be obtained, simultaneously can also extending catalyst work-ing life further.
This preferred embodiment in, the mass ratio of described hollow HTS and described titanium-silicon molecular sieve TS-1 can be 1-10:1, be preferably 1-5:1.
This preferred embodiment in, the superfacial velocity that described liquid mixture flows through hollow HTS and titanium-silicon molecular sieve TS-1 can, for identical, also can be difference.Preferably, described liquid mixture flows through the superfacial velocity of hollow HTS is v
1, the superfacial velocity flowing through titanium-silicon molecular sieve TS-1 is v
2, wherein, v
1< v
2, the one way work-ing life of HTS can be extended so further.More preferably, v
2/ v
1=1.5-10.Further preferably, v
2/ v
1=2-5.
In the present invention, described superfacial velocity to refer in the unit time by the area of the mass rate (in kg/s) of the liquid mixture of beds whole process and a certain cross section of beds (with m
2meter) ratio.Usually, the quality of the liquid mixture of fixed-bed reactor will can be sent in the unit time as " by the mass rate of the liquid mixture of whole beds in the unit time ".In the present invention, superfacial velocity liquid mixture being flow through to hollow HTS does not have particular requirement, generally can at 0.001-200kg/ (m
2s) in scope.
Various method can be adopted to the superfacial velocity regulating described liquid mixture to flow through hollow HTS and titanium-silicon molecular sieve TS-1.Such as, the superfacial velocity of raw mixture can be regulated by the cross-sectional area of selecting catalyst bed.Particularly, the cross-sectional area of the beds containing hollow HTS can be made to be greater than the cross-sectional area of the beds containing titanium-silicon molecular sieve TS-1, thus to make v
1< v
2, preferably make v
2/ v
1for 1.5-10, more preferably make v
2/ v
1for 2-5.Superfacial velocity according to expection determines that the method for the cross-sectional area of beds is known in those skilled in the art, no longer describes in detail herein.
According to method of the present invention, fresh material can be introduced between described hollow HTS and titanium-silicon molecular sieve TS-1, but described liquid mixture flows through the whole process of hollow HTS and the whole process of titanium-silicon molecular sieve TS-1, described liquid mixture not included in the fresh material introduced between hollow HTS and titanium-silicon molecular sieve TS-1, previously described superfacial velocity is determined by described liquid mixture, is not subject to the impact whether introducing fresh material.
Described HTS can be the former powder of HTS, also can be shaping HTS.
Described HTS is as catalyzer, and its consumption is as the criterion can realize catalysis, can carry out catalytic concrete mode select according to HTS and dimethyl thioether and Virahol.Such as: HTS and dimethyl thioether and Virahol are being mixed to form slurry, thus when carrying out contact reacts, the weight ratio of dimethyl thioether and HTS can be 0.01-100:1, be preferably 1-100:1; HTS and dimethyl thioether and Virahol contact carry out in fixed-bed reactor time, the weight space velocity of dimethyl thioether can be 0.1-100h
-1, be preferably 1-50h
-1.In the present invention, weight hourly space velocity with the whole HTS in beds for benchmark.
According to method of the present invention, dimethyl thioether carries out in the presence of oxygen with Virahol and contacting of HTS.Can by passing into oxygen in reactor, make the atmosphere in reactor be oxygen-containing atmosphere, thus realize described contact and carry out in the presence of oxygen.Described oxygen can use the oxygen of pure state, also can use oxygen-containing gas, as long as the gas in oxygen-containing gas except oxygen is non-active gas.Described non-active gas refers to and with reactant (as dimethyl thioether and Virahol) and resultant of reaction (as dimethyl sulfoxide (DMSO) and acetone), chemically interactive gas does not occur, such as: nitrogen and/or neutral element gas (as argon gas).In oxygen-containing gas, the consumption of oxygen can be generally 0.1-99 volume %, is preferably 0.5-50 volume %.Described oxygen-containing gas can be air, also can for the gas mixture by pure oxygen and pure non-active gas being carried out being obtained by mixing.When using air as oxygen-containing gas, directly can use air, also by purifying air, can re-using after removing particulate matter wherein.The function of oxygen is to interact with Virahol, realizes dimethyl thioether to be oxidized into dimethyl sulfoxide (DMSO), and the consumption of oxygen is as the criterion can realize above-mentioned functions.Usually, the consumption of oxygen makes the oxygen partial pressure in reaction system be 0.01-5MPa, is preferably 0.05-3MPa, is more preferably 0.1-2MPa.
