CN110372716A - A kind of method that sorbierite successive reaction prepares isobide - Google Patents
A kind of method that sorbierite successive reaction prepares isobide Download PDFInfo
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- CN110372716A CN110372716A CN201910748764.1A CN201910748764A CN110372716A CN 110372716 A CN110372716 A CN 110372716A CN 201910748764 A CN201910748764 A CN 201910748764A CN 110372716 A CN110372716 A CN 110372716A
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- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
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Abstract
The present invention relates to a kind of methods that sorbierite successive reaction prepares isobide.The invention is characterised in that being mixed in a certain proportion charging using fixed bed reactors with sorbierite and solvent, the porous solid acid catalyst of specific structure being loaded in fixed bed reactors.In the present invention, sorbierite carries out dehydration under certain optimal conditions and prepares isobide, using split-phase kettle recycling design；Isobide obtains isosorbide product after purification, crystallization and separation respectively.Present invention has an advantage that solid acid catalysis sorbierite high-efficiency dehydration prepares isobide using sorbierite and solvent mixed feeding；Realize that catalyst is quickly separated with product serialization, isobide yield 99%, purity 99.9% reaches WS1- (X-379) -2004Z standard.
Description
Technical field
The present invention relates to a kind of preparation methods of isobide, specifically prepare different sorb by raw material serialization of sorbierite
Alcohol.
Background technique
Isobide is the second dehydration product of sorbierite, is known as the following important biology base industrial chemicals, answers extensively
For food, makeup, plastics, medicine and other fields.The medical value of isobide is significant, inherently a kind of effective infiltration
Property oral dehydration and diuresis medicine and cardiovascular drugs Ismo 20 prepare raw material.
Since medical market is relatively small, people are affected to a certain extent in the research of isobide preparation field.
Raising with the increasingly depleted and people of world energy sources resource to synthetic polymeric's substance quality requirement, under study for action it is found that
The unique effect of isobide improvement polymer property, can be used for the polymer such as polyethers, polyester, polyurethane, polycarbonate
Modified, isobide participates in polymerization and is remarkably improved polymer high-temperature behavior and anti-impact force performance, and it is transparent to assign materials optical
Property and biodegradability.The extensive use of isobide, which has also further been pushed, produces different sorb using sorbierite as raw material
The research of alcohol, because its raw material sorbierite is prepared by glucose hydrogenation, abundance is cheap；Isobide is unique again
Can industrialized production biology base glycol, so future market has a extensive future.
CN143061A discloses a kind of continuity method for preparing anhydrosugar alcohol and its reactor used, and this method, which uses, to be contained
The sorbitol aqueous solution and sulfuric acid that amount is 70%, are passed through nitrogen into reactor and are reacted, and finally tie again through distillation, melt again
Crystalline substance obtains product isobide.Though this method cost of material investment is small, entire technique is intermittently operated, and production efficiency is low
Under, and sulfuric acid to production equipment seriously corroded and causes the problems such as seriously polluting to environment as catalyst.
CN108129488A discloses a kind of method that catalyzing sorbitol adds hydrogen to be dehydrated, and this method is using hydrogen as reaction
The sorbitol aqueous solution that content is 50% is passed through in fixed bed reactors plus hydrogen dehydration prepares isobide by gas.This method is adopted
Though avoiding corrosion of the liquid acid catalyst to equipment with heterogeneous catalyst, bed blending water content is too high, leads to dehydration speed
Rate is slow, and sorb alcohol conversion only has 68.2%, and isobide is selectively only 45%, and entire raw materials technology utilization rate is low, raw
Low efficiency is produced, industrialized production is not suitable for.
CN109369666A discloses a kind of method of solid acid synthesis isobide, and this method is original with sorbitol solution
Material, using compound solid-acid as catalyst, dehydration catalyzing sorbitol synthesizes isobide in two steps.This method isobide rubs
You can reach 87.21% by yield, but process flow cannot continuously prepare isobide, and production efficiency is low, and economic benefit is undesirable.
CN107141301A discloses a kind of preparation method for crystallizing isobide, and this method produces different mountain using fusion method
Then pears alcohol reaction solution carries out pure water dilution, filtering, mixed using decoloration deionization and separating mixture device processing isobide
Liquid is closed, then passes through the crystallization of room temperature Aqueous phase, dry acquisition isobide.This method obtains isosorbide content 98% or more,
Preparation flow is without acid-base catalysis, but entire technique is Batch Process, produces low efficiency, production capacity is low, and to device required precision
It is higher, it is suitable only for small lot production.
