CN208949158U - A kind of glucose continuously hydrogen adding prepares the device of sorbierite - Google Patents
A kind of glucose continuously hydrogen adding prepares the device of sorbierite Download PDFInfo
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Abstract
The utility model relates to the device that a kind of glucose continuously hydrogen adding prepares sorbierite, belongs to plus hydrogen produces sorbierite technical field.It include: mixer, for preparing Glucose Liquid；Fixed bed reactors are connected to mixer, for carrying out the first hydrogenation to Glucose Liquid；The first hydrogen inlet is equipped in the bottom of fixed bed reactors；Slurry bed reactor, is connected to fixed bed reactors, for carrying out the second hydrogenation to the feed liquid after the first hydrogenation；Separator is connected to slurry bed reactor, carries out solid-liquid separation treatment for the material to the second hydrogenation；De-watering apparatus is connected to the hydrogen discharge of separator, for carrying out the hydrogen of discharge except water process；Compressor is connected to de-watering apparatus, for the hydrogen repressurization after water removal；The gas vent of compressor is connected to fixed bed reactors and/or slurry bed reactor；The liquid outlet of separator passes sequentially through decoloration kettle, filter, ion exchange resin column and is connected to concentration kettle.
Description
Technical field
The utility model relates to the device that a kind of glucose continuously hydrogen adding prepares sorbierite, belongs to plus hydrogen produces sorbierite skill
Art field.
Background technique
Sorbierite and mannitol, xylitol, maltitol etc. are all edible sugar alcohols, at the same again be production vitamin C, this
The raw material of Pan, tween and plant chemical industry alcohol, purposes are extremely wide.Currently, sorbierite is widely used to medicine, surface-active
The industries such as agent, daily-use chemical industry, food processing.
The industrialized production of sorbierite is mainly based on glucose hydrogenation: in the condition with the presence of catalyst certain temperature
Under, with Glucose Liquid reduction reaction occurs for hydrogen in a kettle, generates sorbierite.Glucose hydrogenation process can release big
The heat of amount, gas reactor expansion will cause system overpressure, bring very big risk, generalling use safety valve to protect is
System, system overpressure safety valve jumping up, high temperature and high pressure gas release, while taking away heat, pressure reduction in kettle.The gas of release
As hydrogen and water vapour are still danger source, simultaneously although reducing risk by modes such as fire arrester, high altitude discharges
Cause hydrogen loss.Reaction process needs hydrogen supersaturated, and to improve inversion rate of glucose, thoroughly, hydrogen is often for hydrogenation
It is excessive, and reacting terminates, recycling hydrogen and continuous circulation plus hydrogen are badly in need of solving, and require continuous flowing stabilized hydrogenation.
Utility model content
The purpose of this utility model is: providing a kind of continuously flow and adds hydrogen production sorbierite new process, effective solution
The critical issue of large-scale sorbitol production device serialization enlargement, keeps hydrogenation reaction safer, reliably, reacts more thorough.
It is widely used in the production of biomass chemical industry alcohol, better than the interval and semi-continuous process of traditional handicraft, greatly improves reaction efficiency, is used
In sorbierite, xylitol, the production of the biomass chemical industry alcohol such as mannitol.
The first aspect of the utility model, provides:
A kind of method that glucose continuously hydrogen adding prepares sorbierite, includes the following steps:
Step 1, prepares the Glucose Liquid of 40~50wt% concentration, and adjusts pH to 6~7；
Glucose Liquid and hydrogen are continuously added into fixed bed reactors by step 2, carry out the first hydrogenation；
Reaction solution obtained in first hydrogenation is continuously added into slurry bed reactor by step 3, carries out second step
Hydrogenation；
Step 4 cools down to reaction solution obtained in the second hydrogenation, and recycles hydrogen, retained and filters out catalyst, and obtained
To Sorbitol solution crude product；
Step 5, Sorbitol solution crude product successively pass through decolorization, filtration treatment, ion exchange desalting processing, are concentrated by evaporation
Processing, obtains sorbierite.
In one embodiment, the Glucose Liquid temperature in step 1 is 80~90 DEG C.
In one embodiment, 10.5~12.5MPa of reactor pressure in step 2, temperature are controlled at 90~130 DEG C,
Residence time of material 1~3 hour.
In one embodiment, 11.0~13.5MPa of reactor pressure in step 3, temperature are controlled at 100~140 DEG C,
Residence time of material 1~3 hour.
In one embodiment, after the Glucose Liquid in step 1 is using the processing of Electro Sorb removing chloride, it is re-fed into step 2
Hydrogenation.
In one embodiment, the hydrogenation in step 2 uses Ru system or Ni series catalysts.