According to method of the present invention, under the acting in conjunction of Virahol and oxygen, dimethyl thioether is oxidized into dimethyl sulfoxide (DMSO), and the consumption of Virahol is as the criterion can realize above-mentioned functions.Usually, the mol ratio of dimethyl thioether and Virahol is 1:1-10.Preferably, the mol ratio of dimethyl thioether and Virahol is 1:3-8.
According to method of the present invention, from the angle improving dimethyl thioether transformation efficiency and selectivity of product further, dimethyl thioether carries out under the existence of at least one superoxide with Virahol and contacting of HTS.That is, dimethyl thioether, Virahol are contacted with HTS with at least one superoxide.The mol ratio of described superoxide and dimethyl thioether can be 0.0001-0.1:1, is preferably 0.0005-0.05:1.
Described superoxide refers to the compound containing-O-O-key in molecular structure, can be hydrogen peroxide and/or organo-peroxide, described organo-peroxide refers to that in hydrogen peroxide molecule structure, one or two hydrogen atom is replaced by organic group and the material formed.The specific examples of described superoxide can include but not limited to: hydrogen peroxide, tertbutyl peroxide, dicumyl peroxide, cyclohexyl hydroperoxide, Peracetic Acid, Perpropionic Acid, dicumyl peroxide, di-t-butyl peroxide, dibenzoyl peroxide and dilauroyl peroxide.In the present invention, described organo-peroxide is preferably R
1-O-O-R
2, R
1and R
2identical or different, can be H, C separately
4-C
12straight or branched alkyl or
r
3for C
4-C
12straight or branched alkyl, R
1and R
2be asynchronously H.
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 7-9, can improve dimethyl thioether transformation efficiency, selectivity of product and catalyzer work-ing life so further.More preferably, the addition of described alkaline matter makes the pH value of this mixture be 7.5-8.5., if use alkali, improve the pH value of this mixture further, still can obtain above-mentioned effect time (or being more than 7.5) in the pH value of the mixture contacted with HTS more than 7.The pH value of described mixture refers at 25 DEG C and 1 standard atmosphere pressure, the pH value of this mixture of mensuration.
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
4, R
5and R
6can be H or C separately
1-C
6alkyl (as C
1-C
6alkyl), and R
4, R
5and R
6be 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
7, R
8, R
9and R
10can 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.Contact with HTS after alkaline matter and dimethyl thioether, Virahol and optional other auxiliary agent (as superoxide) can being mixed, described mixing can be carried out outside reactor, also can carry out in reactor, be not particularly limited.
According to method of the present invention, under the prerequisite guaranteeing dimethyl thioether to be oxidized into dimethyl sulfoxide (DMSO), from improving selectivity of product, particularly acetone optionally angle further, the contact conditions of dimethyl thioether and Virahol and optional auxiliary agent (as superoxide) and HTS preferably makes the transformation efficiency of Virahol be 10-25 % by weight, more preferably 12-18 % by weight.Can select the condition controlling contact, such as catalytic temperature and pressure regulates the transformation efficiency of Virahol.
According to method of the present invention, dimethyl thioether, Virahol and optional other auxiliary agent (as superoxide) and the contact conditions of HTS, be as the criterion dimethyl thioether can be oxidized into dimethyl sulfoxide (DMSO).Usually, described contact can be carried out at the temperature of 40-160 DEG C, preferably 60-140 DEG C, more preferably 40-120 DEG C.In gauge pressure, the pressure carried out in the reactor that contacts can be 0.01-5MPa, is preferably 0.1-3MPa, is more preferably 0.5-3MPa.
Adopt operate continuously according to method of the present invention, also may be carried out batchwise.The contact of HTS and dimethyl thioether, Virahol and optional auxiliary agent (as superoxide) can be carried out, as fixed-bed reactor, slurry bed reactor in conventional various reactors.
