CN105837477B - A kind of preparation method of dimethyl sulfone - Google Patents
A kind of preparation method of dimethyl sulfone Download PDFInfo
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- CN105837477B CN105837477B CN201610420985.2A CN201610420985A CN105837477B CN 105837477 B CN105837477 B CN 105837477B CN 201610420985 A CN201610420985 A CN 201610420985A CN 105837477 B CN105837477 B CN 105837477B
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- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 150
- 239000003054 catalyst Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 239000000376 reactant Substances 0.000 claims abstract description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 92
- 238000006243 chemical reaction Methods 0.000 claims description 61
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 33
- 230000035484 reaction time Effects 0.000 claims description 12
- 239000004615 ingredient Substances 0.000 claims description 11
- 150000003462 sulfoxides Chemical class 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical group C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 9
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- 230000003197 catalytic effect Effects 0.000 description 10
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 238000013019 agitation Methods 0.000 description 7
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 5
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- 150000003457 sulfones Chemical class 0.000 description 4
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- NOESYZHRGYRDHS-UHFFFAOYSA-N insulin Chemical compound N1C(=O)C(NC(=O)C(CCC(N)=O)NC(=O)C(CCC(O)=O)NC(=O)C(C(C)C)NC(=O)C(NC(=O)CN)C(C)CC)CSSCC(C(NC(CO)C(=O)NC(CC(C)C)C(=O)NC(CC=2C=CC(O)=CC=2)C(=O)NC(CCC(N)=O)C(=O)NC(CC(C)C)C(=O)NC(CCC(O)=O)C(=O)NC(CC(N)=O)C(=O)NC(CC=2C=CC(O)=CC=2)C(=O)NC(CSSCC(NC(=O)C(C(C)C)NC(=O)C(CC(C)C)NC(=O)C(CC=2C=CC(O)=CC=2)NC(=O)C(CC(C)C)NC(=O)C(C)NC(=O)C(CCC(O)=O)NC(=O)C(C(C)C)NC(=O)C(CC(C)C)NC(=O)C(CC=2NC=NC=2)NC(=O)C(CO)NC(=O)CNC2=O)C(=O)NCC(=O)NC(CCC(O)=O)C(=O)NC(CCCNC(N)=N)C(=O)NCC(=O)NC(CC=3C=CC=CC=3)C(=O)NC(CC=3C=CC=CC=3)C(=O)NC(CC=3C=CC(O)=CC=3)C(=O)NC(C(C)O)C(=O)N3C(CCC3)C(=O)NC(CCCCN)C(=O)NC(C)C(O)=O)C(=O)NC(CC(N)=O)C(O)=O)=O)NC(=O)C(C(C)CC)NC(=O)C(CO)NC(=O)C(C(C)O)NC(=O)C1CSSCC2NC(=O)C(CC(C)C)NC(=O)C(NC(=O)C(CCC(N)=O)NC(=O)C(CC(N)=O)NC(=O)C(NC(=O)C(N)CC=1C=CC=CC=1)C(C)C)CC1=CN=CN1 NOESYZHRGYRDHS-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- 102000004877 Insulin Human genes 0.000 description 1
- 108090001061 Insulin Proteins 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229930003270 Vitamin B Natural products 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229960002685 biotin Drugs 0.000 description 1
- 235000020958 biotin Nutrition 0.000 description 1
- 239000011616 biotin Substances 0.000 description 1
- 230000023852 carbohydrate metabolic process Effects 0.000 description 1
- 235000021256 carbohydrate metabolism Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 239000002808 molecular sieve Substances 0.000 description 1
- 230000000926 neurological effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 238000004904 shortening Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
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- 235000019156 vitamin B Nutrition 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/06—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to chemical technology field, a kind of preparation method of dimethyl sulfone, including oxidation reaction process are specifically disclosed, the oxidation reaction is：Using dimethyl sulfoxide (DMSO) as reactant, the oxidation generation dimethyl sulfone in the presence of oxidant and catalyst, the catalyst is 2,6 naphthalenedicarboxylic acids.The present invention is by using 2,6 naphthalenedicarboxylic acids aoxidize the catalyst for generating dimethyl sulfone as dimethyl sulfoxide (DMSO), greatly accelerating only needs simple process for refining to can reach the high purity dimethyl sulfone product that purity is more than 99% in the reaction speed of the oxidation reaction, last handling process.The present invention may be such that the energy consumption of dimethyl sulfone is reduced using new catalyst, and the production cycle shortens, and production efficiency is improved, economic benefit increase.