CN104788465A discloses a kind of isobide preparation process, and this method produces different mountain using piston flow reactor
Pears alcohol reaction solution purifies isobide reaction solution using rectifying column and obtains product isobide, though this method raw material availability
Height, and operating flexibility is big, but liquid acid catalyst severe corrosion to equipment is used, and energy consumption is higher, seriously polluted.
Therefore, it on the basis of ensuring isobide purity, realizes industrialized production, and solves energy consumption height, the wasting of resources
And the problems such as environmental pollution, currently to need the difficulty overcome.
Summary of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of methods that sorbierite successive reaction prepares isobide, and
And solvent is Ke Xunhuanliyong in production process, isobide production efficiency is low, raw material cannot make full use of in solution current process,
Energy consumption is higher and production process the problems such as environmental pollution is serious.
To achieve the goals above, technical scheme is as follows:
Method provided by the present invention includes four units interconnected: (1) feed material preparation units；(2) fixed bed
Reaction member；(3) product separative unit；(4) purifying products unit；
As a preferred solution of the present invention, the feed material preparation units include stirred tank and raw material buffering interconnected
Tank；
Preferably, feeding line is connected with stirred tank feed inlet, stirred tank discharge port and raw material surge tank feed inlet phase
Connection；
As the preferred technical solution of the present invention, stirred tank sets heating device.
Because sorbierite is characters powder, need first in a stirring kettle heat temperature raising melt sorbierite for liquid, and it is organic molten
Agent enters fixed bed reactors together.The present invention is not specifically limited heating mode, and what can be enumerated has electric heating or thermally conductive
Medium heating etc..Heat-conducting medium uses but is not limited to conduction oil, steam, any one in fused salt.
As the preferred technical solution of the present invention, fixed bed reactors fill the porosu solid of finite field acidic ion liquid
Acid catalyst.The active confinement group of solid acid catalyst is divided into the acidic ion liquid of sulfonic acid funtionalized, including X in the present invention+
It can be imidazoles, quaternary ammonium, pyridines, pyroles, heterocyclic compound cation；N is 0 or positive integer B, C etc.；Y-For halogen
Ion Cl-、Br、I-、BF4 -、PF6 -、HSO4 -、CF3SO3 -、C(CF3SO2)-,NO3 -、CH3COO-, m is the positive integer between 1~8,
Carrier is porous material, including metal oxide, resin, molecular sieve, CNT, MOF, the cellular solids such as COF but is not limited to it
One of or at least two combination.
Preferably, raw material surge tank bottom discharge port is connected with fixed bed reactors bottom feed inlet.
As the preferred technical solution of the present invention, fixed bed reaction is the endothermic reaction, and fixed bed reactors are equipped with heating dress
It sets, the present invention is not specifically limited heating method, and what can be enumerated has electric heating, steam heat-exchanging, fused salt heat exchanging or conduction oil
One of heat exchange or any two kinds of combinations etc..
As the preferred technical solution of the present invention, product separative unit is knockout drum, separation buffer tank and split-phase kettle.This hair
Bright not to be specifically limited to unpack format, what can be enumerated has flash tank, split-phase kettle or destilling tower etc..
Preferably, fixed bed reactors top discharge mouth is connected with knockout drum feed inlet, and two equipment rooms are equipped with condensation
Device.
Preferably, knockout drum top discharge mouth is connected with separation buffer tank feed inlet.
Preferably, separation buffer tank discharge port is connected with split-phase kettle feed inlet.
Preferably, split-phase kettle side is equipped with one group of shut-off valve, and the other side is equipped with view cup.
Preferably, cut-off valve outlet is connected with solvent collecting tank, and split-phase kettle bottom discharge port and wastewater collection tank are fed
Mouth is connected.
Preferably, solvent collecting tank discharge port is connected with stirred tank other side feed inlet, realizes toluene solvant recycling.
As the preferred technical solution of the present invention, after split-phase kettle watches view cup, water-oil separating is realized in the control of boundary position, is passed through
Side shut-off valve releases oily phase,
As the preferred technical solution of the present invention, purifying products unit include refining kettle interconnected, product surge tank,
Mixer, first degree crystalline separator, level-one evaporator, the second-order separation machine and secondary evaporimeter.
Preferably, flash tank bottom discharge port is connected with refining kettle feed inlet.
Preferably, refining kettle top discharge mouth is connected with product surge tank feed inlet, and two equipment rooms are equipped with condenser.
Preferably, refining kettle bottom is equipped with discharge pipe, and material is heavy constituent.
Preferably, product surge tank discharge port is connected with mixer feed inlet.
Preferably, solvent make-up pipeline is connected with mixer feed inlet.
Preferably, mixer discharge port is connected with first degree crystalline separator feed inlet.
As the preferred technical solution of the present invention, the present invention is not specifically limited crystallizing tank refrigeration form, can be enumerated
Have cooling water freeze or refrigerant refrigeration etc..