According to method of the present invention, will in the presence of oxygen, dimethyl thioether is contacted with HTS with Virahol, obtains the mixture containing dimethyl sulfoxide (DMSO) and acetone.The step isolating dimethyl sulfoxide (DMSO) and acetone from described mixture can also be comprised according to method of the present invention.Conventional various methods can be adopted to go out dimethyl sulfoxide (DMSO) and acetone from described mixture separation, such as, described mixture is carried out fractionation.Isolate that the leftover materials of dimethyl sulfoxide (DMSO) and acetone are purified or not purified can be recycled.
Describe the present invention in detail below in conjunction with embodiment, but therefore do not limit the scope of the invention.
In following examples and comparative example, agents useful for same is commercially available analytical reagent.
In following examples and comparative example, titanium-silicon molecular sieve 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, hollow HTS used is according to the preparation of method disclosed in CN1132699C, 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, iso-propanol conversion rate, dimethyl sulfoxide (DMSO) selectivity and acetone selectivity on this basis respectively:
Dimethyl thioether transformation efficiency=[molar weight of the dimethyl thioether of (molar weight of the molar weight-unreacted dimethyl thioether of the dimethyl thioether added)/add] × 100%;
Iso-propanol conversion rate=[molar weight of the Virahol of (molar weight of the molar weight-unreacted Virahol of the Virahol added)/add] × 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%;
Acetone selectivity=[molar weight/(molar weight of the molar weight-unreacted Virahol of the Virahol added) of the acetone that reaction generates] × 100%.
In following examples, adopt the activity of following methods determination HTS (comprise and draw off agent and fresh titanium si molecular sieves through what regenerate):
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 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 and it can be used as the activity of this HTS
The transformation efficiency of pimelinketone=[molar weight of the pimelinketone of (molar weight-unreacted pimelinketone molar weight of the pimelinketone added)/add] × 100%.
Embodiment 1-23 is for illustration of method of the present invention.
Embodiment 1
In tank reactor, under oxygen atmosphere (being the atmosphere that formed of oxygen of 99% by purity), using dimethyl thioether and Virahol and the former powder contact reacts of titanium-silicon molecular sieve TS-1 as catalyzer, wherein, the mol ratio of dimethyl thioether and Virahol is 1:4, and the weight ratio of dimethyl thioether and catalyzer is 20:1, and temperature is 90 DEG C, pressure is 2.5MPa (gauge pressure), and oxygen partial pressure is 1.5MPa.React after 2 hours, the mixture obtained is filtered, the liquid mixture that collection obtains also is analyzed by gas-chromatography, thus obtains dimethyl thioether transformation efficiency, iso-propanol conversion rate, dimethyl sulfoxide (DMSO) selectivity and acetone selectivity, and result is listed in Table 1.
Embodiment 2
The method identical with embodiment 1 is adopted to be oxidized by dimethyl thioether, unlike, the hollow HTS of the quality such as use replaces titanium-silicon molecular sieve TS-1, and temperature is 60 DEG C.Experimental result is listed in Table 1.
Embodiment 3
The method identical with embodiment 1 is adopted to be oxidized by dimethyl thioether, unlike, temperature of reaction is 120 DEG C.Experimental result is listed in Table 1.
Embodiment 4
The method identical with embodiment 1 is adopted to be oxidized by dimethyl thioether, unlike, in reactor, also add hydrogen peroxide (providing with the form of the hydrogen peroxide of 30 % by weight), wherein, the mol ratio of hydrogen peroxide and dimethyl thioether is 0.0005:1.Experimental result is listed in Table 1.
Embodiment 5
The method identical with embodiment 1 is adopted to be oxidized by dimethyl thioether, unlike, in reactor, also add hydrogen peroxide (providing with the form of the hydrogen peroxide of 30 % by weight), wherein, the mol ratio of hydrogen peroxide and dimethyl thioether is 0.05:1.Experimental result is listed in Table 1.
Embodiment 6
The method identical with embodiment 5 is adopted to be oxidized by dimethyl thioether, unlike, replace hydrogen peroxide with waiting dicumyl peroxide of amount of substance.Experimental result is listed in Table 1.
