CN105985312A - Method for preparing 1, 4-dioxane - Google Patents
Method for preparing 1, 4-dioxane Download PDFInfo
- Publication number
- CN105985312A CN105985312A CN201510069951.9A CN201510069951A CN105985312A CN 105985312 A CN105985312 A CN 105985312A CN 201510069951 A CN201510069951 A CN 201510069951A CN 105985312 A CN105985312 A CN 105985312A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- hydrogen
- dimethyl ether
- dioxane
- glycol dimethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- 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 for preparing anhydrous high-purity 1, 4-dioxane from glycol dimethyl ether through one step. Through the method, high-purity 1, 4-dioxane is prepared from the glycol dimethyl ether raw material at a low temperature at a high conversion rate. In the whole reaction process, water does not react and product water is not produced so that 1, 4-dioxane-containing industrial wastewater is prevented thoroughly. The glycol dimethyl ether raw material has a high conversion ratio at a low temperature, catalyst stability is good, product 1, 4-dioxane selectivity is high and the whole process is simple and environmentally friendly.
Description
Technical field
The application belongs to solid acid catalysis field, prepares Isosorbide-5-Nitrae-dioxane in particular to one
Method.
Background technology
Isosorbide-5-Nitrae-dioxane (Isosorbide-5-Nitrae-Dioxane), Chinese another name dioxane, be one have delicate fragrance ester taste,
Water white flammable liquid, it is possible to form azeotropic mixture with water.Isosorbide-5-Nitrae-dioxane industrial use
Extensively, as solvent, it has the solubility property of excellence, and its solvability is similar to dimethylformamide,
It is eager to excel than oxolane.Can be used as cellulose ethanoate, various kinds of resin, vegetable oil, mineral oil, molten
The solvent of property dyestuff etc..As reaction medium in Synthetic Leather, Amino acid synthesis leather etc. react
Use in a large number with volatile solvent.Isosorbide-5-Nitrae-dioxane is also used in medicine and fine chemical product industry
Make extractant and reaction medium；As solvent and dispersant in coating, dye technology；1,1,1-
Trichloroethane produce in and printing-ink aspect as stabilizer exist.In addition, Isosorbide-5-Nitrae-dioxy
Six rings are also used as the remover etc. of high purity metal surface conditioning agent and varnish and paint.
Industrial, Isosorbide-5-Nitrae-dioxane be by ethylene glycol or polyglycol ether under sulphuric acid or phosphatizing
Dehydration generates, and is then added by highly basic in Isosorbide-5-Nitrae-dioxane aqueous solution, removes acidic materials and (i.e. urges
Agent residual component) and water, after filtering off solid matter, rectification fraction i.e. obtains technical grade finished product.Industry
If level Isosorbide-5-Nitrae-dioxane needs exquisiteness to be high-purity Isosorbide-5-Nitrae-dioxane, due to Isosorbide-5-Nitrae-dioxane and water
Azeotropic mixture can be formed, cause its technique extremely complex, and energy consumption is huge.It is additionally, since two
Alkane (Isosorbide-5-Nitrae-dioxane) is highly soluble in water, so the dioxane of trace cannot use physics in waste water
The method separated removes.There is document report that the method for chemistry, ultraviolet light can be used to decompose or microorganism
The method of degraded removes the dioxane of trace in waste water, but said method only terminates in laboratory research rank
Section, and the degree of not up to commercial application.Therefore, current existing Isosorbide-5-Nitrae-dioxane industry is raw
The process route produced cannot inherently be stopped dioxane and be drained in natural environment with waste water.And two
Alkane is difficult to be biodegradable in natural environment, it is possible to by sucking, eating or be absorbed into through skin
Enter in body, the most progressively accumulate, it is impossible to metabolism goes out external.Its metabolite pair of dioxane
Human body cell has carcinogenesis.Dioxane itself also has anesthesia and stimulation, it is possible to human body
Liver, kidney and nervous system cause damage.Therefore, traditional Isosorbide-5-Nitrae-dioxane preparation technology exists
Shortcomings.Especially remain the industrial wastewater ground cannot inherently avoided containing trace dioxane
Produce.
Summary of the invention
An aspect according to the application, it is provided that a kind of method preparing anhydrous Isosorbide-5-Nitrae-dioxane,
The method can be carried out at a lower temperature, and technique is simple simultaneously, product is easily isolated, process is anhydrous
Participate in and anhydrous generation, inherently stopped the generation of the industrial wastewater containing dioxane, therefore should
Method has prominent environment friendly.