Preferably, first degree crystalline separator bottom discharge port, material are pharmaceutical grade sorbierite.
Preferably, first degree crystalline separator discharge port is connected with level-one evaporation feed liquor mouth.
Preferably, level-one evaporator top discharge mouth is connected with the condenser on refining kettle top discharge pipeline, thus
Realize solvent recovery.
Preferably, level-one base of evaporator discharge port is connected with secondary crystallization separator feed inlet.
Preferably, secondary crystallization separator bottom discharge port, material are technical grade sorbierite.
Preferably, secondary crystallization separator discharge port is connected with secondary evaporimeter feed inlet.
Preferably, secondary evaporimeter top discharge mouth is connected with level-one evaporator top discharge pipeline.
On the other hand, a kind of sorbierite can successive reaction prepare isobide method, comprising the following steps:
(1) feed material preparation units: raw material sorbierite is heated to 60~100 DEG C with solvent after stirred tank mixes, material
From stirred tank bottom, it is spare to enter raw material surge tank for discharging；
(2) fixed bed reaction unit: being preheated to 130~200 DEG C for fixed bed, material from raw material surge tank bottom discharge,
Enter in reactor through fixed bed reactors bottom feed inlet, 2~8h of residence time, 130~180 DEG C of reaction temperature；
(3) product separative unit: material is from fixed bed reactors top discharge, into knockout drum, knockout drum operation temperature
It is 100~200 DEG C, absolute pressure is 1~110kPa, and wherein in knockout drum, gaseous phase materials are mainly solvent and water from top discharge mouth
Enter in separation buffer tank after condenser condenses, after then material enters split-phase kettle from bottom discharge, it is real to pass through the control of boundary position
Existing water-oil separating, oil mutually enter solvent collecting tank, are recycled back to stirred tank from solvent collecting tank bottom discharge and complete solvent recovery, water
Mutually enter wastewater collection tank；
(4) purifying products unit: liquid phase material is mainly isobide reaction solution in knockout drum, enters essence from bottom discharge
Kettle processed, temperature in the kettle steam crude product isobide, residual in refining kettle under conditions of 130~230 DEG C, 1~110kPa of absolute pressure
Material is discharged from bottom pipeline.Isobide crude product passes through with solvent according to the ratio of quality 1:3~4 after being condensed by condenser to be mixed
Clutch enters first degree crystalline separator after mixing, by bottom line, and crystal obtains the different mountain of pharmaceutical grade after filtration drying
Pears alcohol, non-separation of material enter level-one evaporator and steam solvent, and gaseous phase materials enter mixer through condenser and recycle.Liquid phase
Material enters secondary crystallization separator, and crystal obtains technical grade isobide after filtration drying, and non-separation of material enters second level
Evaporator, gaseous phase materials complete solvent recovery after condenser condenses, into mixer.
Preferably as the preferred technical solution of the present invention, sorbierite is toluene as the preferred mixed solvent of raw material, optional
Non-polar system includes benzene,toluene,xylene, ethylbenzene, paraxylene, meta-xylene, isopropylbenzene, styrene or ether etc. but not
It is limited to one such or at least two combinations.
Preferably, the charge-mass ratio of sorbierite and solvent is 1:20~100 in the step (1), such as be can be
1:20,1:30:, 1:40,1:50,1:60,1:70,1:80,1:90 and 1:100 etc..
Preferably, step (2) the fixed bed reactors absolute pressure be 1~110kPa, e.g. absolute pressure 1kPa, 10kPa,
20kPa, 30kPa, 40kPa, 50kPa, 60kPa, 70kPa, 80kPa, 90kPa, 100kPa and 110kPa etc..
Preferably, knockout drum operation temperature is 180~200 DEG C in the step (3), such as can be 100 DEG C, 110
DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C and 200 DEG C etc.；In knockout drum absolute pressure be 1~
110kPa, for example, can be absolute pressure 1kPa, 10kPa, 20kPa, 30kPa, 40kPa, 50kPa, 60kPa, 70kPa, 90kPa,
100kPa and 110kPa etc..
Preferably, in the step (4) refining kettle operation temperature be 130~230 DEG C, such as can be 130 DEG C, 140 DEG C,
150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 220 DEG C and 230 DEG C etc., operating pressure be absolute pressure 1~
110kPa for example can be 1kPa, 10kPa, 20kPa, 30kPa, 40kPa, 50kPa, 60kPa, 70kPa, 90kPa, 100kPa and
110kPa etc.；.
Preferably, in the step (4), recrystallisation solvent is ethyl acetate, such as can be ethyl acetate, acetone or benzene
Deng.
