CN103896907A - Method used for preparing 1,4-dioxane from 1,3-dioxolane - Google Patents
Method used for preparing 1,4-dioxane from 1,3-dioxolane Download PDFInfo
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- CN103896907A CN103896907A CN201210571126.5A CN201210571126A CN103896907A CN 103896907 A CN103896907 A CN 103896907A CN 201210571126 A CN201210571126 A CN 201210571126A CN 103896907 A CN103896907 A CN 103896907A
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- dioxolane
- dioxane
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
- C07D319/12—1,4-Dioxanes; Hydrogenated 1,4-dioxanes not condensed with other rings
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- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a method used for preparing 1,4-dioxane from 1,3-dioxolane. According to the method, raw material gas containing 1,3-dioxolane and carrier gas is delivered into a reactor filled with a solid acid catalyst, and reaction is carried out at a reaction temperature of 120 to 160 DEG C, under a reaction pressure of 0.1 to 2.0MPa, and with gaseous hourly space velocity of 500 to 4500/h so as to obtain 1,4-dioxane, wherein partial pressure ratio of the carrier gas to 1,3-dioxolane in the raw material gas ranges from 1.0 to 50. The method is capable of realizing production of 1,4-dioxane under gas-solid reaction conditions; reaction conditions are mild; and separation of products from the catalyst is simple.
Description
Technical field
The present invention relates to a kind of under gas-solid phase condition by solid acid catalysis 1,3-dioxolane is prepared the method for Isosorbide-5-Nitrae-dioxane.
Background technology
Isosorbide-5-Nitrae-dioxane is a kind of non-proton type solvent, has excellent solubility property, suitable volatility and extremely strong penetrating power, and dissolves each other with water and many organic solvents, is commonly used for solvent and makes in industrial production, has many uses general.Traditional production method is taking the vitriol oil or phosphoric acid as catalyzer, and spent glycol or glycol ether dehydration form.The method not only side reaction is many, separation difficulty, and product yield is low, and used catalyst is mineral acid, and equipment corrosion is serious, contaminate environment.Therefore researchist is devoted to develop a kind of environment-friendly type technique of producing Isosorbide-5-Nitrae-dioxane always for a long time.
Fritz Offenlegungschrifen is [2,430,350 and 2,300,990] disclosed a kind of method with the synthetic Isosorbide-5-Nitrae-dioxane of catalyzing cation exchange resin ethylene glycol polymer, the method can produce efficiently 1 under lower than 170 DEG C of liquid-solid phase conditions, 4-dioxane, but in this reaction system, catalyzer is stable not.Patent [US3,825,568] has disclosed a kind of method that is Isosorbide-5-Nitrae-dioxane by acid catalysis oxyethane dimerization, and used catalyst is SiF
4or BF
3, temperature of reaction is within-50-0 DEG C scope, and in this system, used catalyst can have strong corrodibility.
Recently, we find under gas-solid phase condition in the time of research 1,3-dioxolane carbonylation, solid acid catalysis efficiently 1, and 3-dioxolane is produced Isosorbide-5-Nitrae-dioxane, and shown in (1), this reaction never appears in the newspapers.This reaction is carried out under gas-solid phase condition, and reaction conditions gentleness is simple to operate, and product and catalyst separating easy.
Summary of the invention
A kind of method of producing continuously Isosorbide-5-Nitrae-dioxane by 1,3-dioxolane under gas-solid phase condition that provides is provided.
For achieving the above object, the invention provides one and prepare 1, the method of 4-dioxane, it is characterized in that, to contain 1, the unstripped gas of 3-dioxolane and carrier gas passes into the reactor that is loaded with solid acid catalyst, at temperature of reaction 120-160 DEG C, reaction pressure 0.1～2.0MPa, gas volume air speed 500～4500h
-1lower reaction, generates Isosorbide-5-Nitrae-dioxane; In wherein said unstripped gas, the intrinsic standoff ratio of carrier gas and 1,3-dioxolane is 1.0～50.
In the present invention, described solid acid catalyst is acidic molecular sieve.
In a preferred embodiment of the invention, described solid acid catalyst is H-beta-molecular sieve; Its Si/Al atomic ratio is 10-80;
The beta-molecular sieve of H-described in the application is the microporous crystalline solid acid with BEA topological framework of silica alumina composition.