Comparative example 1
The method identical with embodiment 1 is adopted to be oxidized by dimethyl thioether, unlike, do not use titanium-silicon molecular sieve TS-1.Experimental result is listed in Table 1.
Comparative example 2
The method identical with embodiment 1 is adopted to be oxidized by dimethyl thioether, unlike, do not use Virahol.Experimental result is listed in Table 1.
Comparative example 3
The method identical with embodiment 1 is adopted to be oxidized by dimethyl thioether, unlike, do not use oxygen, but use nitrogen to substitute.Experimental result is listed in Table 1.
Comparative example 4
The method identical with embodiment 1 is adopted to be oxidized by dimethyl thioether, unlike, do not use Virahol, but use hydrogen peroxide (providing with the form of the hydrogen peroxide of 30 % by weight), the mol ratio of dimethyl thioether and hydrogen peroxide is 1:1.Experimental result is listed in Table 1.
Table 1
Embodiment 1 and comparative example 1 are compared and can find out, in the presence of oxygen, under the existence of HTS, by dimethyl thioether and Virahol contact reacts, high dimethyl thioether transformation efficiency can be obtained, higher dimethyl sulfoxide (DMSO) selectivity and acetone selectivity can also be obtained simultaneously.
Embodiment 1 confirms to only have and oxygen and Virahol are combinationally used with the result of comparative example 2 and 3, with higher transformation efficiency, dimethyl thioether could be oxidized into dimethyl sulfoxide (DMSO), simultaneously by-product acetone.
Embodiment 1 confirms with the result of comparative example 4, and dimethyl thioether can not only be oxidized by method of the present invention, can obtain higher dimethyl sulfoxide (DMSO) selectivity, while can also by-product acetone; And present method avoids when using hydrogen peroxide as oxygenant, because hydrogen peroxide provides with hydrogen peroxide form, cause the treatment capacity adding device, but reduce the deficiency of effective treatment capacity of device, reduce cost simultaneously.
Embodiment 7
In tank reactor, in air atmosphere, using dimethyl thioether and Virahol and the former powder contact reacts of titanium-silicon molecular sieve TS-1 as catalyzer, wherein, the mol ratio of dimethyl thioether and Virahol is 1:3, and the weight ratio of dimethyl thioether and catalyzer is 40:1, and temperature is 50 DEG C, pressure is 1.5MPa (gauge pressure), and oxygen partial pressure is 0.3MPa.
React after 2 hours, the mixture obtained is filtered, the liquid mixture that collection obtains also is analyzed by gas-chromatography, thus obtains dimethyl thioether transformation efficiency, iso-propanol conversion rate, dimethyl sulfoxide (DMSO) selectivity and acetone selectivity, and result is listed in table 2.
Embodiment 8
In tank reactor, oxygen-containing atmosphere (by purity be 99% oxygen and purity be the atmosphere that the mixture of the nitrogen of 99% is formed, wherein, the volume ratio of oxygen and nitrogen is 1:1) under, using dimethyl thioether and Virahol and the former powder contact reacts of titanium-silicon molecular sieve TS-1 as catalyzer, wherein, the mol ratio of dimethyl thioether and Virahol is 1:8, the weight ratio of dimethyl thioether and catalyzer is 80:1, temperature is 60 DEG C, pressure is 1.0MPa (gauge pressure), and oxygen partial pressure is 0.5MPa.
React after 2 hours, the mixture obtained is filtered, the liquid mixture that collection obtains also is analyzed by gas-chromatography, thus obtains dimethyl thioether transformation efficiency, iso-propanol conversion rate, dimethyl sulfoxide (DMSO) selectivity and acetone selectivity, and result is listed in table 2.
Embodiment 9
In tank reactor, under oxygen atmosphere (being the atmosphere that formed of oxygen of 99% by purity), using dimethyl thioether and Virahol and the former powder contact reacts of titanium-silicon molecular sieve TS-1 as catalyzer, wherein, the mol ratio of dimethyl thioether and Virahol is 1:6, and the weight ratio of dimethyl thioether and catalyzer is 2:1, and temperature is 40 DEG C, pressure is 1.0MPa (gauge pressure), and oxygen partial pressure is 0.5MPa.