Preferably, first degree crystalline separator and secondary crystallization separator operating temperature are -20~10 in the step (4)
DEG C, such as can be -20 DEG C, -15 DEG C, -10 DEG C, -5 DEG C, 0 DEG C, 5 DEG C etc. or 10 DEG C；Crystallization time is 30~360min, such as
It can be 30min, 90min, 150min, 210min, 270min, 330min and 360min etc..
Preferably, in step (4), level-one evaporator and secondary evaporimeter operation temperature are 70~100 DEG C, such as be can be
70 DEG C, 80 DEG C, 90 DEG C and 100 DEG C etc.；Absolute pressure be 1~110kPa for example can be absolute pressure 1kPa, 10kPa, 20kPa, 30kPa,
40kPa, 50kPa, 60kPa, 70kPa, 90kPa, 100kPa and 110kPa etc..
Compared with prior art, the invention has the following advantages:
(1) present invention uses fixed bed reactors, with sorbierite and solvent in certain proportion mixed feeding, fixed bed reaction
Device loads the porous solid acid catalyst of specific structure, and sorbierite reaction can be made more abundant, and conversion ratio reaches 100%, selection
Property be 97%, isobide yield be 97%, prepared isobide purity reaches pharmaceutical grade, purity 99.9%；
(2) high production efficiency of the present invention solves the deficiency of current discontinuous operation, and 30% is saved compared with traditional handicraft
Energy consumption, process is simple, easy to operate.
(3) catalyst of the present invention has reaction efficiency fast compared with traditional processing technology, and product purity is high,
High activity with it is highly selective, and the features such as no pollution to the environment.
Detailed description of the invention
Fig. 1 is the method structural schematic diagram for the coproduction isobide that the embodiment of the present invention 1 provides:
Wherein 1 stirred tank, 2 heaters, 3 raw material surge tanks, 4 fixed bed reactors, 5 knockout drums, 6 condensers, 7 separation are slow
Rush tank, 8 split-phase kettles, 9 solvent collecting tanks, 10 wastewater collection tanks, 11 refining kettles, 12 condensers, 13 product surge tanks, 14 mixing
Device, 15 first degree crystalline separators, 16 level-one evaporators, 17 secondary crystallization separators, 18 secondary evaporimeters, arrow generation as shown in the figure
Table Flow of Goods and Materials direction.
Specific embodiment
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, the present invention is done further in detail below
Explanation.But following embodiments is only simple example of the invention, does not represent or limit the scope of the present invention,
The scope of the present invention is subject to claims.
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached in the embodiment of the present invention
Figure, technical scheme in the embodiment of the invention is clearly and completely described.Those skilled in the art are it will be clearly understood that described
Specific embodiment is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.Herein in attached drawing description and
The component of the embodiment of the present invention shown can be used as a variety of different configurations to arrange and design.
Therefore, the detailed description of the embodiment of the present invention provided in attached drawing is not intended to limit below and this is claimed
The range of invention, but it is merely representative of selected embodiment of the invention.Based on the embodiments of the present invention, those skilled in the art
Every other embodiment obtained without creative efforts, shall fall within the protection scope of the present invention.
1 further description of the specific embodiments of the present invention with reference to the accompanying drawing, implements to be only used for below more clear
Illustrate to Chu technical solution of the present invention, and not intended to limit the protection scope of the present invention.
Embodiment 1
A kind of sorbierite can the successive reaction method for preparing isobide, as shown in Figure 1: include 1 stirred tank, 2 heaters,
3 raw material surge tanks, 4 fixed bed reactors, 5 knockout drums, 6 condensers, 7 separation buffer tanks, 8 split-phase kettles, 9 solvent collecting tanks, 10
Wastewater collection tank, 11 refining kettles, 12 condensers, 13 product surge tanks, 14 mixers, 15 first degree crystalline separators, 16 level-ones are steamed
Send out device, 17 secondary crystallization separators, 18 secondary evaporimeters；
Wherein 1 stirred tank discharge port is connected with 2 raw material surge tank feed inlets, 3 raw material surge tank discharge ports and 4 fixed beds
Reactor feed mouth is connected；
The discharge port of 4 fixed bed reactors is connected with the feed inlet of 7 knockout drums, and two equipment rooms are equipped with 6 condensers；
7 separation buffer tank top discharge ports are connected with 8 split-phase kettle feed inlets, cut wherein 8 split-phase kettle sides are equipped with one group
Only valve, the other side are equipped with view cup；
9 solvent collecting tanks are connected with 8 split-phase kettle shut-off valves, 8 split-phase kettle bottom discharge ports and 10 wastewater collection tank phases
Connection；
9 solvent collecting tank bottom discharge ports are connected with 1 stirred tank, recycle for solvent recovery；
7 knockout drum bottom discharge ports are connected with 11 refining kettle feed inlets, and 11 refining kettle top discharge mouths and 13 products are slow
It rushes tank to be connected, and two equipment rooms are equipped with 12 condensers；
11 refining kettle bottoms are equipped with discharge pipe, and material is heavy constituent；
Solvent make-up pipeline is connected with 14 mixer feed inlets, 13 product surge tank discharge ports and 14 mixer feed inlets
It is connected；
14 mixer discharge ports are connected with 15 level-one separating feed mouths, and 15 first degree crystalline separator bottoms are equipped with discharge nozzle
Line, material are pharmaceutical grade isobide；
15 first degree crystalline separator other side discharge ports are connected with 16 level-one evaporation feed liquor mouths, 16 level-one evaporator tops
Portion's discharge port is connected with 12 condenser feed inlets；
16 level-one base of evaporator discharge ports are connected with 17 secondary crystallization separator feed inlets, 17 secondary crystallization separators
Bottom is equipped with discharging pipeline, and material is technical grade isobide；
17 secondary crystallization separator other side discharge ports are connected with 18 secondary evaporimeter feed inlets, at the top of secondary evaporimeter
Discharge port is connected with 16 level-one evaporator top discharge pipelines.