Description
Technical field
The invention belongs to chemical technology field, and in particular to a kind of preparation method of dimethyl sulfone.
Background technology
Dimethyl sulfone is as a kind of organic sulfur compound, and the ability with generation insulin in enhancing human body is simultaneously to carbohydrate
Metabolism plays a driving role, and is the necessary material of human collagen albumen synthesis.Dimethyl sulfone can promote wound healing, also can be to new old
Vitamin B, vitamin C, the synthesis of biotin and activation needed for metabolism and neurological health are worked, and are referred to as " naturally beautifying
Carbonizable substance ".
The industrial production of country's dimethyl sulfone is mainly obtained by dimethyl sulfoxide (DMSO) through nitric acid oxidation at present, and this method is present
Reaction temperature height, high energy consumption, technological process length, the problems such as accessory substance is more, while environmental pollution is more serious.In the prior art,
Patent CN 1150164C disclose the preparation method of dimethyl sulfone, and this method includes oxidation reaction, and cooling is separated out, and is filtered, and is taken off
Water, the step such as drying, wherein, oxidation reaction is dimethyl sulfoxide (DMSO) and hydrogen peroxide reaction generation dimethyl sulfone, dimethyl sulfoxide (DMSO) with
The effective ingredient weight ratio of hydrogen peroxide is 1:0.44~0.65, reaction temperature is 80~150 DEG C, 4~40 hours reaction time.Should
Oxidation reaction does not use catalyst in method, although decreased compared to nitrate method reaction temperature, but temperature is still higher,
Reaction time is long.Patent public affairs CN 103288692 B have opened a kind of method that dimethyl sulfone is prepared by dimethyl sulfoxide (DMSO), the party
It is oxidant that method, which is dimethyl sulfoxide (DMSO) in ozone, and HTS is to be oxidized to product dimethyl sulfone under conditions of catalyst, its
Reaction temperature is 40-100 DEG C, and pressure is 0.1-3MPa, and the reaction time is 0.1-10 hours.Its reaction temperature and reaction time model
Enclose value larger, from its specification, its preferred reaction temperature is still higher, and the reaction time is preferably 1~5 hour, still
It is partially long.
In summary, need a kind of new method of exploitation badly or improve existing method progress and prepare dimethyl sulfone so that prepare
Method is simple, accelerates reaction speed, while reducing reaction temperature to a certain extent, reduces energy consumption, shortens the production cycle, improves life
Efficiency is produced, increases economic benefit.
The content of the invention
The purpose of the present invention is a kind of dimethyl sulfone preparation method that reaction speed is fast, reaction temperature is relatively low of exploitation.
Above-mentioned purpose is to be achieved through the following technical solutions：A kind of preparation method of dimethyl sulfone, including oxidation reaction mistake
Journey, the oxidation reaction is：Using dimethyl sulfoxide (DMSO) as reactant, the oxidation generation dimethyl in the presence of oxidant and catalyst
Sulfone, the catalyst is NDA.The present invention is aoxidized as dimethyl sulfoxide (DMSO) by using 2,6- naphthalenedicarboxylic acids and generated
The catalyst of dimethyl sulfone, greatly accelerates the reaction speed of the oxidation reaction, under relatively lower temp (40~60 DEG C), instead
It should only need the short period (20~30min) that the high conversion rate of dimethyl sulfoxide (DMSO) can be made up to 95% or so, therefore crude product dimethyl
The purity of sulfone is of a relatively high, only needs simple process for refining to can reach the high-purity two that purity is more than 99% in last handling process
Methyl sulfone product.The present invention may be such that the energy consumption of dimethyl sulfone is reduced using new catalyst, and the production cycle shortens, raw
Produce efficiency to improve, economic benefit increase.And research show, under relatively lower temp (40~60 DEG C), this catalyst have compared with
High activity, therefore reduction temperature can't slow down the reaction rate of this reaction and the conversion ratio of dimethyl sulfoxide (DMSO).