Described method, by the raw material containing glycol dimethyl ether by being loaded with the reaction of solid acid catalyst
Device, reacts under conditions of reaction temperature 50～200 DEG C, reaction pressure 0.1～10.0MPa, generates
Anhydrous Isosorbide-5-Nitrae-dioxane and dimethyl ether, separated, obtain anhydrous Isosorbide-5-Nitrae-dioxane；
In described raw material, glycol dimethyl ether mass space velocity is 0.05～10.0h-1；
In described raw material, the volumn concentration of glycol dimethyl ether is 1～100%.
In the application, the reaction of glycol dimethyl ether synthesis Isosorbide-5-Nitrae-dioxane is as shown in following formula I:
The present processes, does not has water, only Isosorbide-5-Nitrae-dioxane and dimethyl ether in product.And Isosorbide-5-Nitrae-
The boiling point of dioxane is 101.1 DEG C, and the boiling point of dimethyl ether is-24.9 DEG C, and difference is huge, pole
Easily separated.Therefore the present processes can be in the case of low energy consumption, environmental friendliness, with relatively low one-tenth
Originally anhydrous and high-purity Isosorbide-5-Nitrae-dioxane is obtained.
Preferably, described solid acid catalyst selected from acid molecular sieve catalyst, acid resin catalyst,
At least one in solid sulfoacid catalyst.
In the application, term " solid sulfoacid ", refer to contain in solid, molecular formula under normal temperature and pressure
There is sulfonic group (-SO3H) organic acid, formula is R-SO3H, wherein R is alkyl.The application
In, solid sulfoacid includes but not limited to benzenesulfonic acid, p-methyl benzenesulfonic acid.
It is further preferred that the structure type of described acid molecular sieve catalyst selected from MWW, FER,
At least one in MFI, MOR, FAU, BEA.
It is further preferred that silicon and the atomic ratio of aluminum in described acid molecular sieve catalyst
Si/Al=3～100.
It is further preferred that described acid molecular sieve catalyst is selected from Hydrogen MCM-22 molecular sieve, hydrogen
Type ZSM-35 molecular sieve, Hydrogen ZSM-5 molecular sieve, h-mordenite, Hydrogen Y zeolite,
At least one in Hydrogen Beta molecular sieve.
It is further preferred that silicon and the atomic ratio of aluminum in described Hydrogen MCM-22 molecular sieve
Si/Al=5～100.
It is further preferred that silicon and the atomic ratio of aluminum in described Hydrogen ZSM-35 molecular sieve
Si/Al=5～100.
It is further preferred that silicon and the atomic ratio of aluminum in described Hydrogen ZSM-5 molecular sieve
Si/Al=5～100.
It is further preferred that the atomic ratio Si/Al=5～50 of silicon and aluminum in described h-mordenite.
It is further preferred that silicon and the atomic ratio Si/Al=3～50 of aluminum in described Hydrogen Y molecular sieve.
It is further preferred that silicon and the atomic ratio of aluminum in described Hydrogen Beta molecular sieve
Si/Al=5～100.
Preferably, described acid resin catalyst is selected from the resin containing sulfonate functional groups at least
A kind of.In the application, term " sulfonate functional groups ", refer to sulfuric acid molecule formula H2SO4In lose
One the most remaining part of hydroxyl (-OH), is called for short sulfo group, and chemical formula is-SO3H.Containing sulfonic acid
The resin of base functional group includes but not limited to that sulfonate crosslinked styrene system resin is (such as: sulfonation crosslinking benzene
Ethylene-divinylbenzene interpolymer resin), perfluorinated sulfonic resin (English is Nafion-H).Further
Preferably, at least one in sulfonic acid ion exchange resin of described acid resin catalyst.
Being preferably carried out mode as one, described solid acid catalyst is by Hydrogen MCM-22 molecule
Sieve, Hydrogen ZSM-35 molecular sieve, Hydrogen ZSM-5 molecular sieve, h-mordenite, Hydrogen Y
Zeolite, Hydrogen Beta molecular sieve, sulfonate crosslinked styrene-divinylbenzene interpolymer resin, perfluor sulphur
At least one composition in acid resin, benzenesulfonic acid, p-methyl benzenesulfonic acid.