React after 4 hours, the mixture obtained is filtered, the liquid mixture that collection obtains also is analyzed by gas-chromatography, thus obtains dimethyl thioether transformation efficiency, iso-propanol conversion rate, dimethyl sulfoxide (DMSO) selectivity and acetone selectivity, and result is listed in table 2.
Embodiment 10
In tank reactor, under oxygen atmosphere (being the atmosphere that formed of oxygen of 99% by purity), using dimethyl thioether and Virahol and the former powder contact reacts of titanium-silicon molecular sieve TS-1 as catalyzer, wherein, the mol ratio of dimethyl thioether and Virahol is 1:5, and the weight ratio of dimethyl thioether and catalyzer is 5:1, and temperature is 90 DEG C, pressure is 2.0MPa (gauge pressure), and oxygen partial pressure is 1.0MPa.
React after 1 hour, the mixture obtained is filtered, the liquid mixture that collection obtains also is analyzed by gas-chromatography, thus obtains dimethyl thioether transformation efficiency, iso-propanol conversion rate, dimethyl sulfoxide (DMSO) selectivity and acetone selectivity, and result is listed in table 2.
Table 2
Embodiment 11
By shaping titanium-silicon molecular sieve TS-1, (volume average particle size is 150 μm, with the total amount of shaping titanium-silicon molecular sieve TS-1 for benchmark, the content of titanium-silicon molecular sieve TS-1 is 75 % by weight, the content of silicon oxide is 25 % by weight) be seated in miniature isometrical fixed-bed reactor, form beds.Dimethyl thioether, Virahol and ammoniacal liquor (concentration is 30 % by weight) are sent into reactor and titanium-silicon molecular sieve TS-1 contact reacts from the opening for feed being arranged in reactor bottom, in reaction process, continue to pass in reactor oxygen-containing gas (for purity be 99% oxygen and purity be the gas mixture of the nitrogen of 99%, wherein, the volume ratio of oxygen and nitrogen is 0.25:1).Wherein, the mol ratio of dimethyl thioether and Virahol is 1:5, and the weight space velocity of dimethyl thioether is 2h
-1, the pH value of the liquid mixture formed by dimethyl thioether and Virahol is adjusted to 7.5 by 6.9 by the consumption of ammoniacal liquor.Temperature in beds is 50 DEG C, and the pressure in reactor is 0.5MPa (gauge pressure), and oxygen partial pressure is 0.1MPa.
In operational process, the liquid mixture that reactor exports is carried out to gas chromatographic analysis and calculates dimethyl thioether transformation efficiency, iso-propanol conversion rate, dimethyl sulfoxide (DMSO) selectivity and acetone selectivity, result is listed in table 3.
Embodiment 12
The method identical with embodiment 11 is adopted to be oxidized by dimethyl thioether, unlike, with etc. the shaping hollow HTS of quality (volume average particle size is 150 μm, with the total amount of shaping hollow HTS for benchmark, the content of hollow HTS is 75 % by weight, and the content of silicon oxide is 25 % by weight) replace shaping titanium-silicon molecular sieve TS-1.
In operational process, the liquid mixture that reactor exports is carried out to gas chromatographic analysis and calculates dimethyl thioether transformation efficiency, iso-propanol conversion rate, dimethyl sulfoxide (DMSO) selectivity and acetone selectivity, result is listed in table 3.
Embodiment 13
The method identical with embodiment 11 is adopted to be oxidized by dimethyl thioether, unlike, under the condition that the total filling amount of catalyzer is constant in the reactor, first load shaping hollow HTS (identical with embodiment 12) in the reactor, recharge shaping titanium-silicon molecular sieve TS-1 (identical with embodiment 11), make dimethyl thioether and the Virahol bed first by being formed by shaping hollow HTS, then the bed by being formed by shaping titanium-silicon molecular sieve TS-1.Wherein, the weight ratio of shaping hollow HTS and shaping titanium-silicon molecular sieve TS-1 is 1:1.