In one embodiment, the hydrogenation in step 3 uses nickel ferrite based magnetic loaded/Ru double-layer catalyst of zirconium oxide load,
Preparation method includes the following steps:
S1: it prepares and contains 4~6wt%ZrOCl2·8H2O, 1.5~2.5wt% polystyrene microsphere, 6~8wt% water solubility are formed sediment
The aqueous solution of powder and 30~40wt% ethyl alcohol, wherein the average grain diameter of polystyrene microsphere is 10~20 μm, is added dropwise 2~4wt%'s
HCl solution adjusts pH to 3~4 and 1~2h of reaction is hydrolyzed at 45~50 DEG C, and ammonium hydroxide is then added dropwise again and adjusts pH to 5~6,
Ageing 12~18h of reaction is carried out at 20~25 DEG C, and zirconium colloidal sol is made to be carried on microsphere surface；Microballoon use is centrifugated again,
After drying, it is sintered 1~2h removal polystyrene and water soluble starch in 1080~1120 DEG C of oxygen atmospheres, it is more to obtain zirconium oxide
Hole is microsphere supported；
S2: zirconium oxide porous microsphere carrier, water, water soluble starch are uniformly mixed according to weight ratio 1:5~8:1~3, so
It is evaporated under reduced pressure afterwards and removes solvent, then 600~700 DEG C of 1~2h of roasting in nitrogen atmosphere, the zirconium oxide for obtaining material with carbon-coated surface carries
Body；
S3, by the Zirconia carrier of material with carbon-coated surface and dehydrated alcohol according to the blending constituent dispersion liquid of weight ratio 1:70~80,
The ethanol solution containing 0.5mol/L ferric nitrate and 0.25mol/L nickel nitrate is prepared again, dispersion liquid and dehydrated alcohol is molten
Liquid is mixed according to volume ratio 1:1~1.5, then NaOH solution is added dropwise, and the molar ratio of NaOH and ferric nitrate is 4.5~5:1, and is continued
It is stirred to react 1~2h, then carries out hydrothermal synthesis, hydro-thermal reaction 18 at 170~180 DEG C~for 24 hours, by product centrifugation, deionization
After water washing, freeze-drying obtains the catalyst of load nickel ferrite based magnetic loaded；
S4, will load the catalyst of nickel ferrite based magnetic loaded, ruthenic chloride, water, ethylene glycol according to weight ratio 1:0.2~0.5:180~
200:20~30 are uniformly mixed, and nitre acid for adjusting pH are added to 1~2,10~12h of back flow reaction at 85~90 DEG C, reaction is completed
Afterwards, catalyst obtains nickel ferrite based magnetic loaded/Ru double-layer catalyst of zirconium oxide load after centrifugation, washing, drying.
The second aspect of the utility model, provides:
A kind of glucose continuously hydrogen adding prepares the device of sorbierite, comprising:
Mixer, for preparing Glucose Liquid；
Fixed bed reactors are connected to mixer, for carrying out the first hydrogenation to Glucose Liquid；In fixed bed reaction
The bottom of device is equipped with the first hydrogen inlet；
Slurry bed reactor, is connected to fixed bed reactors, for carrying out the second hydrogen to the feed liquid after the first hydrogenation
Change reaction；
Separator is connected to slurry bed reactor, carries out solid-liquid separation treatment for the material to the second hydrogenation；
De-watering apparatus is connected to the hydrogen discharge of separator, for carrying out the hydrogen of discharge except water process；
Compressor is connected to de-watering apparatus, for the hydrogen repressurization after water removal；The gas vent of compressor connects
In fixed bed reactors and/or slurry bed reactor；
The liquid outlet of separator passes sequentially through decoloration kettle, filter, ion exchange resin column and is connected to concentration kettle；
The Sorbitol solution that decoloration kettle is used to obtain separator carries out decolorization；After filter is used for decolorization
Sorbitol solution is filtered processing；Ion exchange resin column is used to carry out desalting processing to the Sorbitol solution after filtration treatment；It is dense
Contracting kettle is for being evaporated concentration to the Sorbitol solution after desalting processing.
In one embodiment, de-watering apparatus is condensation de-watering apparatus or absorption de-watering apparatus.
In one embodiment, decoloration kettle is filled with active carbon.
In one embodiment, what is filled in ion exchange resin column is acidulous acrylic acid's cation resin or weak
Basicity styrene series anion resin.
In one embodiment, mixer is connected to fixed bed reactors by electric adsorption device.
In terms of the third of the utility model, provide:
Above-mentioned glucose continuously hydrogen adding prepares the device of sorbierite in the application being used to prepare in sorbierite.
Beneficial effect
The utility model uses differential pressure type fixed bed and slurry bed reactor substep hydrogenates, the traditional work of the Summary on technology
On the basis of skill (interval, one-pot) hydrogenation, continuous flowing new process for hydrogenation has been started, it is therefore intended that greatly improve production
Efficiency and product quality.Innovative point is that continuous hydrogenation, hydrogen recycle, and reaction solution discharging is as clear as crystal, simplifies filtering,
With decoloration process, keep reaction mass good, intelligence degree is high, and system operation is more steady, and it is anti-to revolutionize traditional plus hydrogen
Mode is answered, hydrogenates liquid glucose in continuous flow process, reaction speed is fast, and side reaction is few, and product quality is more preferable.
This proprietary technology has the advantage that
(1) this proprietary technology is interlocked, bottom air inlet, kettle using automatic anti-temperature runaway superpressure interlock control system by pressure
Top row gas, thoroughly, side reaction is few, and product residual sugar is low for reaction；(2) this proprietary technology is right when reaction kettle exhaust is separated with high pressure
Hydrogen is recycled, is handled, and hydrogen is recycled, and is equipped with emptying or is explained discharge, and safety problem is guaranteed, and saves
Investment-saving, hydrogen utilization ratio are high；(3) two sections of continuous flowings plus hydrogen, the interior retention of catalyst kettle keep its unit consumption lower, purification essence
System is easier, and effect is more preferable；(4) device high-pressure reactor volume is big, and reaction pressure is high, and hydrogenation product is thorough, can be preferably
Applied to Vc grades of alcohol productions.
Detailed description of the invention
Fig. 1 is the device figure of the utility model.
Fig. 2 is the process flow chart of the utility model.
Wherein, 1, mixer；2, fixed bed reactors；3, slurry bed reactor；4, cooler；5, separator；6, it removes water
Device；7, compressor.
Specific embodiment
The utility model is described in further detail below by specific embodiment.But those skilled in the art will
Understand, the following example is merely to illustrate the utility model, and should not be regarded as limiting the scope of the utility model.In embodiment not
Particular technique or condition person are indicated, described technology or conditions carry out according to the literature in the art.Agents useful for same or instrument
Production firm person is not specified, being can be with conventional products that are commercially available.