Preferably, described range of reaction temperature lower limit selected from 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 100 DEG C,
120 DEG C, the upper limit is selected from 140 DEG C, 150 DEG C, 200 DEG C.It is further preferred that described reaction temperature is
100～150 DEG C.
Preferably, described reaction pressure range lower limit is selected from 0.1Mpa, 1Mpa, 3Mpa, and the upper limit is selected
From 5Mpa, 8Mpa, 10Mpa.It is further preferred that described reaction pressure is 3～8Mpa.
Preferably, in described raw material, glycol dimethyl ether mass space velocity range lower limit is selected from 0.05h-1、0.3
h-1, the upper limit is selected from 2h-1、5h-1。
It is further preferred that glycol dimethyl ether mass space velocity is 0.3～2.0h in described raw material-1。
Preferably, in described raw material the volumn concentration range lower limit of glycol dimethyl ether selected from 1%,
3%, 5%, 10%, the upper limit is selected from 40%, 50%, 80%, 100%.
It is further preferred that the volumn concentration of glycol dimethyl ether is 5～50% in described raw material.
In the application, described raw material can comprise only glycol dimethyl ether, it is also possible to by raw material
Add diluent gas to reduce the volume content of glycol dimethyl ether in raw material.Employing diluent gas is permissible
Preferably alleviating the adverse effect that system is brought by reaction heat, those skilled in the art can be according to reality
Whether needs and concrete catalyst choice add the kind of diluent gas and carrier gas, in principle,
The gas with the reactant in system, product and catalyst reaction not can serve as diluent gas.
Preferably, described raw material possibly together with diluent gas, described diluent gas selected from nitrogen, helium,
At least one in argon.
Different reactor all can realize the technical scheme of the application.Preferably, described reactor is solid
Fixed bed reactor, tank reactor.
The beneficial effect that the application can produce includes:
1) method provided herein, is obtained high-purity Isosorbide-5-Nitrae-dioxy six by glycol dimethyl ether one step
Ring, simplifies processing step.
2) method provided herein, the anhydrous participation of whole course of reaction and anhydrous generation.Cause
This, the Isosorbide-5-Nitrae-dioxane that there is not generation is dissolved in water the problem causing separating difficulty.Also
Avoid the generation of waste water containing Isosorbide-5-Nitrae-dioxane, and then avoid environmental pollution.
3) method provided herein, product is only Isosorbide-5-Nitrae-dioxane and dimethyl ether, condition of normal pressure
Under, two kinds of product boiling point difference are huge, easily separate, and therefore can obtain with low energy consumption low cost
Anhydrous and high-purity Isosorbide-5-Nitrae-dioxane.
Accompanying drawing explanation
Fig. 1 is glycol dimethyl ether conversion ratio and Isosorbide-5-Nitrae-dioxane on H-ZSM-5 in embodiment 1
Selectivity is with the variation relation figure of reaction temperature.
Fig. 2 is glycol dimethyl ether conversion ratio and Isosorbide-5-Nitrae-dioxy six on h-mordenite in embodiment 2
Ring selectivity is with the variation relation figure of reaction temperature.
Fig. 3 is glycol dimethyl ether conversion ratio and Isosorbide-5-Nitrae-dioxane choosing on H-Beta in embodiment 3
Selecting property is with the variation relation figure of reaction temperature.
Fig. 4 be in embodiment 4 on H-Beta glycol dimethyl ether conversion ratio with the change in response time
Graph of a relation.
Fig. 5 is glycol dimethyl ether conversion ratio and Isosorbide-5-Nitrae-dioxane selectivity on H-Y in embodiment 5
Variation relation figure with reaction temperature.
Fig. 6 is glycol dimethyl ether conversion ratio and Isosorbide-5-Nitrae-dioxy six on perfluorinated sulfonic resin in embodiment 6
Ring selectivity is with the variation relation figure of reaction temperature.
Detailed description of the invention
Below in conjunction with specific embodiment, the application is expanded on further.Only should be understood that these embodiments
For the application being described rather than limiting scope of the present application.
If no special instructions, the raw material in embodiments herein and catalyst are all purchased by commercial sources
Buy.
Embodiments herein is analyzed method as follows:
Raw material and product, by the Agilent 7890A gas chromatogram of Agilent company, use Agilent public
The HP-5 capillary column detection of department.