In operational process, the liquid mixture that reactor exports is carried out to gas chromatographic analysis and calculates dimethyl thioether transformation efficiency, iso-propanol conversion rate, dimethyl sulfoxide (DMSO) selectivity and acetone selectivity, result is listed in table 3.
Embodiment 14
The method identical with embodiment 13 is adopted to be oxidized by dimethyl thioether, unlike, under the condition that the total filling amount of catalyzer is constant in the reactor, the weight ratio of shaping hollow HTS and shaping titanium-silicon molecular sieve TS-1 is 5:1.
In operational process, the liquid mixture that reactor exports is carried out to gas chromatographic analysis and calculates dimethyl thioether transformation efficiency, iso-propanol conversion rate, dimethyl sulfoxide (DMSO) selectivity and acetone selectivity, result is listed in table 3.
Embodiment 15
The method identical with embodiment 13 is adopted to be oxidized by dimethyl thioether, unlike, do not use ammoniacal liquor, the pH value of the mixture formed by dimethyl thioether and Virahol is 6.9.
In operational process, the liquid mixture that reactor exports is carried out to gas chromatographic analysis and calculates dimethyl thioether transformation efficiency, iso-propanol conversion rate, dimethyl sulfoxide (DMSO) selectivity and acetone selectivity, result is listed in table 3.
Embodiment 16
The method identical with embodiment 14 is adopted to be oxidized by dimethyl thioether, unlike, the opening for feed also by being arranged in reactor bottom sends into tertbutyl peroxide to reactor, and wherein, the mol ratio of tertbutyl peroxide and dimethyl thioether is 0.02:1.
In operational process, the liquid mixture that reactor exports is carried out to gas chromatographic analysis and calculates dimethyl thioether transformation efficiency, iso-propanol conversion rate, dimethyl sulfoxide (DMSO) selectivity and acetone selectivity, result is listed in table 3.
Embodiment 17
The method identical with embodiment 11 is adopted to be oxidized by dimethyl thioether, unlike, the catalyzer loaded in the reactor is draw off agent through what regenerate, the titanium-silicon molecular sieve TS-1 drawn off from cyclohexanone oxamidinating reaction process (being formed by the fresh shaping titanium-silicon molecular sieve TS-1 identical with embodiment 11) is carried out regenerating obtaining, wherein, regeneration condition is: at 550 DEG C in air atmosphere roasting 4h.The activity drawing off agent through regeneration is 45%, and its activity when fresh is 95%.
In operational process, the liquid mixture that reactor exports is carried out to gas chromatographic analysis and calculates dimethyl thioether transformation efficiency, iso-propanol conversion rate, dimethyl sulfoxide (DMSO) selectivity and acetone selectivity, result is listed in table 3.
Embodiment 18
The catalyzer used in the present embodiment is for drawing off agent through what regenerate, the hollow HTS drawn off from propylene ring oxidation reaction process (being formed by the fresh shaping hollow HTS identical with embodiment 12) is carried out regenerating obtaining, wherein, regeneration condition is: at 570 DEG C in air atmosphere roasting 4h.The activity drawing off agent through regeneration is 30%, and its activity when fresh is 96%.
The agent that draws off through regeneration is seated in micro fixed-bed reactor, forms beds.Dimethyl thioether and Virahol are sent into reactor and beds contact reacts from the opening for feed being arranged in reactor bottom, in reaction process, continue to pass in reactor oxygen-containing gas (for purity be 99% oxygen and purity be the gas mixture of the nitrogen of 99%, wherein, the volume ratio of oxygen and nitrogen is 1:1).Wherein, the mol ratio of dimethyl thioether and Virahol is 1:5, and the weight space velocity of dimethyl thioether is 10h
-1, the temperature in beds is 80 DEG C, and the pressure in reactor is 3.0MPa (gauge pressure), and oxygen partial pressure is 1.5MPa.
In operational process, the liquid mixture that reactor exports is carried out to gas chromatographic analysis and calculates dimethyl thioether transformation efficiency, iso-propanol conversion rate, dimethyl sulfoxide (DMSO) selectivity and acetone selectivity, result is listed in table 3.