" one embodiment " for addressing in the present specification, " another embodiment ", " embodiment " etc., refer to
In conjunction with the specific features of embodiment description, structure or it is included at least one embodiment generally described herein.
It is not centainly to refer to the same embodiment that statement of the same race, which occur, in multiple places in the description.Furthermore, it is understood that in conjunction with any
When embodiment describes a specific features, structure or feature, what is advocated is that this spy is realized in conjunction with other embodiments
Sign, structure or feature are also fallen in the application scope of the claimed.
Word "include", "comprise" used herein, " having " or its any other variant are intended to cover non-exclusionism
Including.E.g., including technique, method, article or the equipment for listing element are not necessarily limited by those elements, but may include
Other are not explicitly listed or belong to this technique, method, article or the intrinsic element of equipment.
The utility model uses differential pressure type fixed bed and slurry bed reactor substep hydrogenates, the traditional work of the Summary on technology
On the basis of skill (interval, one-pot) hydrogenation, continuous flowing new process for hydrogenation has been started, it is therefore intended that greatly improve production
Efficiency and product quality.Innovative point is that continuous hydrogenation, hydrogen recycle, and reaction solution discharging is as clear as crystal, simplifies filtering,
With decoloration process, keep reaction solution high-quality, intelligence degree is high, and system operation is more steady, revolutionizes traditional plus hydrogen
Reactive mode hydrogenates liquid glucose in continuous flow process, and reaction speed is fast, and side reaction is few, and product quality is more preferable.
The method of the utility model is mainly following steps:
Step 1, prepares the Glucose Liquid of 40~50wt% concentration, and adjusts pH to 6~7；
Glucose Liquid and hydrogen are continuously added into fixed bed reactors by step 2, carry out the first hydrogenation；
Reaction solution obtained in first hydrogenation is continuously added into slurry bed reactor by step 3, carries out second step
Hydrogenation；
Step 4 cools down to reaction solution obtained in the second hydrogenation, and recycles hydrogen, retained and filters out catalyst, and obtained
To Sorbitol solution crude product；
Step 5, Sorbitol solution crude product successively pass through decolorization, filtration treatment, ion exchange desalting processing, are concentrated by evaporation
Processing, obtains sorbierite.
In one embodiment, the Glucose Liquid temperature in step 1 is 80~90 DEG C.
In one embodiment, 10.5~12.5MPa of reactor pressure in step 2, temperature are controlled at 90~130 DEG C,
Residence time of material 1~3 hour；Fixed bed pre-hydrogenation, reducing degree reach 90%, remaining 10% is continued to have hydrogenated by slurry bed
At.
In one embodiment, 11.0~13.5MPa of reactor pressure in step 3, temperature are controlled at 100~140 DEG C,
Residence time of material 1~3 hour.
In one embodiment, after the Glucose Liquid in step 1 is using the processing of Electro Sorb removing chloride, it is re-fed into step 2
Hydrogenation.This step can reduce the content of the chloride ion in Glucose Liquid, can be improved in hydrogenation process anti-
The generation of the conversion ratio and inhibition side reaction answered.
In one embodiment, the hydrogenation in step 2 uses Ru system or Ni series catalysts, such as is carried on C
Ru catalyst, be also possible to using conventional Raney Ni catalyst.
In one embodiment, the slurry bed reactor in step 3, also referred to as slurry phase reactor are that a kind of liquid one is solid or gas
One liquid one is reactor, and hydraulically full in reactor, solid is constituted slurry with powder or microgranular deposit in a liquid, and solid is urged
The gas, liquid, solid phase reactor of agent full motion state at reaction liquid material.Hydrogenation in step 3 can also be as
Step 2 is also possible to use using conventional Raney Ni catalyst in this way, using Ru system or Ni series catalysts
Nickel ferrite based magnetic loaded/Ru double-layer catalyst of zirconium oxide load.When nickel ferrite based magnetic loaded/Ru the double-layer catalyst loaded using zirconium oxide, preparation
Process is mainly: S1: preparing and contains 4~6wt%ZrOCl2·8H2O, 1.5~2.5wt% polystyrene microsphere, 6~8wt% are water-soluble
Property starch and 30~40wt% ethyl alcohol aqueous solution, wherein the average grain diameter of polystyrene microsphere is 10~20 μm, be added dropwise 2~
The HCl solution of 4wt% adjusts pH to 3~4 and 1~2h of reaction is hydrolyzed at 45~50 DEG C, and ammonium hydroxide is then added dropwise again and adjusts pH
To 5~6, ageing 12~18h of reaction is carried out at 20~25 DEG C, zirconium colloidal sol is made to be carried on microsphere surface；Again to microballoon use from
After heart separation, drying, in 1080~1120 DEG C of 1~2h of sintering removal polystyrene and water soluble starch, it is more to obtain zirconium oxide
Hole is microsphere supported；S2: zirconium oxide porous microsphere carrier, water, water soluble starch are mixed according to weight ratio 1:5~8:1~3
It is even, it is then evaporated under reduced pressure and removes solvent, then 600~700 DEG C of 1~2h of roasting in nitrogen atmosphere, obtain the oxidation of material with carbon-coated surface
Zirconium carrier；S3, by the Zirconia carrier of material with carbon-coated surface and dehydrated alcohol according to the blending constituent dispersion liquid of weight ratio 1:70~80, then
The ethanol solution containing 0.5mol/L ferric nitrate and 0.25mol/L nickel nitrate is prepared, by dispersion liquid and ethanol solution
It is mixed according to volume ratio 1:1~1.5, then NaOH solution is added dropwise, the molar ratio of NaOH and ferric nitrate is 4.5~5:1, and continues to stir
1~2h of reaction is mixed, hydrothermal synthesis is then carried out, hydro-thermal reaction 18 at 170~180 DEG C~for 24 hours, by product centrifugation, deionized water
After washing, freeze-drying obtains the catalyst of load nickel ferrite based magnetic loaded；S4 presses the catalyst for loading nickel ferrite based magnetic loaded, ruthenic chloride, water, ethylene glycol
It is uniformly mixed according to weight ratio 1:0.2~0.5:180~200:20~30, nitre acid for adjusting pH is added to 1~2, at 85~90 DEG C
10~12h of back flow reaction, after the reaction was completed, catalyst by centrifugation, washing, it is dry after, obtain the nickel ferrite based magnetic loaded of zirconium oxide load/
Ru double-layer catalyst.When this catalyst prepares sorbierite applied to grape continuously hydrogen adding, reaction conversion can be effectively improved
The residual sugar and curl in sorbierite after rate, reduction reaction.
