CN109734722A - A kind of method that sorb dehydration of alcohols prepares isobide - Google Patents
A kind of method that sorb dehydration of alcohols prepares isobide Download PDFInfo
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- CN109734722A CN109734722A CN201910054258.2A CN201910054258A CN109734722A CN 109734722 A CN109734722 A CN 109734722A CN 201910054258 A CN201910054258 A CN 201910054258A CN 109734722 A CN109734722 A CN 109734722A
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- isobide
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Abstract
The invention discloses a kind of methods that sorb dehydration of alcohols prepares isobide, and using the carbon-based solid acid of benzene sulfonic acid group functional modification as catalyst, sorbierite is raw material, in a heated condition, prepare isobide by dehydration.Sorb alcohol conversion 100% of the invention, isobide yield is up to 83%.This method production process is simple, and environmental pollution is small, and it is a kind of method with industrial applications prospect that catalyst effect is good and easily separated reuse.
Description
Technical field
The invention belongs to technical field of fine, and in particular to a kind of method that sorbierite prepares isobide.
Background technique
Isobide is widely used in the fields such as food, medicine and polymer plastic.Isobide usually with liquid acid (such as
H2SO4Deng) be that catalyst is obtained by sorb dehydration of alcohols, but in process of production, strong liquid acid catalyst not only corrode equipment,
Pollution environment with product is difficult to separate, but also there are side reactions drawbacks such as more, products therefrom color depth.Patent US6407266
A kind of isobide production method is disclosed, using the concentrated sulfuric acid as catalyst, 70% sorbitol solution is raw material, different in products therefrom
Sorbitol concentration only has 75% or so, and the subsequent separating step for also needing to remove the complexity such as aqueous solvent.
Solid acid catalyst is environmentally protective, overcomes the defect of liquid acid catalyst.But it is existing to be used for sorb dehydration of alcohols
The solid acid catalyst for preparing isobide, there are reaction temperature higher (200 DEG C or more), isobide yield it is relatively low (<
75%) the problems such as, catalyst is expensive, thermal stability is poor.
Patent CN101691376A discloses a kind of using solid-carrying heteropolyacid as the method for catalyst preparation isobide, the party
For method under the conditions of 250 DEG C, isobide yield is 71.4%.In patent CN101492457A, with H3PO4Modified tetravalent metal
Oxide is catalyst, and at 300 DEG C of reaction temperature, the yield of isobide is 62.23%.In CN108690039A, with
WO3/ZrO2Or MoO3/ZrO2For catalyst, it is up to 8h in 170 DEG C of reactions, obtains 72% isobide yield.It is existing solid
The catalytic condition of body acid catalyst is harsh, and the yield of isobide is low.
Summary of the invention
It is an object of the invention to: above-mentioned deficiency in the prior art is solved, a kind of sorb dehydration of alcohols is provided and prepares different mountain
The method of pears alcohol.This method reaction process is simple, and catalyst is small to equipment corrosion, and isobide yield is up to 83%.
To achieve the goals above, the technical solution adopted by the present invention are as follows: a kind of sorb dehydration of alcohols prepares isobide
Method, using the carbon-based solid acid of benzene sulfonic acid group functional modification as catalyst, sorbierite is raw material, in a heated condition, is led to
It crosses dehydration and prepares isobide.
The temperature of the dehydration is 120-250 DEG C, reaction time 0.5-10h, reaction pressure 5-
101.325kPa.More preferably, reaction temperature is 140-200 DEG C, reaction pressure 30-60kPa.Reaction time is 0.5-10h,
More preferably, reaction time 1-3h；
More preferably, the quality of the carbon-based solid acid is the 0.2-30% of sorbierite quality.More preferably, carbon-based solid
The quality of acid is the 1-10% of sorbierite.The amount of carbon-based solid acid catalyst is less, influences whether the rate and product of reaction
Yield will cause the waste of catalyst, therefore in the present invention, by the use of catalyst and when the dosage of catalyst is more
Amount control is in 0.2-30%, more preferably, reduces catalyst under the premise of guaranteeing good catalytic efficiency for 1-10%
Dosage saves production cost.