Characterized through research, it is oxidation generation two that NDA is applied to dimethyl sulfoxide (DMSO) in the present invention as catalyst
During methyl sulfone, catalytic reaction is carried out on the sour positions of B of NDA, i.e., NDA is in theory
It is used as a kind of solid acid catalyst, its sour position of i.e. B of avtive spot for playing catalytic action.Experimental study shows, solid acid catalyst
Acid amount on surface has obvious relation with its catalytic activity and selectivity, and the acid of NDA catalyst of the present invention is strong
Degree is more suitable, shows higher catalytic activity for it and provides possibility.In addition, solid NDA itself is porous
Structure, even aperture distribution, specific surface area is larger, is a kind of preferable carrier, can as the avtive spot of its own carrier.
Therefore the making of this catalyst is simple, without preparing synthesis in addition.
Preferably, further technical scheme is：The oxidant is hydrogen peroxide or ozone.Using containing ozone or mistake
Hydrogen oxide has higher selectivity as oxidant for the oxidation of dimethyl sulfone, and ozone can voluntarily divide at normal temperatures
Solve as oxygen, decomposing hydrogen dioxide solution is oxygen and water, will not produce accessory substance and harmful substance, product odorless can enter one
Step reduction separation costs, and its operating condition is gentle, and serious corrosion will not be produced to equipment.Therefore, according to the inventive method
It is environment-friendly.
Further technical scheme is：The concentration of the hydrogen peroxide is 25%~45%.The concentration of hydrogen peroxide should not mistake
Greatly, it is to avoid oxidation reaction excessively acutely causes local temperature too high, and then the generation of accessory substance is caused, or even influence catalyst
Activity and service life.
Further technical scheme is：The concentration of the hydrogen peroxide is 30%~40%.It is demonstrated experimentally that hydrogen peroxide is dense
Degree reacts more gentle, the conversion ratio of raw material, the effective rate of utilization of hydrogen peroxide, product yield in the range of 30%~40%
It is all of a relatively high.
It is preferred that, the pH value of hydrogen peroxide is controlled 3~6, and research shows, under the conditions of this, hence it is evident that improved for dimethyl sulfone
Selectivity, while higher dimethyl sulfoxide (DMSO) conversion ratio and oxidant effective rate of utilization can also be obtained.On the one hand, in acid bar
Under part, hydrogen peroxide is relatively stablized, on the other hand, under the conditions of this pH, good acid environment is provided for NDA, is conducive to
Improve its catalytic activity.
Further technical scheme is：The effective ingredient weight ratio of dimethyl sulfoxide (DMSO) and hydrogen peroxide is 1:0.4~0.7.
Under the conditions of this, oxidant effective rate of utilization is higher.
Further technical scheme is：The effective ingredient weight ratio of dimethyl sulfoxide (DMSO) and hydrogen peroxide is 1:0.55.
Further technical scheme is：The mass percent of the 2,6- naphthalenedicarboxylic acids and dimethyl sulfoxide (DMSO) be 2%~
10%.Show through experimental study, service efficiency of catalyst is higher under the conditions of this.
Further technical scheme is：The particle diameter of the NDA is 1.2~1.8mm, and porosity is more than
25%, specific surface area is more than 260m2/g.Under the conditions of this, the better catalytic activity of NDA, service life is longer, and
Easily-activated regeneration.
Further technical scheme is：The reaction temperature of the oxidation reaction be 40~60 DEG C, the reaction time be 20~
30min.The above-mentioned reaction temperature of selection and reaction time, are on the one hand due to have used NDA as catalyst,
So that only needing above-mentioned reaction temperature and reaction time just to reach the conversion ratio of preferable dimethyl sulfoxide (DMSO), it is possible to decrease energy consumption
And production cost, on the other hand at 40~60 DEG C, NDA has preferable catalytic activity.Reaction time herein
And reaction temperature is the preferably result obtained after test of many times, do not represent in other reaction time or reaction temperature
The present invention can not be realized in the range of degree or is reached using the technique effect reached after the present invention.
Further technical scheme is：Also include the subtractive process of dimethyl sulfone, the subtractive process includes cooling, knot
Brilliant, filtering and drying steps.Compared with the prior art, last handling process is simply easily operated, and reacted crude product is only by the present invention
Need to cool down, crystallize, filter and dry the high purity dimethyl sulfone product that can reach that purity is more than 99%.
In summary, NDA catalyst aoxidizes the reaction for generating dimethyl sulfone to dimethyl sulfoxide (DMSO) in the present invention
Higher selectivity is shown, compared with prior art, on the premise of reaction temperature is reduced, the reaction time still can larger journey
The shortening of degree, energy consumption reduction, the production cycle shortens, and production efficiency is improved；Secondly, reacted crude product dimethyl sulfone
Purity is of a relatively high, therefore aftertreatment technology is simple.Again, the source of catalyst and preparation are simple, and catalyst service life
It is longer.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, to help more fully understanding the present invention, but this hair
Bright protection domain is not limited in these embodiments.