According to a kind of embodiment of the application, select fixed bed reactors, catalyst filling quality
0.5～1g, reaction temperature 20～250 DEG C, reaction pressure 0.1～10Mpa.Raw material glycol dimethyl ether is adopted
Reactors are entered with two kinds of input modes:
First kind of way is by nitrogen, carries second two under the conditions of different bath temperatures (20-80 DEG C)
The saturated vapor of diethylene glycol dimethyl ether enters in fixed bed reactors, to obtain the second two of different volumes content
Diethylene glycol dimethyl ether unstrpped gas.The meter of the saturated vapour pressure of raw material glycol dimethyl ether under condition of different temperatures
Calculation method is as shown in Formula II:
ln(p1 */p2 *)=-ΔvapHm/8.3145×(1/T1-1/T2) Formula II
Wherein p1 *And p2 *Represent different temperatures (T respectively1、T2The saturated steaming of glycol dimethyl ether under)
Air pressure.Known glycol dimethyl ether mole vaporization enthalpy ΔvapHm=28.14KJ/mol, when 25 DEG C, it is saturated
Vapour pressure is 13.29Kpa, thus can calculate the saturated vapor of glycol dimethyl ether under arbitrary temp
Pressure.Can be calculated by saturated vapour pressure and in the unit interval, enter into raw material ethylene glycol bisthioglycolate in reactor
The amount of methyl ether material.
The second way be by constant flow pump liquid material glycol dimethyl ether with flow velocity 0.1-10ml/min
Flow velocity is pumped directly in fixed bed reactors, in this mode enter reactor contact with catalyst former
In material gas, the volume content of glycol dimethyl ether is 100%.
In embodiments herein, conversion ratio, selectivity are calculated as follows:
Glycol dimethyl ether conversion ratio=[(glycol dimethyl ether molal quantity in charging)-(second two in discharging
Diethylene glycol dimethyl ether molal quantity)] ÷ (glycol dimethyl ether molal quantity in charging) × (100%)
Isosorbide-5-Nitrae-dioxane selectivity=(the carbon molal quantity of Isosorbide-5-Nitrae-dioxane in discharging) ÷ is [(in charging
The carbon molal quantity of glycol dimethyl ether)-(the carbon molal quantity of glycol dimethyl ether in discharging)] × (100%)
Embodiment 1
By the H-ZSM-5 molecular sieve of silica alumina ratio Si/Al=50 at 40Mpa pressure lower sheeting, it is crushed to
20～40 mesh, obtain catalyst.
1g catalyst is filled in fixed bed reactors, carries out pre-treatment.Catalyst pre-treatment bar
Part is: N2Flow velocity 30ml/min, rises to 500 DEG C from 25 DEG C of beginnings through 150min, and at 500 DEG C
Under the conditions of keep 180min.
By reaction raw materials glycol dimethyl ether under the conditions of bath temperature 40 DEG C, by N2With 30ml/min
Flow velocity is brought in reactor, and air speed is 0.08h-1, reaction pressure 3.0Mpa.
Feed stock conversion and selectivity of product vary with temperature figure as shown in Figure 1.From Fig. 1 permissible
Seeing, on H-ZSM-5 (Si/Al=50) catalyst, when reaction temperature is less than 80 DEG C, raw material turns
Rate is less than 40%.But along with reaction temperature gradually rises, feed stock conversion increases rapidly, works as reaction
When temperature is 120 DEG C, feed stock conversion is close to 100% (about 99%).Product Isosorbide-5-Nitrae-dioxane
Selectivity maintains about 50% in range of reaction temperature always.As it is shown in figure 1, in reaction temperature
In the range of 45～120 DEG C, feed stock conversion is close to 100%, and product easily separates (dimethyl ether
Boiling point be-24.9 DEG C；The boiling point of Isosorbide-5-Nitrae-dioxane is 101 DEG C).So it is believed that this reaction
Process route is capable of raw material glycol dimethyl ether and is totally converted, and the liquid product simultaneously collected is only
For Isosorbide-5-Nitrae-dioxane, thus obtained high-purity Isosorbide-5-Nitrae-dioxane by glycol dimethyl ether one step.Whole
The anhydrous participation of individual course of reaction, anhydrous generation, environmental friendliness.
Embodiment 2
By the h-mordenite of silica alumina ratio Si/Al=14.5 at 40Mpa pressure lower sheeting, it is crushed to
20-40 mesh, obtains catalyst.