Further, the preparation method of the carbon-based solid acid of the benzene sulfonic acid group functional modification is, by carbon-based material,
P-aminobenzene sulfonic acid and inorganic base are dissolved in the water, and stir in 0-100 DEG C, add diazo reagent and inorganic acid, be stirred to react,
It is filtered, washed, dried.
In the present invention, first carbon-based material and p-aminobenzene sulfonic acid and inorganic base are dissolved in water, then into system
Diazo reagent is added, under the action of inorganic acid, by diazotising and arylation reaction, functionalization grafting is carried out to carbon-based material
Benzene sulfonic acid group.The high catalytic efficiency of the carbon-based solid acid of functionalization, reaction condition are mild.
The carbon-based material is microporous carbon or mesoporous carbon.Wood activated charcoal of the microporous carbon finger-hole diameter less than 2nm, coconut husk are living
Property charcoal, mineral active charcoal etc., the aperture of mesoporous carbon is in 2-50nm.The inorganic base is sodium hydroxide, potassium hydroxide, hydroxide
One of lithium or calcium hydroxide.The inorganic acid is one of hydrochloric acid, sulfuric acid, nitric acid.The diazo reagent is nitrous
Acid compound, predominantly sodium nitrite or isoamyl nitrite, the mass ratio of the p-aminobenzene sulfonic acid and the diazo reagent
For 1:0.5-5.The mass ratio of the p-aminobenzene sulfonic acid and the carbon-based material is 1-10:1.
In the present invention, catalyst is the carbon-based solid acid of benzene sulfonic acid group functional modification, and high catalytic efficiency reacts item
Part is mild, and is not necessarily to carry out the separating step of removing aqueous solvent after the reaction, environmentally protective, and the thermostabilization of the catalyst
Property it is good, it is reusable, have certain economy and practicability.
Carbon-based solid acid of the invention is to pass through diazotising using carbon-based material, p-aminobenzene sulfonic acid, diazo reagent as raw material
And arylation reaction, benzene sulfonic acid group and carbon material are grafted, the carbon-based solid acid of benzene sulfonic acid group functional modification is formed.It is more
Hole carbon material utilizes the grafting of benzene sulfonic acid group, and the benzene sulfonic acid group of grafting is more, and the density in sour site is bigger, to improve solid
The catalytic efficiency of body catalyst.
By adopting the above-described technical solution, the beneficial effects of the present invention are:
(1) in preparation method of the invention, the carbon-based solid acid catalyst of used benzene sulfonic acid group functional modification
High catalytic efficiency, reaction condition is mild, and 1.5h is reacted at 160 DEG C can be obtained 83% isobide yield.
(2) carbon-based solid acid catalyst of benzene sulfonic acid group functional modification employed in the method for the present invention is through simple mistake
It is i.e. reusable after filter separation, there is certain economy and practicability.
Specific embodiment
Embodiment 1:
1g cocos active carbon, 2g p-aminobenzene sulfonic acid and 1g sodium hydroxide is weighed to be added in the deionized water of 150ml sufficiently
After being heated to 80 DEG C, 1g sodium nitrite and 5ml dilute hydrochloric acid (2mol/L) are added into mixture for stirring, filtered after reaction 10h,
Washing, in the moisture content that 100 DEG C dry and remove in solid to get the carbon-supported catalysts A of the benzene sulfonic acid group functional modification.
Embodiment 2:
It weighs and is sufficiently stirred in the deionized water of 1g mesoporous carbon, 2g p-aminobenzene sulfonic acid and 1g potassium hydroxide addition 150ml,
It is heated to that 1g sodium nitrite and 5ml dilute hydrochloric acid (2mol/L) are added in 20 DEG C of backward mixtures, is filtered, washed after reacting 10h,
Up to the carbon-supported catalysts B of the benzene sulfonic acid group functional modification after 100 DEG C of dryings.