Embodiment 2
A kind of successive reaction method for preparing isobide provided using embodiment 1 is included the following steps:
(1) feed material preparation units: raw material sorbierite and toluene are that 1:40 enters 1 stirred tank according to mass ratio, in 1 stirring
80 DEG C are heated to after kettle mixing, material is spare from the discharging of stirred tank bottom into 3 raw material surge tanks；
(2) fixed bed reaction unit: 4 fixed beds are preheated to 150 DEG C, material is from 3 raw material surge tank bottom discharges, through 4
Fixed bed reactors bottom feed inlet enters in reactor, residence time 6h, and 160 DEG C of reaction temperature；
(3) product separative unit: material is from 4 fixed bed reactors top discharges, into 5 knockout drums, knockout drum operation temperature
Degree is 150 DEG C, absolute pressure 30kPa, wherein gaseous phase materials are mainly that toluene and water are condensed from top discharge mouth through 6 in 5 knockout drums
Enter in 7 separation buffer tanks after device condensation, after then material is from bottom discharge into 8 split-phase kettles, oil is realized by the control of boundary position
Water separation after oil mutually enters 9 solvent collecting tanks, is recycled back to 1 stirred tank from bottom discharge port and completes solvent recovery, water phase enters 10
Wastewater collection tank；
(4) purifying products unit: liquid phase material is mainly isobide reaction solution in 5 knockout drums, is entered from bottom discharge
11 refining kettles, for temperature in the kettle at 200 DEG C, operating pressure steams crude product isobide, residual in refining kettle under conditions of being 10kPa
Material is discharged from bottom pipeline.Crude product isobide by 12 condensers condense after and ethyl acetate according to quality 1:3.5 ratio
Example is by 14 mixers, after mixing by bottom line into 15 first degree crystalline separators, crystal filtered, dry after obtain
Pharmaceutical grade isobide, non-separation of material enter 16 level-one evaporators and steam solvent, and gaseous phase materials are cold by 12 through overhead line
Condenser enters 14 mixers and recycles.Liquid phase material enters 17 secondary crystallization separators, and crystal obtains work after filtration drying
Industry grade isobide, non-separation of material enter 18 secondary evaporimeters, and gaseous phase materials are after the condensation of 12 condensers, into 14 mixers
Complete solvent recovery.
Wherein in step (2), 4 fixed bed reactors, absolute pressure 10kPa；
Wherein in step (4), crude product isobide and ethyl acetate are matched in 14 mixers as 1:3,15 first degree crystallines point
From with 17 secondary crystallization separator crystallization temperatures being -5 DEG C in device, level-one evaporator and secondary evaporimeter operation temperature are 85 DEG C,
Absolute pressure is 10kPa.
In the present embodiment, after being mixed according to a certain percentage after sorbierite and toluene heating, into being mounted with solid acid
Catalyst --- the fixed bed reactors of the metal oxide of confinement azochlorosulfonate acid ion liquid can continuously prepare isobide, and institute
Isobide purity reaches pharmaceutical grade 99.9%, solve that production efficiency caused by the intermittently operated of traditional handicraft is low and liquid
The problems such as acid catalyst is to the corrosion of production equipment, and saving energy consumption to improve raw material availability is optimal case, specific reaction ginseng
Number is referring to table 1.
Embodiment 3
The difference from example 2 is that sorbierite is anti-into 4 fixed bed reactors after 1 stirred tank mixes with dimethylbenzene
It answers, the operation temperature of 7 knockout drums is 190 DEG C, other techniques are same as Example 2.