1g catalyst is filled in fixed bed reactors, carries out pre-treatment.Pretreatment is:
N2Flow velocity 30ml/min, rises to 500 DEG C from 25 DEG C of beginnings through 150min, and under the conditions of 500 DEG C
Keep 180min.
By reaction raw materials glycol dimethyl ether under the conditions of bath temperature 40 DEG C, by N2With 30ml/min
Flow velocity is brought in reactor, and air speed is 0.4h-1, reaction pressure is 0.5Mpa.
Feed stock conversion and selectivity of product vary with temperature figure as shown in Figure 2.Can from Fig. 2
Going out, when being catalyst when using h-mordenite (Si/Al=14.5), feed stock conversion is along with reaction
The rising of temperature and be gradually increased, at 200 DEG C, conversion ratio reaches maximum, stable about 30%.
The selectivity of product Isosorbide-5-Nitrae-dioxane reduces along with the rising of reaction temperature.In relatively low reaction temperature
Under degree (60～100 DEG C), the selectivity of product Isosorbide-5-Nitrae-dioxane maintains 40～45%, but when reaction
When temperature is higher than 120 DEG C, the side reaction that reaction raw materials occurs on h-mordenite is more, main product
Thing selectivity declines rapidly.At 200 DEG C, selectivity of product is only about 10%.
Embodiment 3
By the H-Beta molecular sieve of silica alumina ratio Si/Al=16 at 40Mpa pressure lower sheeting, it is crushed to
20-40 mesh obtains catalyst.
1g catalyst is filled in fixed bed reactors, carries out pre-treatment.Pretreatment is:
N2 flow velocity 30ml/min, rises to 500 DEG C from 25 DEG C of beginnings through 150min, and under the conditions of 500 DEG C
Keep 180min.Reaction raw materials glycol dimethyl ether is under the conditions of bath temperature 40 DEG C, by N2With
30ml/min flow velocity is brought in reactor, and air speed is 0.05h-1, reaction pressure 5.0Mpa.
Feed stock conversion and selectivity of product vary with temperature figure as shown in Figure 3.Can from Fig. 3
Going out, when being catalyst when using H-Beta (Si/Al=16), raw material is (25 DEG C) under relatively low room temperature condition
Conversion ratio just can reach 60%, and when reaction temperature is higher than 50 DEG C, raw material glycol dimethyl ether converts
Rate can reach 98%.When reaction temperature is higher than 60 DEG C, and feed stock conversion is close to 100%.Product 1,
4-dioxane selectivity maintains near 50% in full response temperature range always, except dimethyl ether with
Outward, entirely without the generation other by-product being detected.Illustrate on H-Beta catalyst, raw material
Glycol dimethyl ether is carried out fully according to the response path in Formulas I, without other side reactions.
Embodiment 4
The Pretreatment of catalyst and catalyst is with embodiment 3, by stable for reaction temperature at 60 DEG C,
Raw material glycol dimethyl ether conversion ratio changes over as shown in Figure 4.From fig. 4, it can be seen that
60 DEG C, H-Beta molecular sieve reactivity is highly stable, and within the response time of 20h, raw material converts
Rate is not changed in substantially, maintains near 98.5% always.Select H-Beta molecular sieve as catalyst,
Under the conditions of 30～80 DEG C of relatively low reaction temperatures, raw material glycol dimethyl ether conversion ratio close to 100%,
And liquid product is entirely Isosorbide-5-Nitrae-dioxane.
Embodiment 5
By the H-Y molecular sieve of silica alumina ratio Si/Al=10.6 at 40Mpa pressure lower sheeting, it is crushed to 20-40
Mesh, obtains catalyst.
1g catalyst is filled in fixed bed reactors, carries out pre-treatment.Pretreatment is:
N2Flow velocity 30ml/min, rises to 500 DEG C from 25 DEG C of beginnings through 150min, and under the conditions of 500 DEG C
Keep 180min.
Having trace constant flow pump to pump into reaction raw materials glycol dimethyl ether, flow velocity is 0.1ml/min, empty
Speed is 5.0h-1, reaction pressure 0.1Mpa.