Embodiment 3:
It weighs and is sufficiently stirred in the deionized water of 1g mesoporous carbon, 4g p-aminobenzene sulfonic acid and 1g calcium hydroxide addition 150ml,
It is heated to that 2g sodium nitrite and 5ml dilute hydrochloric acid (2mol/L) are added in 60 DEG C of backward mixtures, is filtered, washed after reacting 15h,
Up to the carbon-supported catalysts C of the benzene sulfonic acid group functional modification after 100 DEG C of dryings.
Embodiment 4:
It weighs and is sufficiently stirred in the deionized water of 1g mesoporous carbon, 6g p-aminobenzene sulfonic acid and 1g sodium hydroxide addition 150ml,
It is heated to that 2g isoamyl nitrite and 10ml dilute hydrochloric acid (2mol/L) are added in 80 DEG C of backward mixtures, filters, washes after reaction 10h
It washs, up to the carbon-supported catalysts D of the benzene sulfonic acid group functional modification after 100 DEG C of dryings.
Embodiment 5:
Sorb dehydration of alcohols prepares isobide: the solid acid catalyst by 10g sorbierite respectively with 0.4g embodiment 1-4 adds
After entering reactor, it is brought rapidly up to 160 DEG C, reacts 1.5h under pressure 50kPa, 500r/min mechanical stirring.To mixed after reaction
It closes addition deionized water in product to make it completely dissolved, centrifugation separates catalyst with reaction product, the efficient liquid of reaction mixture
Analysis of hplc, the results are shown in Table 1:
Each catalyst of table 1 is used for the catalytic performance of sorb dehydration of alcohols isobide
From the result of the present embodiment it can be concluded that, using the catalyst prepared in the embodiment of the present invention 1-4, with sorb
Alcohol is raw material, and decompression dehydration reaction prepares isobide, and isobide yield can reach 83%, and the conversion ratio of sorbierite can
Reach 100%, the selectivity of isobide can reach 83%.
Embodiment 6: by catalyst prepared by embodiment 4 with 5 the method for embodiment be used for sorb dehydration of alcohols prepare it is different
Sorbierite reaction.Catalysts dosage is 0.1g, and reaction temperature is 150 DEG C, and other conditions are same as Example 5.Through efficient
Liquid-phase chromatographic analysis, sorb alcohol conversion are 100%, and isobide yield is up to 62%.
Embodiment 7:
With catalyst D made from embodiment 4, sorb dehydration of alcohols is carried out in the method for embodiment 5 and prepares isobide reaction,
Catalyst circulation service performance is investigated, the results are shown in Table 2:
2 catalyst circulation service performance of table is investigated
From the above results, it can be seen that, under the cited reaction conditions, the carbon-based solid acid circulation of benzene sulfonic acid group functional modification
After 5 times, the conversion ratio of sorbierite is 100%, and the yield of isobide is still up to 70%.
Embodiment 8:
Mesoporous carbon described in embodiment 4 is replaced with the catalyst after using five times in embodiment 7, according to 4 institute of embodiment
The method of stating obtains the carbon-supported catalysts E of regenerated benzene sulfonic acid group functional modification.Sorb is used in method described in embodiment 5
Dehydration of alcohols prepares isobide reaction, as a result can get 80% isobide yield.
Embodiment 9:
1g cocos active carbon, 1g p-aminobenzene sulfonic acid and 1g lithium hydroxide is weighed to be added in the deionized water of 150ml sufficiently
After being heated to 100 DEG C, 0.5g sodium nitrite and 5ml dust technology (2mol/L) are added into mixture, reacts mistake after 10h for stirring
Filter, washing, in the moisture content that 100 DEG C dry and remove in solid to get solid acid catalyst.