In the present embodiment, the mixed solvent of raw material sorbierite and the operation temperature of 7 knockout drums are had adjusted, is ensuring not influence
It can be purchased according to the market price under the premise of isobide purity, specific response parameter is referring to table 1.
Embodiment 4
The difference from example 2 is that sorbierite is anti-into 4 fixed bed reactors after 1 stirred tank mixes with paraxylene
It answers, the operation temperature of 7 knockout drums is 190 DEG C, other techniques are same as Example 2.
In the present embodiment, the mixed solvent of raw material sorbierite and the operation temperature of 7 knockout drums are had adjusted, is ensuring not influence
It can be purchased according to the market price under the premise of isobide purity, specific response parameter is referring to table 1.
Embodiment 5
The difference from example 2 is that sorbierite is anti-into 4 fixed bed reactors after 1 stirred tank mixes with to ethylbenzene
It answers, the operation temperature of 7 knockout drums is 180 DEG C, other techniques are same as Example 2.
In the present embodiment, the mixed solvent of raw material sorbierite and the operation temperature of 7 knockout drums are had adjusted, is ensuring not influence
It can be purchased according to the market price under the premise of isobide purity, specific response parameter is referring to table 1.
Embodiment 6
The difference from example 2 is that using solid acid catalyst is filled with --- the resin of confinement azochlorosulfonate acid ion liquid
4 fixed bed reactors, other process conditions are same as Example 2.
In the present embodiment, the catalyst filled in fixed bed is had adjusted, it is ensured that under the premise of not influencing isobide purity
It can be purchased according to the market price.
Embodiment 7
The difference from example 2 is that using solid acid catalyst is filled with --- the CNT's of confinement azochlorosulfonate acid ion liquid
Fixed bed reactors, other process conditions are same as Example 2.
In the present embodiment, the catalyst filled in fixed bed is had adjusted, it is ensured that under the premise of not influencing isobide purity
It can be purchased according to the market price, specific response parameter is referring to table 1.
Embodiment 8
The difference from example 2 is that using solid acid catalyst is filled with --- the MOF's of confinement azochlorosulfonate acid ion liquid
Fixed bed reactors, other process conditions are same as Example 2.
In the present embodiment, the catalyst filled in fixed bed is had adjusted, it is ensured that under the premise of not influencing isobide purity
It can be purchased according to the market price, specific response parameter is referring to table 1.
Embodiment 9
The difference from example 2 is that using solid acid catalyst is filled with --- the COF's of confinement azochlorosulfonate acid ion liquid
Fixed bed reactors, other process conditions are same as Example 2.
In the present embodiment, the catalyst filled in fixed bed is had adjusted, it is ensured that under the premise of not influencing isobide purity
It can be purchased according to the market price, specific response parameter is referring to table 1.
Embodiment 10
The difference from example 2 is that using solid acid catalyst --- the molecular sieve of confinement azochlorosulfonate acid ion liquid is filled with
Fixed bed reactors, other process conditions are same as Example 2.
In the present embodiment, the catalyst filled in fixed bed is had adjusted, it is ensured that under the premise of not influencing isobide purity
It can be purchased according to the market price, specific response parameter is referring to table 1.
Embodiment 11
The difference from example 2 is that 1 stirred tank operation temperature is 60 DEG C, 4 fixed bed reactors reaction temperatures are 130
DEG C, operating pressure is absolute pressure 110kPa, reaction time 2h, other process conditions are same as Example 2.
In the present embodiment, the operating condition of raw material Yu processing unit and fixed bed reaction unit is had adjusted, energy consumption is reduced,
But the disadvantage is that raw material availability is low, the conversion ratio of sorbierite only has 96%, and isobide is selectively only 87%, and isobide
Purity is reduced by up to can only achieve technical grade≤98%.
Embodiment 12
The difference from example 2 is that 1 stirred tank operation temperature is 100 DEG C, 4 fixed bed reactors reaction temperatures are 230
DEG C, operating pressure is absolute pressure 1kPa, reaction time 6h, other process conditions are same as Example 2.
In the present embodiment, the operating condition of raw material Yu processing unit and fixed bed reaction unit is had adjusted, keeps sorbierite anti-
Should more sufficiently, while isobide purity remains at pharmaceutical grade 99.9%, but the disadvantage is that isobide is selectively fallen to
90%, and energy consumption is high, high production cost.