Feed stock conversion and selectivity of product vary with temperature figure as shown in Figure 5.From Fig. 5 permissible
Finding out, when using H-Y (Si/Al=10.6) as catalyst, raw material glycol dimethyl ether is at low temperature bar
Under part, (25～120 DEG C) do not react.When reaction temperature is higher than 120 DEG C, raw material converts
Rate is gradually increased along with the rising of reaction temperature, and when 200 DEG C, conversion ratio reaches about 25%.
But the selectivity of product Isosorbide-5-Nitrae-dioxane is along with the rising of reaction temperature, and straight line declines, at 200 DEG C
Time, selectivity of product is only 25%.This shows under the high temperature conditions, and raw material is at H-Y molecular sieve table
There is more side reaction in face.
Embodiment 6
0.5g perfluorinated sulfonic resin is filled in fixed bed reactors, carries out pre-treatment.Pre-treatment bar
Part is: N2Flow velocity 30ml/min, rises to 150 DEG C through 60min, 150 DEG C of conditions from 25 DEG C of beginnings
Lower holding 180min.
By trace constant flow pump, reaction raw materials glycol dimethyl ether is pumped into reactor, and flow velocity is
0.1ml/min, air speed is 10.0h-1, reaction pressure 0.1Mpa.
Feed stock conversion and selectivity of product vary with temperature figure as shown in Figure 6.From Fig. 6 permissible
Find out, be catalyst when using perfluorinated sulfonic resin, under the conditions of relatively low reaction temperatures (25～80 DEG C),
The conversion ratio of raw material glycol dimethyl ether is the highest (30～40%).When reaction temperature is higher than 80 DEG C, former
Material conversion ratio ramps along with the rising of reaction temperature, when temperature is higher than 120 DEG C, and conversion ratio
Reach more than 90%.When reaction temperature is higher than 135 DEG C, feed stock conversion is close to 99%.In product
Only detecting Isosorbide-5-Nitrae-dioxane and dimethyl ether, Isosorbide-5-Nitrae-dioxane selectivity is at full response temperature model
Maintain about 50% in enclosing always.
Embodiment 7
Fill different catalysts 1g respectively in fixed bed reactors, and carry out pre-treatment.Molecular sieve
Type catalyst pre-treatment condition is: N2Flow velocity 30ml/min, rises to through 150min from 25 DEG C of beginnings
500 DEG C, and under the conditions of 500 DEG C, keep 180min.Perfluorinated sulfonic resin, benzenesulfonic acid and to methyl
The Pretreatment of benzenesulfonic acid is: N2Flow velocity 30ml/min, rises to through 60min from 25 DEG C of beginnings
150 DEG C, under the conditions of 150 DEG C, keep 180min.
By reaction raw materials glycol dimethyl ether under the conditions of bath temperature 40 DEG C, by N2With 30ml/min
Flow velocity is brought in reactor, reaction pressure 0.1-10Mpa, reaction temperature 50-200 DEG C.
On each catalyst, reaction result and selectivity of product are as shown in table 1.Select perfluorinated sulfonic resin
(Nafion-H) as catalyst, under the conditions of 80-150 DEG C of reaction temperature, raw material glycol dinitrate
Ether conversion ratio is close to 100%, and liquid product only detects Isosorbide-5-Nitrae-dioxane.Through long-time reaction,
Appealing two kinds of catalyst to occur without obvious deactivation phenomenom, stability is preferable.
Table 1 glycol dimethyl ether is catalytic reaction result in different solid acid catalyst surfaces and duct
The above, be only several embodiments of the application, and the application not does any type of limit
System, although the application with preferred embodiment disclose as above, but and be not used to limit the application, any
Those skilled in the art, in the range of without departing from technical scheme, utilize above-mentioned taking off
The technology contents shown makes a little variation or modification is all equal to equivalence case study on implementation, belongs to technology
In aspects.
Claims (10)
1. the method preparing anhydrous Isosorbide-5-Nitrae-dioxane, it is characterised in that will be containing ethylene glycol bisthioglycolate
The raw material of methyl ether is by being loaded with the reactor of solid acid catalyst, in reaction temperature 50～200 DEG C, reaction
React under conditions of pressure 0.1～10.0MPa, generate anhydrous Isosorbide-5-Nitrae-dioxane and dimethyl ether, through dividing
From, obtain anhydrous Isosorbide-5-Nitrae-dioxane；
In described raw material, glycol dimethyl ether mass space velocity is 0.05～10.0h-1；
In described raw material, the volumn concentration of glycol dimethyl ether is 1～100%.