Based on above method, a typical operating process is as follows:
1, molten sugar allotment: Glucose Liquid is deployed to 40~50% concentration, and pH value is adjusted to 6~7, and 80~90 DEG C of temperature；
2, hydrogenation: deployed glucose solution is continuously pumped into the fixed bed reaction equipped with catalyst with pump
In device, it is continually fed into high pressure hydrogen from reactor bottom, keeps 10.5~12.5MPa of pressure in kettle, temperature is controlled 90~130
DEG C, residence time of material 1~3 hour, empty Transmission Ratio Control, discharged to obtain thick sorbierite；
3, crude glycol solution discharging enters slurry bed reactor again, continues to hydrogenate, after reaction, use through HP cooler
After circulating water cooling, into high-pressure separator vapor-liquid separation, the hydrogen isolated through supercooling, separate again after return compressor before
(or before pressure-variable adsorption) is re-compressed utilization；
4, sedimentation separation: separated hydrogen crude glycol it is hydraulic enter low pressure separation pot carry out secondary settlement separation, supernatant into
Enter bleaching process, the catalyst separated carries out activating and regenerating and returns to filling system；
5, crude glycol refine: the sorbitol solution concentration after sedimentation separation is about 45~50%, through decoloration, filtering, ion-exchange,
Evaporation and etc., obtain sorbitol finished product；
6, the high pressure hydrogen of reaction kettle is passed through described in step 2, be freshly prepd hydrogen and recycling hydrogen, new hydrogen and return
Receipts hydrogen ratio is 1:1~1:1.3；
7, after crude glycol solution tentatively cools down in step 3, hydrogen is isolated in high-pressure separator, hydrogen is cooled, divides again
Before compression utilizes or removes pressure-variable adsorption again before rear return compressor, purification recompression again.
Device used by the utility model is as shown in Figure 2, comprising:
Mixer 1, for preparing Glucose Liquid；
Fixed bed reactors 2 are connected to mixer 1, for carrying out the first hydrogenation to Glucose Liquid；It is anti-in fixed bed
The bottom of device 2 is answered to be equipped with the first hydrogen inlet；
Slurry bed reactor 3 is connected to fixed bed reactors 2, for carrying out second to the feed liquid after the first hydrogenation
Hydrogenation；
Separator 5 is connected to slurry bed reactor 3, carries out solid-liquid separation treatment for the material to the second hydrogenation；
De-watering apparatus 6 is connected to the hydrogen discharge of separator 5, for carrying out the hydrogen of discharge except water process；
Compressor 7 is connected to de-watering apparatus 6, for the hydrogen repressurization after water removal, de-watering apparatus 6 here can
In a manner of being to use condensation, it can also be removed water for example, by modes such as molecular sieve absorption；The gas vent of compressor 7 is connected to
Fixed bed reactors 2 and/or slurry bed reactor 3, effect is to return again to extra hydrogen into reactor；
The liquid outlet of separator 5 passes sequentially through decoloration kettle, filter, ion exchange resin column and is connected to concentration kettle；
The Sorbitol solution that decoloration kettle is used to obtain separator 5 carries out decolorization, can use active carbon decolorization；
Filter is for being filtered processing to the Sorbitol solution after decolorization；After ion exchange resin column is used for filtration treatment
Sorbitol solution carries out desalting processing, can be using acidulous acrylic acid's cation resin or alkalescent polystyrene yin
Ion exchange resin；Concentration kettle is for being evaporated concentration to the Sorbitol solution after desalting processing.
Embodiment 1
Step 1,80 DEG C of Glucose Liquids for preparing 40wt% concentration (contain about 100ppm Na+ and 220ppm Cl-Impurity),
And pH to 6~7 is adjusted with HCl；
Glucose Liquid and hydrogen are added into fixed bed reactors step 2, carry out the first hydrogenation；Using
Raney Ni catalyst, reactor pressure 10.5MPa, temperature are controlled at 90 DEG C, residence time of material 1 hour；
Reaction solution obtained in first hydrogenation is added into slurry bed reactor step 3, and it is anti-to carry out the second hydrogenation
It answers；Using activated carbon supported Ru catalyst；Reactor pressure 11.0MPa, temperature are controlled at 100 DEG C, material stop
Between 1 hour；
Step 4 cools down to reaction solution obtained in the second hydrogenation, and recycles hydrogen, after removing catalyst, obtains mountain
Pears alcohol liquid crude product；
Step 5, Sorbitol solution crude product successively pass through active carbon decolorization, filter-cloth filtering processing, acidulous acrylic acid system
Resin cation ion exchange desalting processing, evaporation and concentration processing, obtain sorbierite.