After reactor is added with 0.02g solid acid catalyst obtained respectively in 10g sorbierite, it is brought rapidly up to 160 DEG C,
3h is reacted under pressure 5kPa, 500r/min mechanical stirring.Deionized water is added after reaction into mix products keeps it completely molten
Solution, centrifugation separate catalyst with reaction product, reaction mixture efficient liquid phase chromatographic analysis, the yield of obtained isobide
It is 65%.
Embodiment 10:
1g cocos active carbon, 10g p-aminobenzene sulfonic acid and 3g calcium hydroxide is weighed to be added in the deionized water of 200ml sufficiently
10g sodium nitrite and 10ml dilute sulfuric acid (2mol/L) are added into mixture to after 0 DEG C for stirring, ice bath, react filtering after 10h,
Washing, in the moisture content that 100 DEG C dry and remove in solid to get solid acid catalyst.
After reactor is added with 3g solid acid catalyst obtained respectively in 10g sorbierite, it is brought rapidly up to 250 DEG C,
6h is reacted under pressure 60kPa, 500r/min mechanical stirring.Deionized water is added after reaction into mix products keeps it completely molten
Solution, centrifugation separate catalyst with reaction product, reaction mixture efficient liquid phase chromatographic analysis, the yield of obtained isobide
It is 75%.
Embodiment 11:
1g cocos active carbon, 5g p-aminobenzene sulfonic acid and 3g potassium hydroxide is weighed to be added in the deionized water of 200ml sufficiently
After being heated to 100 DEG C, 25g sodium nitrite and 10ml dilute sulfuric acid (2mol/L) are added into mixture, reacts mistake after 10h for stirring
Filter, washing, in the moisture content that 100 DEG C dry and remove in solid to get solid acid catalyst.
After reactor is added with 3g solid acid catalyst obtained respectively in 10g sorbierite, it is brought rapidly up to 100 DEG C,
3h is reacted under pressure 100kPa, 500r/min mechanical stirring.Deionized water is added after reaction into mix products keeps it completely molten
Solution, centrifugation separate catalyst with reaction product, reaction mixture efficient liquid phase chromatographic analysis, the yield of obtained isobide
It is 79%.
It should be noted that in the present invention, used raw material sorbierite is solid.
In conclusion being heated under solvent-free conditions in preparation method of the invention, after the completion of reaction, it is only necessary to pass through
Simple centrifuge separation is crossed, product and reactants separate can be not necessarily to prolapse solvent processing step, it is easy to operate.
The product yield that preparation method of the invention obtains is high, and the selectivity of isobide is good, uses in the present invention
The high catalytic efficiency of carbon-based solid acid catalyst, it is reusable, same solid catalyst after multiple catalysis reaction,
Catalytic activity still with higher, obtained product yield are also higher.
Describe the present invention and its several embodiments by way of example rather than limitation above.It should be pointed out that
For those of ordinary skill in the art, under the premise of not departing from technical scheme design, if can also make
Dry modification and improvement, these belong to the protection scope of the application.
Claims (3)
1. a kind of method that sorb dehydration of alcohols prepares isobide, it is characterised in that: with the carbon of benzene sulfonic acid group functional modification
Based solid acid is catalyst, and sorbierite is raw material, in a heated condition, prepares isobide by dehydration.
2. the method that sorb dehydration of alcohols according to claim 1 prepares isobide, it is characterised in that: the dehydration
Temperature be 120-250 DEG C, reaction time 0.5-10h, reaction pressure 5-101.325kPa.
3. the method that sorb dehydration of alcohols according to claim 1 prepares isobide, it is characterised in that: the carbon-based solid
The preparation method of acid is that carbon-based material, p-aminobenzene sulfonic acid and inorganic base are dissolved in the water, and stirs, adds in 0-100 DEG C
Diazo reagent and inorganic acid, are stirred to react, and are filtered, washed, are dried.
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| CN114437099A (en) * | 2020-11-02 | 2022-05-06 | 中国石油化工股份有限公司 | Preparation method of high-purity isosorbide |
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