CN110152743A - A kind of solid acid catalyst and its in supercritical CO2The application of 5 hydroxymethyl furfural is synthesized in methanol system - Google Patents
A kind of solid acid catalyst and its in supercritical CO2The application of 5 hydroxymethyl furfural is synthesized in methanol system Download PDFInfo
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- CN110152743A CN110152743A CN201910533819.7A CN201910533819A CN110152743A CN 110152743 A CN110152743 A CN 110152743A CN 201910533819 A CN201910533819 A CN 201910533819A CN 110152743 A CN110152743 A CN 110152743A
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Abstract
The present invention relates to a kind of supercritical COs2The method and a kind of preparation method of carried superstrong solid acid catalyst of 5 hydroxymethyl furfural are synthesized in methanol;Carrier, solid metal oxide are impregnated into sulfuric acid solution together, stirred, is filtered, it is dry, it roasts up to carried superstrong solid acid catalyst.Carbohydrate or biomass material, catalyst and anhydrous methanol are added in autoclave with certain proportion.Heating is forced into reaction required temperature and pressure, sealing reaction a period of time.After reaction, it is cooled to room temperature, after reaction mixture filtering, rotates methanol, obtain 5 hydroxymethyl furfural.Using dissolving in supercritical CO2Catalyst preparation 5 hydroxymethyl furfural, and select low-boiling methanol as organic phase, not only can and CO2Reach supercriticality jointly, and avoid the generation of 5 hydroxymethyl furfural hydration side reaction and solid insoluble, selectivity and yield keep higher level.
Description
Technical field
The invention belongs to supercritical fluid techniques and biomass chemical utilization technical field, and in particular to a kind of overcritical
CO2The method and a kind of preparation method of carried superstrong solid acid catalyst of 5 hydroxymethyl furfural are synthesized in methanol.
Background technique
5 hydroxymethyl furfural is as bio-based materials monomer and as the raw material of high molecule plastic, extensively at present
Applied to the industries such as medicine, pesticide, plastic cement, daily-use chemical industry, fuel, functional material and other important fine chemistry industries, purposes
Wide market is big, can partially substitute fossil, coal resources, and be confirmed as changing for establishing following " green " by U.S. Department of Energy
Learn " one of the 12 most potential biomass-based plateform molecules " of industry.But according to current research level from the point of view of, 5- hydroxyl first
Base furfural can generally synthesize in organic solvent, and be extracted with organic solvent, can cause environment pollution in this way.
CO2Itself is incombustible and harmless, inexpensively and easily reaches critical condition, is based on plurality of advantages institute
With ScCO2It can be applied in the extraction and synthesis of 5 hydroxymethyl furfural.Supercritical carbon dioxide is more than critical point
A kind of and approximate good solvent of hydro carbons can dissolve organic micromolecule compound and polymer monomer, to replace tradition
Organic solvent, after reaction CO2Direct gasification is discharged into air, and noresidue in the product, is not both polluted to environment,
Also it is contaminated product not, so supercritical CO2It is one of the green medium for meeting current " Green Chemistry " development.
Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences successfully uses supercritical carbon dioxide extraction method, with grape
Sugar and cellulose are Material synthesis 5 hydroxymethyl furfural (CN 101628902B) (CN 101628901B), but bibliography
In be by CO2The acid generated in water phase is dissolved into as catalyst, acidity is according to CO2Solvability obtain, belong to can not
Control factor, and in addition to supercritical CO in system2There is also water phases outside, and 5 hydroxymethyl furfural presence is prepared in water phase and is much asked
Topic, such as levulic acid and formic acid by-product are generated, so yield and selectivity be not high always.High-temperature water can also have catalyst
Corrosiveness substantially reduces access times and the service life of catalyst.Liu etc. is faced as catalyst super using oil tea shell charcoal sulfonic acid
Boundary CO2Fructose converting middle catalysis is 5 hydroxymethyl furfural (Jiaotong University Of East China's journal, 2016,33 (6): 118-123), but is examined
Supercritical CO can not be dissolved by considering oil tea shell charcoal sulfonic acid2In, reactor bottom can only be sunk to and connect by stirring with raw material
Touching, this greatly reduces the contact area of catalyst and raw material, and catalytic efficiency is not high, so yield is lower.