Embodiment 2
Step 1,90 DEG C of Glucose Liquids for preparing 50wt% concentration (contain about 100ppm Na+ and 220ppm Cl-Impurity),
And pH to 6~7 is adjusted with HCl；
Glucose Liquid and hydrogen are added into fixed bed reactors step 2, carry out the first hydrogenation；Using
Raney Ni catalyst, reactor pressure 12.5MPa, temperature are controlled at 130 DEG C, residence time of material 3 hours；
Reaction solution obtained in first hydrogenation is added into slurry bed reactor step 3, and it is anti-to carry out the second hydrogenation
It answers；Using activated carbon supported Ru catalyst；Reactor pressure 13.5MPa, temperature are controlled at 140 DEG C, material stop
Between 1~3 hour
Step 4 cools down to reaction solution obtained in the second hydrogenation, and recycles hydrogen, after removing catalyst, obtains mountain
Pears alcohol liquid crude product；
Step 5, Sorbitol solution crude product successively pass through active carbon decolorization, filter-cloth filtering processing, acidulous acrylic acid system
Resin cation ion exchange desalting processing, evaporation and concentration processing, obtain sorbierite.
Embodiment 3
Step 1,85 DEG C of Glucose Liquids for preparing 45wt% concentration (contain about 100ppm Na+ and 220ppm Cl-Impurity),
And pH to 6~7 is adjusted with HCl；
Glucose Liquid and hydrogen are added into fixed bed reactors step 2, carry out the first hydrogenation；Using
Raney Ni catalyst, reactor pressure 11.5MPa, temperature are controlled at 120 DEG C, residence time of material 2 hours；
Reaction solution obtained in first hydrogenation is added into slurry bed reactor step 3, and it is anti-to carry out the second hydrogenation
It answers；Using activated carbon supported Ru catalyst；Reactor pressure 12.0MPa, temperature are controlled at 125 DEG C, material stop
Between 2 hours
Step 4 cools down to reaction solution obtained in the second hydrogenation, and recycles hydrogen, after removing catalyst, obtains mountain
Pears alcohol liquid crude product；
Step 5, Sorbitol solution crude product successively pass through active carbon decolorization, filter-cloth filtering processing, acidulous acrylic acid system
Resin cation ion exchange desalting processing, evaporation and concentration processing, obtain sorbierite.
Embodiment 4
Difference with embodiment 3 is: after Glucose Liquid is using the processing of Electro Sorb removing chloride, being re-fed into the hydrogenation of step 2
Reaction.
Step 1,85 DEG C of Glucose Liquids for preparing 40~50wt% concentration (contain about 100ppm Na+ and 220ppm Cl-It is miscellaneous
Matter), then by carrying out Electro Sorb processing, hydraulic detention time 20min, Cl under 8V voltage-Concentration drops to the left side 50ppm
It is right), then and pH to 6~7 is adjusted with HCl；
Glucose Liquid and hydrogen are added into fixed bed reactors step 2, carry out the first hydrogenation；Using
Raney Ni catalyst, reactor pressure 11.5MPa, temperature are controlled at 120 DEG C, residence time of material 2 hours；
Reaction solution obtained in first hydrogenation is added into slurry bed reactor step 3, and it is anti-to carry out the second hydrogenation
It answers；Using activated carbon supported Ru catalyst；Reactor pressure 12.0MPa, temperature are controlled at 125 DEG C, material stop
Between 2 hours
Step 4 cools down to reaction solution obtained in the second hydrogenation, and recycles hydrogen, after removing catalyst, obtains mountain
Pears alcohol liquid crude product；
Step 5, Sorbitol solution crude product successively pass through active carbon decolorization, filter-cloth filtering processing, acidulous acrylic acid system
Resin cation ion exchange desalting processing, crystallization treatment, obtain sorbierite.
Embodiment 5
Step 1,85 DEG C of Glucose Liquids for preparing 45wt% concentration (contain about 100ppm Na+ and 220ppm Cl-Impurity),
And pH to 6~7 is adjusted with HCl；
Glucose Liquid and hydrogen are added into fixed bed reactors step 2, carry out the first hydrogenation；Using
Raney Ni catalyst, reactor pressure 11.5MPa, temperature are controlled at 120 DEG C, residence time of material 2 hours；
Reaction solution obtained in first hydrogenation is added into slurry bed reactor step 3, and it is anti-to carry out the second hydrogenation
It answers；Nickel ferrite based magnetic loaded/Ru the double-layer catalyst loaded using zirconium oxide；Reactor pressure 12.0MPa, temperature are controlled at 125 DEG C,
Residence time of material 2 hours；Catalyst is prepared via a method which to obtain:
S1: preparation contains 4wt%ZrOCl2·8H2O, 1.5wt% polystyrene microsphere, 6wt% water soluble starch and 30wt% second
The aqueous solution of alcohol, wherein the average grain diameter of polystyrene microsphere is 10~20 μm, is added dropwise the HCl solution of 2wt%, adjust pH to 3~
4 are hydrolyzed 1~h of reaction at 45 DEG C, and ammonium hydroxide is then added dropwise again and adjusts pH to 5~6, and ageing reaction 12h is carried out at 20 DEG C,
Zirconium colloidal sol is set to be carried on microsphere surface；After again to microballoon using centrifuge separation, drying, gone in 1080 DEG C of oxygen atmospheres sintering 1h
Except polystyrene and water soluble starch, zirconium oxide porous microsphere carrier is obtained；
S2: zirconium oxide porous microsphere carrier, water, water soluble starch are uniformly mixed according to weight ratio 1:5:1, then depressurized
Evaporation removes solvent, then 600 DEG C of roasting 1h in nitrogen atmosphere, obtains the Zirconia carrier of material with carbon-coated surface；
S3 by the Zirconia carrier of material with carbon-coated surface and dehydrated alcohol according to weight ratio 1:70 blending constituent dispersion liquid, then matches
The ethanol solution containing 0.5mol/L ferric nitrate and 0.25mol/L nickel nitrate is made, dispersion liquid and ethanol solution are pressed
It being mixed according to volume ratio 1:1, then NaOH solution is added dropwise, the molar ratio of NaOH and ferric nitrate is 4.5:1, and continues to be stirred to react 1h,
Then hydrothermal synthesis is carried out, hydro-thermal reaction 18h at 170 DEG C, after product centrifugation, deionized water washing, freeze-drying obtains load iron
The catalyst of sour nickel；
S4 mixes the catalyst for loading nickel ferrite based magnetic loaded, ruthenic chloride, water, ethylene glycol according to weight ratio 1:0.2:180:20
It is even, nitre acid for adjusting pH is added to 1~2, the back flow reaction 10h at 85 DEG C, after the reaction was completed, catalyst is by being centrifuged, washing, do
After dry, nickel ferrite based magnetic loaded/Ru double-layer catalyst of zirconium oxide load is obtained.