Method the most according to claim 1, it is characterised in that described solid acid catalyst selects
At least one in acid molecular sieve catalyst, acid resin catalyst, solid sulfoacid catalyst.
Method the most according to claim 2, it is characterised in that described acidic molecular sieve is catalyzed
The atomic ratio Si/Al=3～100 of silicon and aluminum in agent.
Method the most according to claim 2, it is characterised in that described acidic molecular sieve is catalyzed
Agent selected from Hydrogen MCM-22 molecular sieve, Hydrogen ZSM-35 molecular sieve, Hydrogen ZSM-5 molecular sieve,
At least one in h-mordenite, Hydrogen Y zeolite, Hydrogen Beta molecular sieve.
Method the most according to claim 4, it is characterised in that described Hydrogen MCM-22
The atomic ratio Si/Al=5～100 of silicon and aluminum in molecular sieve；
Silicon and the atomic ratio Si/Al=5～100 of aluminum in described Hydrogen ZSM-35 molecular sieve；
Silicon and the atomic ratio Si/Al=5～100 of aluminum in described Hydrogen ZSM-5 molecular sieve；
The atomic ratio Si/Al=5～50 of silicon and aluminum in described h-mordenite；
Silicon and the atomic ratio Si/Al=3～50 of aluminum in described Hydrogen Y molecular sieve；
Silicon and the atomic ratio Si/Al=5～100 of aluminum in described Hydrogen Beta molecular sieve.
Method the most according to claim 2, it is characterised in that described acid resin catalyst
At least one in the resin containing sulfonate functional groups.
Method the most according to claim 1, it is characterised in that described solid acid catalyst by
Hydrogen MCM-22 molecular sieve, Hydrogen ZSM-35 molecular sieve, Hydrogen ZSM-5 molecular sieve, Hydrogen
Modenite, Hydrogen Y zeolite, Hydrogen Beta molecular sieve, sulfonate crosslinked styrene-divinylbenzene are common
At least one composition in polyimide precursor resin, perfluorinated sulfonic resin, benzenesulfonic acid, p-methyl benzenesulfonic acid.
Method the most according to claim 1, it is characterised in that described reaction temperature is
100～150 DEG C；Described reaction pressure is 3～8Mpa；Glycol dimethyl ether mass space velocity in described raw material
It is 0.3～2.0h-1；In described raw material, the volumn concentration of glycol dimethyl ether is 5～50%.
Method the most according to claim 1, it is characterised in that possibly together with dilute in described raw material
Outgassing body, at least one in nitrogen, helium, argon of described diluent gas.
Method the most according to claim 1, it is characterised in that described reactor is fixed bed
Reactor or tank reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510069951.9A CN105985312B (en) | 2015-02-09 | 2015-02-09 | A method of preparing Isosorbide-5-Nitrae-dioxane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510069951.9A CN105985312B (en) | 2015-02-09 | 2015-02-09 | A method of preparing Isosorbide-5-Nitrae-dioxane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105985312A true CN105985312A (en) | 2016-10-05 |
| CN105985312B CN105985312B (en) | 2018-11-02 |
Family
ID=57041714
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510069951.9A Expired - Fee Related CN105985312B (en) | 2015-02-09 | 2015-02-09 | A method of preparing Isosorbide-5-Nitrae-dioxane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105985312B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108129444A (en) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | A kind of method that serialization catalyzed conversion prepares 1,4- dioxane |
| CN110028484A (en) * | 2019-03-26 | 2019-07-19 | 铜仁学院 | A kind of oxygen-containing higher boiling aprotic polar solvent and preparation method thereof |
| CN114437018A (en) * | 2020-11-05 | 2022-05-06 | 中国科学院化学研究所 | Method for preparing 1, 4-dioxane compound by dehydrating and cyclizing diol compound |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5283472A (en) * | 1975-12-29 | 1977-07-12 | Nippon Oil Co Ltd | Preparation of #-dioxane and its substituted compounds |
| CN102659812A (en) * | 2012-05-17 | 2012-09-12 | 陈群 | Simple method for preparing 3,4-ethylenedioxythiophene |
| CN103130768A (en) * | 2011-11-30 | 2013-06-05 | 中国科学院大连化学物理研究所 | Preparation method of compound with 1,3-dioxane structure |