Embodiment 1
The effective ingredient weight ratio of dimethyl sulfoxide (DMSO) and hydrogen peroxide is 1:0.55, catalyst NDA and dimethyl
The mass percent of sulfoxide is 5%, and the concentration of hydrogen peroxide is 35%, and the pH value for controlling hydrogen peroxide is 4；The grain of 2,6- naphthalenedicarboxylic acids
Footpath is 1.5mm, porosity 31%, specific surface area 305m2/g.First catalyst NDA is added in reactor, so
After add DMSO, add hydrogen peroxide under agitation, controlling reaction temperature is 50 DEG C, closed synthesis under normal pressure 30min, through cold
But the conversion ratio of dimethyl sulfone product, wherein dimethyl sulfoxide (DMSO) that purity is 99.83% is can obtain after, crystallizing, filter and drying
For 96.7%, dimethyl sulfone is selectively 99.6%.
Embodiment 2
The effective ingredient weight ratio of dimethyl sulfoxide (DMSO) and hydrogen peroxide is 1:0.7, catalyst NDA and dimethyl
The mass percent of sulfoxide is 10%, and the concentration of hydrogen peroxide is 25%.The pH value for controlling hydrogen peroxide is 6；2,6- naphthalenedicarboxylic acids
Particle diameter is 1.2~1.8mm, and porosity is more than 25%, and specific surface area is more than 260m2/g.First catalyst 2,6- naphthalenedicarboxylic acids are added
Enter into reactor, then add DMSO, hydrogen peroxide is added under agitation, controlling reaction temperature is 40 DEG C, closed normal
Pressure reaction 20min, can obtain the dimethyl sulfone product that purity is 99.51%, wherein two after cooling down, crystallizing, filter and dry
The conversion ratio of methyl sulfoxide is 95.1%, and dimethyl sulfone is selectively 98.6%.
Embodiment 3
The effective ingredient weight ratio of dimethyl sulfoxide (DMSO) and hydrogen peroxide is 1:0.4, catalyst NDA and dimethyl
The mass percent of sulfoxide is 2%, and the concentration of hydrogen peroxide is 45%.The pH value for controlling hydrogen peroxide is 3；The grain of 2,6- naphthalenedicarboxylic acids
Footpath is 1.2~1.8mm, and porosity is more than 25%, and specific surface area is more than 260m2/g.First catalyst 2,6- naphthalenedicarboxylic acids are added
Into reactor, DMSO is then added, hydrogen peroxide is added under agitation, controlling reaction temperature is 60 DEG C, closed normal pressure
25min is reacted, the dimethyl sulfone product that purity is 99.52%, wherein diformazan are can obtain after cooling down, crystallizing, filter and dry
The conversion ratio of base sulfoxide is 92.2%, and dimethyl sulfone is selectively 97.3%.
Embodiment 4
The effective ingredient weight ratio of dimethyl sulfoxide (DMSO) and hydrogen peroxide is 1:0.55, catalyst NDA and dimethyl
The mass percent of sulfoxide is 5%, and the concentration of hydrogen peroxide is 40%.The pH value for controlling hydrogen peroxide is 4；The grain of 2,6- naphthalenedicarboxylic acids
Footpath is 1.2~1.8mm, and porosity is more than 25%, and specific surface area is more than 260m2/g.First catalyst 2,6- naphthalenedicarboxylic acids are added
Into reactor, DMSO is then added, hydrogen peroxide is added under agitation, controlling reaction temperature is 50 DEG C, closed normal pressure
30min is reacted, the dimethyl sulfone product that purity is 99.55%, wherein diformazan are can obtain after cooling down, crystallizing, filter and dry
The conversion ratio of base sulfoxide is 97.1%, and dimethyl sulfone is selectively 99.1%.