Step 4 cools down to reaction solution obtained in the second hydrogenation, and recycles hydrogen, after removing catalyst, obtains mountain
Pears alcohol liquid crude product；
Step 5, Sorbitol solution crude product successively pass through active carbon decolorization, filter-cloth filtering processing, acidulous acrylic acid system
Resin cation ion exchange desalting processing, evaporation and concentration processing, obtain sorbierite.
Embodiment 6
Step 1,85 DEG C of Glucose Liquids for preparing 45wt% concentration (contain about 100ppm Na+ and 220ppm Cl-Impurity),
And pH to 6~7 is adjusted with HCl；
Glucose Liquid and hydrogen are added into fixed bed reactors step 2, carry out the first hydrogenation；Using
Raney Ni catalyst, reactor pressure 11.5MPa, temperature are controlled at 120 DEG C, residence time of material 2 hours；
Reaction solution obtained in first hydrogenation is added into slurry bed reactor step 3, and it is anti-to carry out the second hydrogenation
It answers；Nickel ferrite based magnetic loaded/Ru the double-layer catalyst loaded using zirconium oxide；Reactor pressure 12.0MPa, temperature are controlled at 125 DEG C,
Residence time of material 2 hours；Catalyst is prepared via a method which to obtain:
S1: preparation contains 6wt%ZrOCl2·8H2O, 2.5wt% polystyrene microsphere, 8wt% water soluble starch and 40wt% second
The aqueous solution of alcohol, wherein the average grain diameter of polystyrene microsphere is 10~20 μm, is added dropwise the HCl solution of 4wt%, adjust pH to 3~
4 are hydrolyzed reaction 2h at 50 DEG C, and ammonium hydroxide is then added dropwise again and adjusts pH to 5~6, and ageing reaction 18h is carried out at 25 DEG C, is made
Zirconium colloidal sol is carried on microsphere surface；After again to microballoon using centrifuge separation, drying, in 1120 DEG C of oxygen atmospheres sintering 2h removals
Polystyrene and water soluble starch obtain zirconium oxide porous microsphere carrier；
S2: zirconium oxide porous microsphere carrier, water, water soluble starch are uniformly mixed according to weight ratio 1:8:3, then subtracted
Pressure evaporation removes solvent, then 700 DEG C of roasting 2h in nitrogen atmosphere, obtains the Zirconia carrier of material with carbon-coated surface；
S3 by the Zirconia carrier of material with carbon-coated surface and dehydrated alcohol according to weight ratio 1:80 blending constituent dispersion liquid, then matches
The ethanol solution containing 0.5mol/L ferric nitrate and 0.25mol/L nickel nitrate is made, dispersion liquid and ethanol solution are pressed
It being mixed according to volume ratio 1:1.5, then NaOH solution is added dropwise, the molar ratio of NaOH and ferric nitrate is 5:1, and continues to be stirred to react 2h,
Then hydrothermal synthesis is carried out, for 24 hours, after product centrifugation, deionized water washing, freeze-drying obtains load iron to hydro-thermal reaction at 180 DEG C
The catalyst of sour nickel；
S4 mixes the catalyst for loading nickel ferrite based magnetic loaded, ruthenic chloride, water, ethylene glycol according to weight ratio 1:0.5:200:30
Uniformly, be added nitre acid for adjusting pH to 1~2, the back flow reaction 12h at 90 DEG C, after the reaction was completed, catalyst by centrifugation, washing,
After drying, nickel ferrite based magnetic loaded/Ru double-layer catalyst of zirconium oxide load is obtained.
Step 4 cools down to reaction solution obtained in the second hydrogenation, and recycles hydrogen, after removing catalyst, obtains mountain
Pears alcohol liquid crude product；
Step 5, Sorbitol solution crude product successively pass through active carbon decolorization, filter-cloth filtering processing, acidulous acrylic acid system
Resin cation ion exchange desalting processing, evaporation and concentration processing, obtain sorbierite.
Reference examples 1
Difference with embodiment 3 is: being reacted using a fixed bed hydrogenation, and extends the reaction time.
Step 1,85 DEG C of Glucose Liquids for preparing 45wt% concentration (contain about 100ppm Na+ and 220ppm Cl-Impurity),
And pH to 6~7 is adjusted with HCl；
Glucose Liquid and hydrogen are added into fixed bed reactors step 2, carry out hydrogenation；Using Raney
Ni catalyst, reactor pressure 11.5MPa, temperature are controlled at 120 DEG C, residence time of material 3 hours；
Step 3 cools down to reaction solution obtained in hydrogenation, and recycles hydrogen, after removing catalyst, obtains sorbierite
Liquid crude product；
Step 4, Sorbitol solution crude product successively pass through active carbon decolorization, filter-cloth filtering processing, acidulous acrylic acid system
Resin cation ion exchange desalting processing, evaporation and concentration processing, obtain sorbierite.