Described carrier gas is a kind of or any several mixture being selected from carbon monoxide, nitrogen, hydrogen, helium, carbonic acid gas.In unstripped gas, the intrinsic standoff ratio of carrier gas and 1,3-dioxolane is 1.4～46.
Described reactor is continuous fixed-bed reactor, fluidized-bed reactor or moving-burden bed reactor.
Embodiment
The following examples will be further described the present invention, but not thereby limiting the invention.
In embodiment, the transformation efficiency of 1,3-dioxolane and the selectivity of Isosorbide-5-Nitrae-dioxane are calculated by following two formulas
1,3-dioxolane transformation efficiency=[(in unstripped gas 1, the volumetric molar concentration of 3-dioxolane)-(in product 1, the volumetric molar concentration of 3-dioxolane)] ÷ (in unstripped gas 1, the volumetric molar concentration of 3-dioxolane) × (100%)
1,4-dioxane selectivity=2 × (in product 1,4-dioxane volumetric molar concentration) ÷ [(in unstripped gas 1, the volumetric molar concentration of 3-dioxolane)-(in product 1, the volumetric molar concentration of 3-dioxolane)] × (100%)
The beta-molecular sieve of H-described in the application is purchased from Nankai's catalyst plant.
Embodiment 1
By H-β (Si/Al=25) molecular sieve powder compressing tablet, pulverize, sieve the 40-60 object catalyzer obtaining.0.6g catalyzer is packed in the reactor that internal diameter is 8mm, be warming up to 500 DEG C in nitrogen atmosphere, constant temperature 1h at this temperature, is cooled under 130 DEG C of temperature of reaction afterwards naturally.Utilize carrier gas CO to carry 1,3-dioxolane is carried into reaction tubes, 1,3-dioxolane dividing potential drop is 42KPa (utilizing Clausius-carat pendant dragon to calculate), and CO volume space velocity is 2120h
-1, reaction is carried out under normal pressure.Reactant is analyzed by on-line chromatograph, and the transformation efficiency of 1,3-dioxolane is 64.3%, and Isosorbide-5-Nitrae-dioxane selectivity is 91.2%.
Embodiment 2
Other conditions are identical with embodiment 1, evaluate different solid acid catalyst catalysis 1, and 3-dioxy five generates Isosorbide-5-Nitrae-dioxane reactivity worth, and reaction effluent adopts on-line chromatograph analysis.Result is as shown in table 1.
Table 1
| Solid acid | 1,3-dioxolane transformation efficiency (%) | Isosorbide-5-Nitrae-dioxane selectivity (%) |
| H-β(Si/Al＝40) | 63.6 | 92.1 |
| H-β(Si/Al＝80) | 43.8 | 93.3 |
Embodiment 3
At 120 DEG C, 140 DEG C, 160 DEG C, other conditions are identical with embodiment 1 respectively, investigate temperature 1,3-dioxolane disproportionation is generated to the impact that Isosorbide-5-Nitrae-dioxane reacts, and reaction effluent adopts on-line chromatograph analysis.Result is as shown in table 2.
Table 2
| Temperature (DEG C) | 1,3-dioxolane transformation efficiency (%) | Isosorbide-5-Nitrae-dioxane selectivity (%) |
| 120 | 53.1 | 94.5 |
| 140 | 76.0 | 91.2 |
| 160 | 83.3 | 86.4 |
Embodiment 4
CO (carbon monoxide converter) gas volume space velocity is respectively 530h
-1, 1060h
-1, 3180h
-1, 4240h
-1time, other conditions are identical with embodiment 1, investigate the impact of air speed on reactivity worth.Reaction effluent adopts on-line chromatograph analysis.Result is as shown in table 4.
Table 3
Embodiment 5
Investigate different carrier gas (nitrogen, carbonic acid gas, hydrogen, helium) and 1,3-dioxolane is produced to the impact of Isosorbide-5-Nitrae-dioxane, other conditions are identical with embodiment 1, and result is as shown in table 4.
Table 4
Embodiment 6
Keep 1,3-dioxolane saturation vapour pressure constant, investigate the impact of differential responses pressure to 1,3-dioxolane production Isosorbide-5-Nitrae-dioxane, other conditions are identical with embodiment 1, and result is as shown in table 5.
Table 5
Claims (7)
1. prepare 1 for one kind, the method of 4-dioxane, is characterized in that, will contain 1, the unstripped gas of 3-dioxolane and carrier gas passes into the reactor that is loaded with solid acid catalyst, at temperature of reaction 120-160 DEG C, reaction pressure 0.1～2.0MPa, gas volume air speed 500～4500h
-1lower reaction, generates Isosorbide-5-Nitrae-dioxane; In wherein said unstripped gas, the intrinsic standoff ratio of carrier gas and 1,3-dioxolane is 1.0～50.