Embodiment 13
The difference from example 2 is that it is 60 DEG C that 1 knockout drum absolute pressure, which is 90kPa operation temperature, purification temperature in the kettle is 130
DEG C, operating pressure is absolute pressure 90kPa, and the charge-mass ratio of ethyl acetate and crude product isobide is 1:3, the separation of 15 first degree crystallines
Device and 17 secondary crystallization separator crystallization temperatures are 10 DEG C, and the operation temperature of 16 level-one evaporators and 18 secondary evaporimeters is 70
DEG C, other process conditions are same as Example 2.
In the present embodiment, the operating condition of product separative unit Yu purifying products unit is had adjusted, reduces energy consumption, but lack
Point is that the decline of isobide purity only up to reach technical grade≤98%.
Embodiment 14
The difference from example 2 is that it is 180 DEG C that 1 knockout drum absolute pressure, which is 10kPa operation temperature, purification temperature in the kettle is
230 DEG C, operating pressure is absolute pressure 1kPa, and the charge-mass ratio of ethyl acetate and crude product isobide is 1:4,15 first degree crystallines point
It is -20 DEG C from device and 17 secondary crystallization separator crystallization temperatures, the operation temperature of 16 level-one evaporators and 18 secondary evaporimeters is
100 DEG C, other process conditions are same as Example 2.
In the present embodiment, the operating condition of product separative unit Yu purifying products unit is had adjusted, isobide is separated
With purify more abundant, gained isobide purity >=99.9%, but the disadvantage is that energy consumption is larger, high production cost.
Applicant's statement: of the invention is described in detail in above embodiments, but the content is only of the invention
Preferred embodiment should not be considered as limiting the scope of the invention.It is all to become according to equalization made by the present patent application range
Change and improve etc., it should still be within the scope of the patent of the present invention.
Table 1
| Serial number | Catalyst carrier | Solvent | Sorb alcohol conversion | Isobide selectivity |
| Embodiment 2 | Metal oxide | Toluene | 100 | 97 |
| Embodiment 3 | —— | Dimethylbenzene | 100 | 98 |
| Embodiment 4 | —— | Paraxylene | 99 | 95 |
| Embodiment 5 | —— | Ethylbenzene | 98 | 97 |
| Embodiment 6 | Resin | Toluene | 100 | 96 |
| Embodiment 7 | CNT | Toluene | 100 | 93 |
| Embodiment 8 | MOF | Toluene | 100 | 94.5 |
| Embodiment 9 | COF | Toluene | 100 | 93 |
| Embodiment 10 | Molecular sieve | Toluene | 100 | 92 |
Claims (8)
1. a kind of method that sorbierite successive reaction prepares isobide, after being mixed with sorbierite with solvent, in certain temperature and
The method for continuously preparing isobide is reacted under pressure, main feature includes four units interconnected: (1) raw material is located in advance
Manage unit (2) fixed bed reaction unit (3) product separative unit (4) purifying products unit.
Wherein the feed material preparation units are connect with fixed bed reaction unit, and the fixed bed reaction unit separates list with product
Member connection, the product separative unit are connect with purifying products unit；
The feed material preparation units include stirred tank and raw material surge tank；
The porous solid acid catalyst of the fixed bed reactors filling finite field acidic ion liquid, molecular structure such as following formula institute
Show；
The product separative unit is knockout drum and split-phase kettle includes but is not limited to one or both of flash tank, destilling tower
Combination；
The purifying products unit includes refining kettle, product surge tank, mixer, first degree crystalline separator, level-one evaporator, two
Grade crystal separator, secondary evaporimeter.
2. a kind of method that sorbierite successive reaction prepares isobide, it is characterised in that the method mainly includes following step
It is rapid:
(1) feed material preparation units: sorbierite and solvent enter stirred tank according to the charge ratio of quality 1:20~100, are stirring
After kettle mixing, 60~100 DEG C are heated to, material is spare from the discharging of stirred tank bottom into raw material surge tank；
(2) fixed bed reaction unit: fixed bed is preheated to 130~180 DEG C, material is from raw material surge tank bottom discharge, through solid
Fixed bed reactor bottom feed inlet enters in reactor, 2~8h of residence time, and 130~180 DEG C of reaction temperature, operating pressure is
1~110kPa of absolute pressure；
(3) product separative unit: material is from fixed bed reactors top discharge, and into knockout drum, knockout drum operation temperature is 100
~200 DEG C, absolute pressure be 1~110kPa, wherein in knockout drum, gaseous phase materials be mainly solvent and water from top discharge mouth through condensing
Enter in separation buffer tank after device condensation, then material enters in split-phase kettle from bottom discharge, realizes grease by the control of boundary position
Separation, oil mutually enter solvent collecting tank, are recycled back to stirred tank from solvent collecting tank bottom discharge and complete solvent recovery, water phase enters
Wastewater collection tank；
(4) purifying products unit: liquid phase material is mainly isobide reaction solution in knockout drum, enters purification from bottom discharge
Kettle steams the purification of crude product isobide under conditions of 130~230 DEG C of temperature in the kettle, and residual material is arranged from bottom pipeline in kettle
Out.Crude product isobide passes through mixer according to quality 1:3~4 with solvent after condensing by condenser and passes through bottom after mixing
Portion's pipeline enters first degree crystalline separator, crystal filtered, dry after obtain pharmaceutical grade isobide, non-separation of material enters one
Grade evaporator steams solvent, and gaseous phase materials enter mixer through condenser and recycle.Liquid phase material enters secondary crystallization separation
Device, crystal obtain technical grade isobide after filtration drying, and non-separation of material enters secondary evaporimeter, and gaseous phase materials are through condensing
After device condensation, solvent recovery is completed into mixer.