Embodiment 5
The effective ingredient weight ratio of dimethyl sulfoxide (DMSO) and hydrogen peroxide is 1:0.6, catalyst NDA and dimethyl
The mass percent of sulfoxide is 5%, and the concentration of hydrogen peroxide is 30%.The pH value for controlling hydrogen peroxide is 5；The grain of 2,6- naphthalenedicarboxylic acids
Footpath is 1.2~1.8mm, and porosity is more than 25%, and specific surface area is more than 260m2/g.First catalyst 2,6- naphthalenedicarboxylic acids are added
Into reactor, DMSO is then added, hydrogen peroxide is added under agitation, controlling reaction temperature is 45 DEG C, closed normal pressure
20min is reacted, the dimethyl sulfone product that purity is 99.64%, wherein diformazan are can obtain after cooling down, crystallizing, filter and dry
The conversion ratio of base sulfoxide is 96.4%, and dimethyl sulfone is selectively 98.1%.
Embodiment 6
The effective ingredient weight ratio of dimethyl sulfoxide (DMSO) and hydrogen peroxide is 1:0.55, catalyst NDA and dimethyl
The mass percent of sulfoxide is 5%, and the concentration of hydrogen peroxide is 40%.The pH value for controlling hydrogen peroxide is 5；The grain of 2,6- naphthalenedicarboxylic acids
Footpath is 1.2~1.8mm, and porosity is more than 25%, and specific surface area is more than 260m2/g.First catalyst 2,6- naphthalenedicarboxylic acids are added
Into reactor, DMSO is then added, hydrogen peroxide is added under agitation, controlling reaction temperature is 40 DEG C, closed normal pressure
30min is reacted, the dimethyl sulfone product that purity is 99.50%, wherein diformazan are can obtain after cooling down, crystallizing, filter and dry
The conversion ratio of base sulfoxide is 96.2%, and dimethyl sulfone is selectively 99.2%.
Embodiment 7
The mol ratio of dimethyl sulfoxide (DMSO) and ozone is 1:1, the quality hundred of catalyst NDA and dimethyl sulfoxide (DMSO)
Divide than being 5%, the concentration of hydrogen peroxide is 30%.The pH value for controlling hydrogen peroxide is 5；The particle diameter of 2,6- naphthalenedicarboxylic acids be 1.2~
1.8mm, porosity is more than 25%, and specific surface area is more than 260m2/g.Catalyst 2,6- naphthalenedicarboxylic acids are first added to reactor
In, DMSO is then added, hydrogen peroxide is passed through under agitation, controlling reaction temperature is 45 DEG C, and seal-off pressure is 0.2MPa
This lower reaction 30min, can obtain the dimethyl sulfone product that purity is 99.64% after cooling down, crystallizing, filter and dry, wherein
The conversion ratio of dimethyl sulfoxide (DMSO) is 93.2%, and dimethyl sulfone is selectively 76.3%.
Comparative example 1
Except being not added with NDA catalyst, other be the same as Examples 1.The purity of dimethyl sulfone product after refined is only
91.35%, the wherein conversion ratio of dimethyl sulfoxide (DMSO) is 24.8%, and dimethyl sulfone is selectively 86.4%.
Comparative example 2
NDA catalyst is replaced with into titanium-silicon molecular sieve catalyst, other be the same as Examples 1.Diformazan after refined
The purity of base sulfone product is only 98.28%, and wherein the conversion ratio of dimethyl sulfoxide (DMSO) is 66.7%, and dimethyl sulfone is selectively
97.2%.
Pass through comparative example 1 and comparative example 1 and comparative example 2, it is known that, the present invention in use NDA as with
The catalyst of dimethyl sulfoxide (DMSO) oxidation generation dimethyl sulfone, under identical stoichiometry and reaction condition, dimethyl is sub-
The conversion ratio of sulfone and the selectivity of dimethyl sulfone are greatly improved, i.e. the purity of crude product dimethyl sulfone can be greatly
Increase, the refined dimethyl sulfone product that purity is more than 99% is can reach by the method for the identical purification condition present invention.Therefore
Compared with the prior art, energy consumption reduction, the production cycle shortens the present invention, and production efficiency is improved, and aftertreatment technology is simple in addition.
Experiment proves that, after NDA catalyst used in the present invention is recycled through 5 times, its catalytic efficiency
Still there are 95~98% used for the first time, through 10 recyclings, its catalytic efficiency still has 90% or so used for the first time.