2. method according to claim 1, is characterized in that, described solid acid catalyst is acid molecular sieve catalyst.
3. method according to claim 1, is characterized in that, described solid acid catalyst is H-beta-molecular sieve.
4. method according to claim 3, is characterized in that, the Si/Al atomic ratio of described H-beta-molecular sieve is 10-80.
5. method according to claim 1, is characterized in that, described carrier gas is one or more the mixture being selected from carbon monoxide, nitrogen, hydrogen, helium, carbonic acid gas.
6. method according to claim 1, is characterized in that, in described unstripped gas, the intrinsic standoff ratio of carrier gas and 1,3-dioxolane is 1.4～46.
7. state method according to claim 1, it is characterized in that, described reactor is selected from continuous fixed-bed reactor, fluidized-bed reactor or moving-burden bed reactor.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210571126.5A CN103896907B (en) | 2012-12-25 | 2012-12-25 | A kind of method being prepared Isosorbide-5-Nitrae-dioxane by 1,3-dioxolane |
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|---|---|---|---|
| CN201210571126.5A CN103896907B (en) | 2012-12-25 | 2012-12-25 | A kind of method being prepared Isosorbide-5-Nitrae-dioxane by 1,3-dioxolane |
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| CN103896907B CN103896907B (en) | 2016-01-20 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104857992A (en) * | 2015-05-13 | 2015-08-26 | 安徽金邦医药化工有限公司 | Complex solid acid catalyst with high catalytic efficiency and preparation method thereof |
| CN104888747A (en) * | 2015-05-13 | 2015-09-09 | 安徽金邦医药化工有限公司 | Magnetic composite solid acid catalyst and preparation method thereof |
| CN104888814A (en) * | 2015-05-13 | 2015-09-09 | 安徽金邦医药化工有限公司 | Low-temperature high-activity composite solid acid catalyst and preparation method thereof |
| CN105985312A (en) * | 2015-02-09 | 2016-10-05 | 中国科学院大连化学物理研究所 | Method for preparing 1, 4-dioxane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1003799B1 (en) * | 1997-08-19 | 2003-11-19 | E.I. Du Pont De Nemours And Company | Process for copolymerization of formaldehyde with cyclic ethers in the presence of organic nitro compounds |
| CN1473824A (en) * | 2003-08-01 | 2004-02-11 | 曲阜师范大学 | Method for catalytically synthesizing 1,4-dioxane using granular solid super strong acid |
-
2012
- 2012-12-25 CN CN201210571126.5A patent/CN103896907B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1003799B1 (en) * | 1997-08-19 | 2003-11-19 | E.I. Du Pont De Nemours And Company | Process for copolymerization of formaldehyde with cyclic ethers in the presence of organic nitro compounds |
| CN1473824A (en) * | 2003-08-01 | 2004-02-11 | 曲阜师范大学 | Method for catalytically synthesizing 1,4-dioxane using granular solid super strong acid |
Non-Patent Citations (1)
| Title |
|---|
| FABIO MARCHETTI ET.AL.: "Activation reactions of 1,1-dialkoxoalkanes and unsaturated O-donors by titanium tetrafluoride", 《INORGANICA CHIMICA ACTA》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105985312A (en) * | 2015-02-09 | 2016-10-05 | 中国科学院大连化学物理研究所 | Method for preparing 1, 4-dioxane |
| CN105985312B (en) * | 2015-02-09 | 2018-11-02 | 中国科学院大连化学物理研究所 | A method of preparing Isosorbide-5-Nitrae-dioxane |
| CN104857992A (en) * | 2015-05-13 | 2015-08-26 | 安徽金邦医药化工有限公司 | Complex solid acid catalyst with high catalytic efficiency and preparation method thereof |
| CN104888747A (en) * | 2015-05-13 | 2015-09-09 | 安徽金邦医药化工有限公司 | Magnetic composite solid acid catalyst and preparation method thereof |
| CN104888814A (en) * | 2015-05-13 | 2015-09-09 | 安徽金邦医药化工有限公司 | Low-temperature high-activity composite solid acid catalyst and preparation method thereof |
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| CN103896907B (en) | 2016-01-20 |
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