| CN103896907A (en) * | 2012-12-25 | 2014-07-02 | 中国科学院大连化学物理研究所 | Method used for preparing 1,4-dioxane from 1,3-dioxolane |
-
2015
- 2015-02-09 CN CN201510069951.9A patent/CN105985312B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5283472A (en) * | 1975-12-29 | 1977-07-12 | Nippon Oil Co Ltd | Preparation of #-dioxane and its substituted compounds |
| CN103130768A (en) * | 2011-11-30 | 2013-06-05 | 中国科学院大连化学物理研究所 | Preparation method of compound with 1,3-dioxane structure |
| CN102659812A (en) * | 2012-05-17 | 2012-09-12 | 陈群 | Simple method for preparing 3,4-ethylenedioxythiophene |
| CN103896907A (en) * | 2012-12-25 | 2014-07-02 | 中国科学院大连化学物理研究所 | Method used for preparing 1,4-dioxane from 1,3-dioxolane |
Non-Patent Citations (1)
| Title |
|---|
| RICCARDO BINI等: "Further insights into the chemistry of niobium and tantalum pentahalides with 1,2-dialkoxyalkanes: Synthesis of bromo- and iodoalkoxides, spectroscopic and computational studies", 《POLYHEDRON》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108129444A (en) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | A kind of method that serialization catalyzed conversion prepares 1,4- dioxane |
| CN110028484A (en) * | 2019-03-26 | 2019-07-19 | 铜仁学院 | A kind of oxygen-containing higher boiling aprotic polar solvent and preparation method thereof |
| CN114437018A (en) * | 2020-11-05 | 2022-05-06 | 中国科学院化学研究所 | Method for preparing 1, 4-dioxane compound by dehydrating and cyclizing diol compound |
| CN114437018B (en) * | 2020-11-05 | 2023-06-20 | 中国科学院化学研究所 | Method for preparing 1, 4-dioxane compound by dehydration cyclization of diol compound |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105985312B (en) | 2018-11-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103848730B (en) | Production device system and production process for polymethoxy dimethyl ether (PODE) | |
| CN1895776B (en) | Catalyst for producing dimethyl ether by methanol liquid-phase or mixed-phase dewatering method | |
| CN103172517B (en) | Methyl methoxyacetate preparation method | |
| WO2011143976A1 (en) | Method for preparing polymethoxy dimethyl ethers by acetalization reaction of formaldehyde and methanol | |
| CN101265152B (en) | Application of ionic liquid used as solvent in benzene and cyclohexane extraction, rectification and separation | |
| CN103172516B (en) | Method for producing methyl methoxyacetate by methylal vapor-phase carbonylation by using supported heteropoly acid catalyst | |
| CN102249869A (en) | Technical process for catalytically synthesizing polymethoxy dimethyl ether by ionic liquid | |
| CN103506171B (en) | Modification acid cation exchange resin and uses thereof | |
| US10377689B2 (en) | Process for preparing polyoxymethylene dimethyl ethers from formaldehyde and methanol in aqueous solutions | |
| JP6549793B2 (en) | Process for producing ethylene glycol by directly producing ethylene glycol dimethyl ether from ethylene glycol monomethyl ether | |
| CN105985312A (en) | Method for preparing 1, 4-dioxane | |
| CN109721462B (en) | Method for preparing long-chain alkyl benzene | |
| CN106588589A (en) | Purification method for polyoxymethylene dimethyl ether(PODE) | |
| CN105585455A (en) | Method of preparing ethylene glycol monomethyl ether through continuous etherification method | |
| Wang et al. | Constructing ternary deep eutectic solvents with multiple sites for ammonia storage | |
| CN108250053B (en) | Method and system for preparing glycerin alkyl ether | |
| CN102452934A (en) | Preparation method of sec-butyl acetate | |
| KR970001489B1 (en) | Process for producing trioxan | |
| CN103664520B (en) | The method of Virahol is prepared in a kind of propylene hydration reaction | |
| CN104058941B (en) | The method of dimethyl ether by methanol dehydration | |
| CN106588597A (en) | Method for purifying polyoxyethene dimethyl ether | |
| CN109694044A (en) | A kind of preparation method of Zoamix azanol | |
| CN106542977B (en) | A method of synthesis polymethoxy dimethyl ether | |
| CN109721584B (en) | Method for preparing 1, 4-dioxane | |
| CN104230941B (en) | The production method of triethylene diamine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20181102 Termination date: 20220209 |