The present invention can be applied to industrial production, a variety of reactors can be used, exemplified by this sentences fixed bed as reactor：It is first
NDA catalyst in being filled in first fixed bed, mixed liquor is mixed to form by DMSO and hydrogen peroxide in proportion,
Mixed liquor is continuously squeezed into the entrance of fixed bed, mixed liquor carries out anti-along catalyst bed laminar flow and in the presence of catalyst
Should, mixed liquor, along catalyst bed laminar flow, reaction solution is flowed continually out in fixed bed exit in fixed bed；By fixed bed go out
Outflow reaction solution, which is pumped in crystallizer, at mouthful carries out crystallization treatment, generates dimethyl sulfone crystal；By solidliquid mixture in
Liquid is separated with dimethyl sulfone crystal, obtains dimethyl sulfone crystal；Processing is dried in dimethyl sulfone crystal, obtains pure
Product dimethyl sulfone.
Fixed bed reactors, which are divided into, to be separated with porous plate between at least two reaction zones, each reaction zone and is provided with gap.
Because bed pressure drop is directly proportional to bed height, bed increases, and flow resistance just increases.It is so designed that, can prevents anti-in bed
The problem of answering liquid concentration and non-uniform temperature, effectively reduces bed pressure drop, and resistance is small；Between liquid-liquid interface and liquid-solid interface it
Between Surface Renewal it is fast, improve the conversion ratio and selectivity of reaction.In order to reduce bed pressure drop, beds are can control
Voidage, the voidage of preferred catalyst bed is 0.3~0.4.
The temperature for the reaction zone that the temperature for the reaction zone that mixed liquor is first flowed through is flowed through after being higher than.Because this oxidation reaction is to put
Thermal response, with the flowing of mixed liquor beds, temperature gradually height is to ensure that catalyst has preferably catalysis effect
Rate, mixed liquor is preheated so that reaction after the latter reaction zone of inflow of a reaction zone to the catalyst of latter reaction zone
Temperature stabilization is in preferably condition, it is to avoid too high and influence catalytic efficiency in fixed bed outlet section reacting liquid temperature, or even occurs
Temperature runaway phenomenon.The temperature of reaction zone of the temperature for the reaction zone that mixed liquor is first flowed through than being flowed through after mixed liquor is high 3~8 DEG C.Reaction
Area is settable 2~4, experiment proves that, catalytic efficiency of catalyst is higher under the conditions of this, and oxidation reaction is relatively stable, gentle.
Also filler can be filled with the reaction zone.It is so designed that, on the one hand advantageously reduces bed pressure drop, the opposing party
Face dilute catalyst, it is to avoid temperature runaway.The filler and the catalyst in the form of the mixture of the two in loading described anti-
Answer beds and loaded in the reaction region by the packing layer interval that filler is formed that Qu Zhonghuo is formed by catalyst.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention
Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of dimethyl sulfone, including oxidation reaction process, it is characterised in that the oxidation reaction is：With two
Methyl sulfoxide is reactant, the oxidation generation dimethyl sulfone in the presence of oxidant and catalyst, and the catalyst is 2,6- naphthalenes
Dioctyl phthalate.
2. the preparation method of dimethyl sulfone according to claim 1, it is characterised in that the oxidant is hydrogen peroxide or smelly
Oxygen.
3. the preparation method of dimethyl sulfone according to claim 2, it is characterised in that the concentration of the hydrogen peroxide is 25%
~45%.
4. the preparation method of dimethyl sulfone according to claim 3, it is characterised in that the concentration of the hydrogen peroxide is 30%
~40%.
5. the preparation method of dimethyl sulfone according to claim 4, it is characterised in that dimethyl sulfoxide (DMSO) and hydrogen peroxide have
It is 1 to imitate Ingredient Wt ratio:0.4~0.7.
6. the preparation method of dimethyl sulfone according to claim 5, it is characterised in that dimethyl sulfoxide (DMSO) and hydrogen peroxide have
It is 1 to imitate Ingredient Wt ratio:0.55.
7. the preparation method of dimethyl sulfone according to claim 6, it is characterised in that the NDA and diformazan
The mass percent of base sulfoxide is 2%~10%.
8. the preparation method of dimethyl sulfone according to claim 7, it is characterised in that the particle diameter of the NDA
For 1.2~1.8mm, porosity is more than 25%, and specific surface area is more than 260m2/g。
9. the preparation method of the dimethyl sulfone according to claim 1~8 any one, it is characterised in that the oxidation is anti-
The reaction temperature answered is 40~60 DEG C, and the reaction time is 20~30min.
10. the preparation method of dimethyl sulfone according to claim 9, it is characterised in that refined also including dimethyl sulfone
Process, the subtractive process includes cooling, crystallization, filtering and drying steps.
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