Reference examples 2
Difference with embodiment 5 is: directlying adopt Zirconium powder as catalyst carrier.
Step 1,85 DEG C of Glucose Liquids for preparing 45wt% concentration (contain about 100ppm Na+ and 220ppm Cl-Impurity),
And pH to 6~7 is adjusted with HCl；
Glucose Liquid and hydrogen are added into fixed bed reactors step 2, carry out the first hydrogenation；Using
Raney Ni catalyst, reactor pressure 11.5MPa, temperature are controlled at 120 DEG C, residence time of material 2 hours；
Reaction solution obtained in first hydrogenation is added into slurry bed reactor step 3, and it is anti-to carry out the second hydrogenation
It answers；Nickel ferrite based magnetic loaded/Ru the double-layer catalyst loaded using zirconium oxide；Reactor pressure 12.0MPa, temperature are controlled at 125 DEG C,
Residence time of material 2 hours；Catalyst is prepared via a method which to obtain:
S1: Zirconium powder, water, water soluble starch that average grain diameter is 200~400 μm are mixed according to weight ratio 1:5:1
It closes uniformly, is then evaporated under reduced pressure and removes solvent, then 600 DEG C of roasting 1h in nitrogen atmosphere, the zirconium oxide for obtaining material with carbon-coated surface carries
Body；
S2 by the Zirconia carrier of material with carbon-coated surface and dehydrated alcohol according to weight ratio 1:70 blending constituent dispersion liquid, then matches
The ethanol solution containing 0.5mol/L ferric nitrate and 0.25mol/L nickel nitrate is made, dispersion liquid and ethanol solution are pressed
It being mixed according to volume ratio 1:1, then NaOH solution is added dropwise, the molar ratio of NaOH and ferric nitrate is 4.5:1, and continues to be stirred to react 1h,
Then hydrothermal synthesis is carried out, hydro-thermal reaction 18h at 170 DEG C, after product centrifugation, deionized water washing, freeze-drying obtains load iron
The catalyst of sour nickel；
S3 mixes the catalyst for loading nickel ferrite based magnetic loaded, ruthenic chloride, water, ethylene glycol according to weight ratio 1:0.2:180:20
It is even, nitre acid for adjusting pH is added to 1~2, the back flow reaction 10h at 85 DEG C, after the reaction was completed, catalyst is by being centrifuged, washing, do
After dry, nickel ferrite based magnetic loaded/Ru double-layer catalyst of zirconium oxide load is obtained.
Step 4 cools down to reaction solution obtained in the second hydrogenation, and recycles hydrogen, after removing catalyst, obtains mountain
Pears alcohol liquid crude product；
Step 5, Sorbitol solution crude product successively pass through active carbon decolorization, filter-cloth filtering processing, acidulous acrylic acid system
Resin cation ion exchange desalting processing, evaporation and concentration processing, obtain sorbierite.
Reference examples 3
Difference with embodiment 5 is: not loading ferrous acid nickel layer in the catalyst.
Step 1,85 DEG C of Glucose Liquids for preparing 45wt% concentration (contain about 100ppm Na+ and 220ppm Cl-Impurity),
And pH to 6~7 is adjusted with HCl；
Glucose Liquid and hydrogen are added into fixed bed reactors step 2, carry out the first hydrogenation；Using
Raney Ni catalyst, reactor pressure 11.5MPa, temperature are controlled at 120 DEG C, residence time of material 2 hours；
Reaction solution obtained in first hydrogenation is added into slurry bed reactor step 3, and it is anti-to carry out the second hydrogenation
It answers；Nickel ferrite based magnetic loaded/Ru the double-layer catalyst loaded using zirconium oxide；Reactor pressure 12.0MPa, temperature are controlled at 125 DEG C,
Residence time of material 2 hours；Catalyst is prepared via a method which to obtain:
S1: preparation contains 4wt%ZrOCl2·8H2O, 1.5wt% polystyrene microsphere, 6wt% water soluble starch and 30wt% second
The aqueous solution of alcohol, wherein the average grain diameter of polystyrene microsphere is 10~20 μm, is added dropwise the HCl solution of 2wt%, adjust pH to 3~
4 are hydrolyzed 1~h of reaction at 45 DEG C, and ammonium hydroxide is then added dropwise again and adjusts pH to 5~6, and ageing reaction 12h is carried out at 20 DEG C,
Zirconium colloidal sol is set to be carried on microsphere surface；After again to microballoon using centrifuge separation, drying, gone in 1080 DEG C of oxygen atmospheres sintering 1h
Except polystyrene and water soluble starch, zirconium oxide porous microsphere carrier is obtained；
S2: zirconium oxide porous microsphere carrier, water, water soluble starch are uniformly mixed according to weight ratio 1:5:1, then depressurized
Evaporation removes solvent, then 600 DEG C of roasting 1h in nitrogen atmosphere, obtains the Zirconia carrier of material with carbon-coated surface；
S3 by the Zirconia carrier of material with carbon-coated surface and dehydrated alcohol according to weight ratio 1:70 blending constituent dispersion liquid, then matches
The ethanol solution containing 0.5mol/L ferric nitrate and 0.25mol/L nickel nitrate is made, dispersion liquid and ethanol solution are pressed
It being mixed according to volume ratio 1:1, then NaOH solution is added dropwise, the molar ratio of NaOH and ferric nitrate is 4.5:1, and continues to be stirred to react 1h,
Then hydrothermal synthesis is carried out, hydro-thermal reaction 18h at 170 DEG C, after product centrifugation, deionized water washing, freeze-drying obtains load iron
The catalyst of sour nickel；
S4 mixes the catalyst for loading nickel ferrite based magnetic loaded, ruthenic chloride, water, ethylene glycol according to weight ratio 1:0.2:180:20
It is even, nitre acid for adjusting pH is added to 1~2, the back flow reaction 10h at 85 DEG C, after the reaction was completed, catalyst is by being centrifuged, washing, do
After dry, nickel ferrite based magnetic loaded/Ru double-layer catalyst of zirconium oxide load is obtained.