Embodiment 19
The catalyzer used in the present embodiment is for drawing off agent through what regenerate, that (its volume average particle size is 250 μm by the titanium-silicon molecular sieve TS-1 drawn off from phenol hydroxylation reaction process, in fresh titanium silicalite TS-1, the content of titanium-silicon molecular sieve TS-1 is 80 % by weight, the content of silicon oxide is 20 % by weight) carry out regenerating obtaining, wherein, regeneration condition is: at 570 DEG C in air atmosphere roasting 4h.The activity drawing off agent through regeneration is 75%, and its activity when fresh is 96%.
The agent that draws off through regeneration is seated in micro fixed-bed reactor, forms beds.Dimethyl thioether, Virahol and pyridine are sent into reactor and beds contact reacts from the opening for feed being arranged in reactor bottom, in reaction process, continue to pass in reactor oxygen-containing gas (for purity be 99% oxygen and purity be the gas mixture of the nitrogen of 99%, wherein, the volume ratio of oxygen and nitrogen is 0.2:1).Wherein, the mol ratio of dimethyl thioether and Virahol is 1:4, and the pH value of the liquid mixture formed by dimethyl thioether and Virahol is adjusted to 8.5 by 6.8 by the consumption of pyridine, and the weight space velocity of dimethyl thioether is 20h
-1, the temperature in beds is 90 DEG C, and the pressure in reactor is 2.4MPa (gauge pressure), and oxygen partial pressure is 1.2MPa.
In operational process, the liquid mixture that reactor exports is carried out to gas chromatographic analysis and calculates dimethyl thioether transformation efficiency, iso-propanol conversion rate, dimethyl sulfoxide (DMSO) selectivity and acetone selectivity, result is listed in table 3.
Embodiment 20
The method identical with embodiment 19 is adopted to be oxidized by dimethyl thioether, unlike, the activity drawing off agent through regeneration is 35%.In operational process, the liquid mixture that reactor exports is carried out to gas chromatographic analysis and calculates dimethyl thioether transformation efficiency, iso-propanol conversion rate, dimethyl sulfoxide (DMSO) selectivity and acetone selectivity, result is listed in table 3.
Embodiment 21
Adopt the method cacodyl oxide base thioether identical with embodiment 14, unlike, adopt miniature reducing fixed-bed reactor, wherein, the internal diameter loading the beds of shaping hollow HTS is 2:1 with the ratio of the internal diameter of the beds of the shaping titanium-silicon molecular sieve TS-1 of filling, and the internal diameter loading the beds of shaping titanium-silicon molecular sieve TS-1 is identical with embodiment 14.
In operational process, the liquid mixture that reactor exports is carried out to gas chromatographic analysis and calculates dimethyl thioether transformation efficiency, iso-propanol conversion rate, dimethyl sulfoxide (DMSO) selectivity and acetone selectivity, result is listed in table 3.
Embodiment 22
Adopt the method cacodyl oxide base thioether identical with embodiment 14, unlike, adopt miniature reducing fixed-bed reactor, wherein, the internal diameter loading the beds of shaping hollow HTS is 1:2 with the ratio of the internal diameter of the beds of the shaping titanium-silicon molecular sieve TS-1 of filling, and the internal diameter loading the beds of shaping titanium-silicon molecular sieve TS-1 is identical with embodiment 14.
In operational process, the liquid mixture that reactor exports is carried out to gas chromatographic analysis and calculates dimethyl thioether transformation efficiency, iso-propanol conversion rate, dimethyl sulfoxide (DMSO) selectivity and acetone selectivity, result is listed in table 3.
Embodiment 23
Adopt the method cacodyl oxide base thioether identical with embodiment 14, unlike, adopt miniature reducing fixed-bed reactor, wherein, the internal diameter loading the beds of shaping hollow HTS is 5:1 with the ratio of the internal diameter of the beds of the shaping titanium-silicon molecular sieve TS-1 of filling, and the internal diameter loading the beds of shaping titanium-silicon molecular sieve TS-1 is identical with embodiment 14.