Summary of the invention
Based on background above technology, the purpose of the present invention is to provide a kind of gold of siliceous and/or fluoro containing polymers load
Belong to the preparation method of oxide solid super acidic catalyst and in supercritical CO2The side of 5 hydroxymethyl furfural is synthesized in methanol
Method.Supercritical CO is dissolved in using one kind2Catalyst preparation 5 hydroxymethyl furfural, and select low-boiling methanol as having
Machine phase, not only can and CO2Reach supercriticality jointly, and avoid 5 hydroxymethyl furfural hydration side reaction and solid it is insoluble
The generation of object, selectivity and yield keep higher level, include the following steps:
Carried superstrong solid acid catalyst and synthesis 5 hydroxymethyl furfural are prepared, is specifically comprised the following steps:
Carrier, metal oxide are added in sulfuric acid solution, stirred, is filtered, it is dry, it is roasted at 450 DEG C~650 DEG C
12~for 24 hours, obtain the carried superstrong solid acid catalyst.
Based on above technical scheme, it is preferred that the carrier is siliceous and/or fluorine macromolecule;The oxide is dioxy
Change zirconium (ZrO2), titanium dioxide (TiO2), cobalt oxide (CoO), cobalt sesquioxide (Co2O3), molybdenum oxide (MoO3), bismuth oxide
(Bi2O3), at least one of nickel oxide (NiO).
Based on above technical scheme, it is preferred that the usage ratio (g/g/mL) of carrier, metal oxide and sulfuric acid solution is
1:(1~5): (10~40).
Based on above technical scheme, it is preferred that the sulfuric acid solution concentration is 0.5M~2M.
Based on above technical scheme, it is preferred that the mixing time is 6~12h.
Based on above technical scheme, it is preferred that the polymeric silicon that contains is excellent for polysiloxane rubber or polyorganosiloxane resin
It is selected as poly- methyl silicon resin, amino silicone, fluorine silicon resin, silicone-epoxy resin, methyl silicone rubber (MQ), ethylene methacrylic
Base silicon rubber (VMQ), methyl vinyl phenyl silicon rubber (PVMQ), nitrile silicone rubber, fluorine silicone rubber at least one of;It is described
Fluoro containing polymers are fluorochemical acrylate polymer, preferably polyacrylic acid 1,1- dihydro perfluor monooctyl ester (PFOA), polytetrafluoroethylene (PTFE)
At least one of.
The present invention also provides a kind of method for synthesizing 5 hydroxymethyl furfural, the support type being prepared using the above method is solid
Body super acidic catalyst, specifically comprises the following steps:
(1) raw material, anhydrous methanol and the catalyst are added in autoclave;
(2) heating is forced into reaction required temperature and pressure, after sealing reaction kettle, is stirred to react;
(3) after reaction, it is cooled to room temperature, after reaction mixture filtering, revolving removal methanol obtains 5- methylol chaff
Aldehyde.
Based on above technical scheme, it is preferred that the raw material is glucose, fructose, chitosan, chitin, cellulose, half
Cellulose, lignin, lactose and protist matter;The protist matter is trees, pericarp, bamboo, agricultural crop straw.
Based on above technical scheme, it is preferred that the amount ratio (g/g/mL) of the catalyst, raw material and anhydrous methanol is 1:
(10~20): (50~100).
Based on above technical scheme, it is preferred that the reaction temperature is 240 DEG C~320 DEG C;The reaction pressure is 8.1
~22MPa;The reaction time is 3-10 hours.
Beneficial effect
(1) present invention is easy to and CO using low-boiling methanol as organic phase2Reach supercriticality jointly, not only
So that system is possessed more good dissolubility and diffusivity, and greatly reduce the generation of side reaction, avoids previous addition
Water phase bring catalytic erosion and side reaction is led to the problem of, improves the catalytic efficiency and service life of catalyst.
(2) present invention uses and is easily soluble in supercritical CO2Siliceous and/or fluorine-containing high molecular material as carrier, can
So that catalyst better disperses in system, catalytic efficiency is substantially increased.CO after system cooling2With methanol liquid phase point
From product is dissolved in methanol, can obtain purer 5 hydroxymethyl furfural by revolving, environmentally protective, simplicity is easy to get.
(3) solid acid catalyst of the invention uses and is directly acidified and is loaded in dilute sulfuric acid, rather than passes through acid
Alkali process carrier, is then loaded in organic solvent.It avoids and forms hydrogen bond between organic solvent and carrier, thus to urging
The load of agent impacts, and influences load factor.
Specific embodiment
Embodiment 1
Different carriers are respectively adopted and prepare carried superstrong solid acid catalyst, by carrier, titanium dioxide (TiO2) and 1M
Sulfuric acid solution mixed with the ratio (g/g/mL) of 1:5:30, after stirring 10h, filter, dry, 600 DEG C of roastings are for 24 hours in Muffle furnace
Up to carried superstrong solid acid catalyst.