3. the method that sorbierite successive reaction according to claim 2 prepares isobide, it is characterised in that step (1)
In, for sorbierite as raw material, the solvent is that non-polar system includes benzene,toluene,xylene, ethylbenzene, paraxylene, diformazan
Benzene, isopropylbenzene, styrene or ether etc. but be not limited to it is one such or at least two combination.
4. the method that sorbierite successive reaction according to claim 2 prepares isobide, the spy of fixed bed reactors
Sign is the porous solid acid catalyst of the confinement acidic ion liquid, the active confinement of solid acid catalyst in the present invention
Group is divided into the acidic ion liquid of sulfonic acid funtionalized, including X+It can be imidazoles, quaternary ammonium, pyridines, pyroles, jeterocyclic chemistry
Close object cation；N is 0 or positive integer etc.；Y-For halide ion Cl-、Br、I-、BF4 -、PF6 -、HSO4 -、CF3SO3 -、C
(CF3SO2)-,NO3 -、CH3COO-, m is the positive integer between 1~8, and carrier is porous material, including metal oxide, resin,
Molecular sieve, CNT, MOF but are not limited to one such or at least two combinations at the cellular solids such as COF.
5. the method that sorbierite successive reaction according to claim 1 prepares isobide, the spy of fixed bed reactors
Sign is that the fixed bed reactors are equipped with heating device, and the heating device is electric heating, steam heat-exchanging, fused salt heat exchanging or leads
Hot oil heat exchange one of or at least two combination.
6. the method that sorbierite successive reaction according to claim 1 prepares isobide, feed material preparation units
It is characterized in that stirred tank is equipped with heat exchanger, the heat transferring medium uses but be not limited to conduction oil, steam, any one in fused salt
Kind.
7. the method that sorbierite successive reaction according to claim 1 prepares isobide, purifying products element characteristic
It is that the purifying products unit includes distillation, crystallization, separation and dry middle a kind of or at least two processes combination.
8. the method that sorbierite successive reaction according to claim 1 prepares isobide, crystal separator feature exist
Include centrifuge, crystallizer, destilling tower or flash tank etc. in the unpack format but is not limited to one such or at least two
Combination.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114849637A (en) * | 2022-06-17 | 2022-08-05 | 郑州中科新兴产业技术研究院 | Device and method capable of continuously reacting and purifying isosorbide |
| CN115959973A (en) * | 2022-12-30 | 2023-04-14 | 广东希必达新材料科技有限公司 | Method for continuously producing dicyclopentadiene glycol ether |
| CN117550621A (en) * | 2024-01-11 | 2024-02-13 | 恒泰军航高分子材料(山东)有限公司 | Method and device for preparing high-purity BN ceramic precursor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107955012A (en) * | 2017-12-05 | 2018-04-24 | 中国科学院过程工程研究所 | A kind of product preparative separation system and its processing method and purposes for being less than product and raw material for accessory substance boiling point |
-
2019
- 2019-08-14 CN CN201910748764.1A patent/CN110372716A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107955012A (en) * | 2017-12-05 | 2018-04-24 | 中国科学院过程工程研究所 | A kind of product preparative separation system and its processing method and purposes for being less than product and raw material for accessory substance boiling point |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114849637A (en) * | 2022-06-17 | 2022-08-05 | 郑州中科新兴产业技术研究院 | Device and method capable of continuously reacting and purifying isosorbide |
| CN115959973A (en) * | 2022-12-30 | 2023-04-14 | 广东希必达新材料科技有限公司 | Method for continuously producing dicyclopentadiene glycol ether |
| CN117550621A (en) * | 2024-01-11 | 2024-02-13 | 恒泰军航高分子材料(山东)有限公司 | Method and device for preparing high-purity BN ceramic precursor |
| CN117550621B (en) * | 2024-01-11 | 2024-03-22 | 恒泰军航高分子材料(山东)有限公司 | Method and device for preparing high-purity BN ceramic precursor |
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