In operational process, the liquid mixture that reactor exports is carried out to gas chromatographic analysis and calculates dimethyl thioether transformation efficiency, iso-propanol conversion rate, dimethyl sulfoxide (DMSO) selectivity and acetone selectivity, result is listed in table 3.
Table 3
Embodiment 13 and 14 and embodiment 11 and 12 are compared and can find out, by hollow HTS and titanium-silicon molecular sieve TS-1 layering are loaded in the reactor, make dimethyl thioether and Virahol successively and hollow HTS and hollow titanium-silicon molecular sieve TS-1 contact reacts, higher selectivity of product can be obtained, simultaneously the work-ing life of extending catalyst effectively.
Embodiment 14 is compared can find out with embodiment 21-23, hollow HTS and titanium-silicon molecular sieve TS-1 layering are being seated in reactor, and when hollow HTS is positioned at the upstream of titanium-silicon molecular sieve TS-1, the superfacial velocity that reaction solution flows through hollow HTS is made to be less than the superfacial velocity flowing through titanium-silicon molecular sieve TS-1, can work-ing life of extending catalyst further.
The result of embodiment 17-20 confirms, even if method of the present invention be used in other reaction active obviously reduced draw off agent as catalyzer through what regenerate, also high dimethyl thioether transformation efficiency and dimethyl sulfoxide (DMSO) selectivity can be obtained, simultaneously in long-time continuous reaction process, catalyzer demonstrates good activity stability.
Claims (13)
1. a method for production dimethyl sulfoxide (DMSO) simultaneously and acetone, the method comprises in the presence of oxygen, is contacted by dimethyl thioether with Virahol with HTS, obtains the mixture containing dimethyl sulfoxide (DMSO) and acetone.
2. method according to claim 1, wherein, the mol ratio of dimethyl thioether and Virahol is 1:1-10.
3. method according to claim 1 and 2, wherein, described contact is carried out under the existence of at least one superoxide, and the mol ratio of described superoxide and dimethyl thioether is 0.0001-0.1:1, is preferably 0.0005-0.05:1.
4. method according to claim 1, wherein, described HTS is the HTS with MFI structure.
5. method according to claim 4, wherein, at least part of described HTS is hollow HTS, and the crystal grain of described hollow 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.
6. method according to claim 5, wherein, described contact is carried out in fixed-bed reactor, be filled with hollow HTS and titanium-silicon molecular sieve TS-1 in described fixed-bed reactor, hollow HTS and the filling order of titanium-silicon molecular sieve TS-1 make successively to contact with described titanium-silicon molecular sieve TS-1 with described hollow HTS with the liquid mixture of Virahol containing dimethyl thioether.
7. method according to claim 6, wherein, the mass ratio of described hollow HTS and described titanium-silicon molecular sieve TS-1 is 1-10:1.
8. the method according to claim 6 or 7, wherein, the superfacial velocity that described liquid mixture flows through described hollow HTS is v
1, the superfacial velocity flowing through described titanium-silicon molecular sieve TS-1 is v
2, v
1< v
2; Preferably, v
2/ v
1=1.5-10.
9. according to the method in claim 1 and 4-8 described in any one, wherein, at least part of described HTS be through regeneration the reaction unit using HTS as catalyzer draw off agent, 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.
10. according to the method in claim 1-9 described in any one, wherein, the method also comprises adds at least one alkaline matter in the mixture contacted with described HTS, and the addition of described alkaline matter makes the pH value of this mixture be 7-9.
11. methods according to claim 1, wherein, the weight ratio of dimethyl thioether and HTS is 0.01-100:1; Or the weight space velocity of dimethyl thioether is 0.1-100h
-1.
12. methods according to claim 1, wherein, the condition of described contact makes the transformation efficiency of Virahol be 10-25 % by weight.
13. according to claim 1,2, method in 4-7,11 and 12 described in any one, wherein, the condition of described contact comprises: temperature is 40-160 DEG C, and in gauge pressure, pressure is 0.01-5MPa, and oxygen partial pressure is 0.01-5MPa.
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| CN106631935A (en) * | 2015-10-29 | 2017-05-10 | 中国石油化工股份有限公司 | Method for simultaneous production of dimethyl sulfone and acetone |
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