Catalyst, fructose and anhydrous methanol are added in autoclave with the ratio of 1:15:60 (g/g/mL).Heating
To 260 DEG C, it is forced into 16MPa, after sealing reaction kettle, 8h is reacted in stirring.After reaction, it is cooled to room temperature, reaction mixture mistake
After filter, methanol is rotated, obtains product, is analyzed with HPLC.Different silicon-containing and fluorine-containing carrier material are investigated to synthesis 5- methylol
The influence of furfural, is specifically shown in Table 1.
The influence of 1. different silicon-containing of table and fluorine-containing carrier material to synthesis 5 hydroxymethyl furfural
Embodiment 2
It uses fluorine silicon resin for carrier material, changes metal oxide type.Other experiment conditions are the same as embodiment 1.It investigates
Influence of the different metal oxides to synthesis 5 hydroxymethyl furfural, is specifically shown in Table 2.
Influence of 2. different metal oxides of table to synthesis 5 hydroxymethyl furfural
Embodiment 3
It uses fluorine silicon resin for carrier material, changes the ratio of carrier, titanium dioxide and sulfuric acid solution.Other experiment conditions
With embodiment 1.Influence of the ratio for changing carrier, titanium dioxide and sulfuric acid solution to synthesis 5 hydroxymethyl furfural is investigated, specifically
It is shown in Table 3.
Table 3. changes influence of the ratio of carrier, titanium dioxide and sulfuric acid solution to synthesis 5 hydroxymethyl furfural
Embodiment 4
It uses fluorine silicon resin for carrier material, changes the concentration of sulfuric acid solution.Other experiment conditions are the same as embodiment 1.It investigates
Influence of the concentration of different sulfuric acid solutions to synthesis 5 hydroxymethyl furfural, is specifically shown in Table 4.
Influence of the concentration of the different sulfuric acid solutions of table 4. to synthesis 5 hydroxymethyl furfural
Embodiment 5
It uses fluorine silicon resin for carrier material, changes mixing time.Other experiment conditions are the same as embodiment 1.Difference is investigated to stir
Influence of the time to synthesis 5 hydroxymethyl furfural is mixed, is specifically shown in Table 5.
Influence of the different mixings time of table 5. to synthesis 5 hydroxymethyl furfural
Embodiment 6
It uses fluorine silicon resin for carrier material, changes maturing temperature.Other experiment conditions are the same as embodiment 1.Investigate different roastings
Influence of the temperature to synthesis 5 hydroxymethyl furfural is burnt, is specifically shown in Table 6.
Influence of the different maturing temperatures of table 6. to synthesis 5 hydroxymethyl furfural
Embodiment 7
It uses fluorine silicon resin for carrier material, changes calcining time.Other experiment conditions are the same as embodiment 1.Investigate different roastings
Influence of the time to synthesis 5 hydroxymethyl furfural is burnt, is specifically shown in Table 7.
Influence of the different calcining times of table 7. to synthesis 5 hydroxymethyl furfural
Embodiment 8
Use fluorine silicon resin for carrier material, feed change type.Other experiment conditions are the same as embodiment 1.Investigate different originals
Expect specifically to be shown in Table 8 to the influence of synthesis 5 hydroxymethyl furfural.
Influence of 8. different material of table to synthesis 5 hydroxymethyl furfural
Embodiment 9
It uses fluorine silicon resin for carrier material, changes the ratio (g/g/mL) of catalyst, fructose and anhydrous methanol.Other realities
Condition is tested with embodiment 1.Influence of the ratio for changing catalyst, fructose and anhydrous methanol to synthesis 5 hydroxymethyl furfural is investigated,
Specifically it is shown in Table 9.
Table 9. changes influence of the ratio of catalyst, fructose and anhydrous methanol to synthesis 5 hydroxymethyl furfural
Embodiment 10
It uses fluorine silicon resin for carrier material, changes reaction temperature.Other experiment conditions are the same as embodiment 1.It investigates different anti-
Temperature is answered specifically to be shown in Table 10 to the influence of synthesis 5 hydroxymethyl furfural.
Influence of the 10. differential responses temperature of table to synthesis 5 hydroxymethyl furfural
Embodiment 11
It uses fluorine silicon resin for carrier material, changes reaction pressure.Other experiment conditions are the same as embodiment 1.It investigates different anti-
Pressure is answered specifically to be shown in Table 11 to the influence of synthesis 5 hydroxymethyl furfural.
Influence of the 11. differential responses pressure of table to synthesis 5 hydroxymethyl furfural
Embodiment 12
It uses fluorine silicon resin for carrier material, changes the reaction time.Other experiment conditions are the same as embodiment 1.It investigates different anti-
To the influence of synthesis 5 hydroxymethyl furfural between seasonable, it is specifically shown in Table 12.