Step 4 cools down to reaction solution obtained in the second hydrogenation, and recycles hydrogen, after removing catalyst, obtains mountain
Pears alcohol liquid crude product；
Step 5, Sorbitol solution crude product successively pass through active carbon decolorization, filter-cloth filtering processing, acidulous acrylic acid system
Resin cation ion exchange desalting processing, evaporation and concentration processing, obtain sorbierite.
The process operation situation of the above various embodiments and reference examples is as follows:
As can be seen from the above table, the method for the utility model conversion per pass with higher, can reach 98.5% with
On；The sorbierite obtained simultaneously has the advantages that purity is high, and 99.5% or more, residual sugar is below 0.20%；In addition, from embodiment
3 and the comparison of embodiment 4 can be seen that glucose feed can be effectively reduced and be reacted using the processing of Electro Sorb removing chloride
The generation of the side reaction of journey, improves the purity of sorbierite, and reduces specific rotation；Meanwhile it can from embodiment 5 and embodiment 3
Out, there is higher conversion ratio using the double-deck nickel ferrite based magnetic loaded/ruthenium composite catalyst；Using traditional fixed bed in reference examples 1
Reactor, company of the hydrogenation conversion significantly lower than fixed bed reactors and slurry bed reactor employed in the utility model
Continuous hydrogenation technique, and the technique of the utility model can reduce the specific rotation of Sorbitol solution；It can from reference examples 2 and embodiment 5
To find out, using zirconium oxide micro mist as carrier, the zirconium oxide of catalytic effect load carbon not as good as used by the utility model
Porous hollow microballoon.
Continuous flowing hydrogenation plant is compared with domestic and international advanced level
Continuous flowing plus hydrogen sorbitol production new process are transformation on the basis of traditional handicraft, perfect, the collection of innovation
At, so that the hydrogenation plant enlargement of sorbierite and other sugar alcohols is had guarantee, production is safer, and is able to achieve intelligent automation,
And production cost is greatly reduced, it is worthy of popularization.
Claims (5)
1. the device that a kind of glucose continuously hydrogen adding prepares sorbierite characterized by comprising
Mixer (1), for preparing Glucose Liquid；
Fixed bed reactors (2) are connected to mixer (1), for carrying out the first hydrogenation to Glucose Liquid；It is anti-in fixed bed
The bottom of device (2) is answered to be equipped with the first hydrogen inlet；
Slurry bed reactor (3) is connected to fixed bed reactors (2), for carrying out second to the feed liquid after the first hydrogenation
Hydrogenation；
Separator (5) is connected to slurry bed reactor (3), carries out solid-liquid separation treatment for the material to the second hydrogenation；
De-watering apparatus (6), is connected to the hydrogen discharge of separator (5), for carrying out the hydrogen of discharge except water process；
Compressor (7) is connected to de-watering apparatus (6), for the hydrogen repressurization after water removal；The gas of compressor (7) goes out
Mouth is connected to fixed bed reactors (2) and/or slurry bed reactor (3)；
The liquid outlet of separator (5) passes sequentially through decoloration kettle, filter, ion exchange resin column and is connected to concentration kettle；
The Sorbitol solution that decoloration kettle is used to obtain separator (5) carries out decolorization；After filter is used for decolorization
Sorbitol solution is filtered processing；Ion exchange resin column is used to carry out desalting processing to the Sorbitol solution after filtration treatment；It is dense
Contracting kettle is for being evaporated concentration to the Sorbitol solution after desalting processing.
2. the device that glucose continuously hydrogen adding according to claim 1 prepares sorbierite, which is characterized in that de-watering apparatus
It (6) is condensation de-watering apparatus or absorption de-watering apparatus.
3. the device that glucose continuously hydrogen adding according to claim 1 prepares sorbierite, which is characterized in that decoloration kettle filling
Active charcoal.
4. the device that glucose continuously hydrogen adding according to claim 1 prepares sorbierite, which is characterized in that amberlite
What is filled in rouge column is acidulous acrylic acid's cation resin or alkalescent styrene series anion resin.
5. the device that glucose continuously hydrogen adding according to claim 1 prepares sorbierite, which is characterized in that mixer (1)
Fixed bed reactors (2) are connected to by electric adsorption device.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109305882A (en) * | 2018-09-28 | 2019-02-05 | 吉林省石油化工设计研究院 | A kind of glucose continuously hydrogen adding prepares the method and device of sorbierite |
| CN110862298A (en) * | 2019-11-08 | 2020-03-06 | 黑龙江新和成生物科技有限公司 | Preparation method of sorbitol |
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2018
- 2018-09-28 CN CN201821586587.9U patent/CN208949158U/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109305882A (en) * | 2018-09-28 | 2019-02-05 | 吉林省石油化工设计研究院 | A kind of glucose continuously hydrogen adding prepares the method and device of sorbierite |
| CN109305882B (en) * | 2018-09-28 | 2023-12-19 | 吉林省石油化工设计研究院 | Method and device for preparing sorbitol by continuous hydrogenation of glucose |
| CN110862298A (en) * | 2019-11-08 | 2020-03-06 | 黑龙江新和成生物科技有限公司 | Preparation method of sorbitol |
| CN110862298B (en) * | 2019-11-08 | 2023-04-11 | 黑龙江新和成生物科技有限公司 | Preparation method of sorbitol |
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