Influence of the 12. differential responses time of table to synthesis 5 hydroxymethyl furfural
Comparative example 1
Water and anhydrous methanol is respectively adopted as liquid phase solvent, uses fluorine silicon resin for carrier material, other experiment conditions
With embodiment 1, influence of the different solvents to synthesis 5 hydroxymethyl furfural is investigated.Specifically it is shown in Table 13.
Influence of 13. different solvents of table to synthesis 5 hydroxymethyl furfural
Comparative example 2
The titanium dioxide of titanium dioxide solids super acids and floride-free silicon carrier that fluorine silicon resin is carrier preparation is respectively adopted
For titanium solid super-strong acid as catalyst, other experiment conditions investigate soluble catalyst and insolubility with embodiment 1 respectively
Influence of the catalyst to synthesis 5 hydroxymethyl furfural.Specifically it is shown in Table 14.
Influence of 14. different solvents of table to synthesis 5 hydroxymethyl furfural
Can be seen that by the result of comparative example 1 and comparative example 2 uses methanol as liquid phase solvent, greatly reduces pair
The generation of reaction improves the selectivity of 5 hydroxymethyl furfural, uses high molecular material as carrier, catalyst can be made more preferable
Ground is distributed in system, substantially increases catalytic efficiency.
Claims (10)
1. a kind of preparation method of carried superstrong solid acid catalyst, which is characterized in that specifically comprise the following steps:
Carrier, metal oxide are added in sulfuric acid solution, stirred, is filtered, it is dry, roast 12 at 450 DEG C~650 DEG C~
For 24 hours, the carried superstrong solid acid catalyst is obtained.
2. preparation method according to claim 1, which is characterized in that the carrier is siliceous and/or fluorine macromolecule;It is described
Oxide is zirconium dioxide (ZrO2), titanium dioxide (TiO2), cobalt oxide (CoO), cobalt sesquioxide (Co2O3), molybdenum oxide
(MoO3), bismuth oxide (Bi2O3), at least one of nickel oxide (NiO).
3. preparation method according to claim 1, which is characterized in that the dosage of carrier, metal oxide and sulfuric acid solution
Ratio (g/g/mL) is 1:(1~5): (10~40).
4. preparation method according to claim 1, which is characterized in that the sulfuric acid solution concentration is 0.5M~2M.
5. preparation method according to claim 1, which is characterized in that the mixing time is 6~12h.
6. preparation method according to claim 2, which is characterized in that described for polysiloxane rubber or to gather containing polymeric silicon
Silicone resin, preferably poly- methyl silicon resin, amino silicone, fluorine silicon resin, silicone-epoxy resin, methyl silicone rubber
(MQ), methyl vinyl silicone rubber (VMQ), methyl vinyl phenyl silicon rubber (PVMQ), among nitrile silicone rubber, fluorine silicone rubber
It is at least one;The fluoro containing polymers are fluorochemical acrylate polymer, preferably polyacrylic acid 1,1- dihydro perfluor monooctyl ester
(PFOA), at least one of polytetrafluoroethylene (PTFE).
7. a kind of method for synthesizing 5 hydroxymethyl furfural, which is characterized in that use claim 1-6 any one the method system
Standby obtained carried superstrong solid acid catalyst, specifically comprises the following steps:
(1) raw material, anhydrous methanol and the catalyst are added in autoclave;
(2) heating is forced into reaction required temperature and pressure, after sealing reaction kettle, is stirred to react;
(3) after reaction, it is cooled to room temperature, after reaction mixture filtering, revolving removal methanol obtains 5 hydroxymethyl furfural.
8. it is according to claim 7 synthesis 5 hydroxymethyl furfural method, which is characterized in that the raw material be glucose,
Fructose, chitosan, chitin, cellulose, hemicellulose, lignin, lactose and protist matter;The protist matter is
Trees, pericarp, bamboo, agricultural crop straw.
9. it is according to claim 7 synthesis 5 hydroxymethyl furfural method, which is characterized in that the catalyst, raw material and
The amount ratio (g/g/mL) of anhydrous methanol is 1:(10~20): (50~100).
10. the method for synthesis 5 hydroxymethyl furfural according to claim 7, which is characterized in that the reaction temperature is 240
DEG C~320 DEG C;The reaction pressure is 8.1~22MPa;The reaction time is 3-10 hours.
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CN111484877A (en) * | 2020-05-08 | 2020-08-04 | 成都理工大学 | Microwave hydrothermal carbon decoupling chemical chain gasification method for regulating and controlling quality of synthesis gas |
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