CN106475145A - A kind of immobilized ionic-liquid catalyst for preparing 5 hydroxymethylfurfurals and its preparation - Google Patents
A kind of immobilized ionic-liquid catalyst for preparing 5 hydroxymethylfurfurals and its preparation Download PDFInfo
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- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
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Abstract
The invention belongs to method for preparing catalyst and biomass efficient transformation technology field, disclose a kind of immobilized ionic-liquid catalyst for preparing 5 hydroxymethylfurfurals and its preparation.The catalyst is to be obtained immobilized for functionalized acidic ionic liquid in the carrier, and wherein load capacity of the ionic liquid on carrier is 5%～30%.The catalyst is used for preparing 5 hydroxymethylfurfurals.The mild condition of the present invention, running cost are low, the excellent catalytic effect of catalyst, and the problems such as can be prevented effectively from loss and the solvent loss of catalyst caused during the course of the reaction, catalyst regeneration is convenient, recycles effect good.
Description
Technical field
The invention belongs to method for preparing catalyst and biomass efficient transformation technology field, and in particular to a kind of with immobilized
The novel preparation method in situ of ionic liquid and its application of 5 hydroxymethyl furfural is prepared in biomass catalyzing conversion.
Background technology
It is well known that the non-renewable resources such as coal and oil are the fast-developing bases of human society, however as society
Civilization continuous progress, traditional fossil energy increasingly depleted, therefore people have to find a kind of regenerative resource as fossil
The substitute of resource.Living beings refer to the various organisms produced using big gas and water, soil etc. by photosynthesis, be only
Inferior to oil, coal, natural gas the fourth-largest energy, be modal renewable resource on the earth.The current profit to living beings
Direct-Combustion Technology, materialization switch technology, biochemical switch technology and several sides of plant oil tech are broadly divided into transformation technology
Method.The orientation conversion of carbohydrate is the basis that biomass resource makes full use of, and only realizes selective orientation conversion, ability
Realize biomass resource and progressively replace fossil resource.And in the product of catalytic production 5 hydroxymethyl furfural (HMF) be across carbon water
A kind of important industrial chemicals between compound and petrochemical industry, it is considered to be the bridge of connection petrochemical industry and living beings industry
Beam.5 hydroxymethyl furfural (5-HMF) contains methylol, aldehyde radical and the biomass-based platform chemicals of furan nucleus for one kind, available
Existing chemical technology is converted into liquid alkane, industrial solvent and biological based high molecular, with each 2,5- furans which is raw material production
Dicarbaldehyde, 2,5- furandicarboxylic acid, levulic acid, formic acid etc. have in key areas such as medicine, high molecule plastic, fuel oil additives
There is huge potential using value.
Existing at present many researchs report the catalyst for preparing 5-HMF with living beings as substrate, mainly include homogeneous acid
Catalyst and two big class of heterogeneous acid catalyst.Specifically include inorganic acid catalyst, organic acid catalyst, Louis acid catalysis
Agent, solid acid catalyst, ionic-liquid catalyst, saline catalyst etc..At present, biomass-based HMF mainly with fructose or
Person's fructose class presoma is raw material, with homogeneous acidity (inorganic acid, organic acid, lewis acid etc.) and solid acid (acid zeolite, acid
Property resin etc.) be catalyst.Roman-Leshkov etc.[1]Concentration is the salt acid as catalyst of 0.25mol/L, and glucose is molten
In the 35% NaCl aqueous solution, 180 DEG C of reaction 3min, the conversion ratio of glucose can reach 56%, 5-HMF and be selectively solution
48%；The seminar that Carlinia is located[2]A series of modified niobium phosphates are attempted for being catalyzed the preparation 5- of fructose dehydration
HMF, the conversion ratio of gained fructose are only the selectivity of 30%, 5-HMF and are up to 90%；Qi etc.[3]Condition in heating using microwave
Under, have studied the reaction of fructose dehydration production HMF.Used catalyst is cation exchange tree Dowex50wx82100, and solvent is
Acetone-water mixture, at 150 DEG C, the yield of 5-HMF can reach 73.4%, and the conversion ratio of fructose is 94%.However, this
A series of use of catalyst more or less all exist recovery difficulty, etching apparatus, environmental pollution, low substrate conversion efficiency,
Poor catalyst preparation process of heat endurance, relatively low catalysis activity and complexity etc..
Serious cost, the recovery use of catalysts and solvents and product is there is in the catalyst system and catalyzing of research before
The problems such as separating and purify, therefore developing high, sustainable production, the green HMF production process of large-scale, economy is
Its commercial Application first has to the problem for solving.
Bibliography：
[1]Román-Leshkov Y,Chheda J N,Dumesic J A.Phase modifiers promote
efficient production of hydroxymethylfurfural from fructose[J].Science,2006,
312(5782):1933-1937.
[2]Carlini C,Giuttari M,Galletti A M R,et al.Selective saccharides
dehydration to 5-hydroxymethyl-2-furaldehyde by heterogeneous niobium
catalysts[J].Applied Catalysis A:General,1999,183(2):295-302.
[3]Qi X,Watanabe M,Aida T M,et al.Selective conversion of D-fructose
to 5-hydroxymethylfurfural by ion-exchange resin in acetone/dimethyl
sulfoxide solvent mixtures[J].Industrial&Engineering Chemistry Research,2008,
47(23):9234-9239.
Content of the invention
In place of solving the shortcoming and defect of prior art, the primary and foremost purpose of the present invention is to provide one kind for preparing
The immobilized ionic-liquid catalyst of 5 hydroxymethyl furfural (5-HMF).The immobilized ionic liquid overcomes conventional ion liquid
Body and solvent are difficult to the shortcomings of recycling, and take into account the advantage of homogeneous and heterogeneous catalyst, with good catalytic effect, and
The rate of recovery is high, environmentally safe.
Another object of the present invention is to providing above-mentioned for preparing the immobilized ionic liquid-catalyzed of 5 hydroxymethyl furfural
The preparation method of agent.
It is still another object of the present invention to provide the application of above-mentioned immobilized ionic-liquid catalyst.
The object of the invention is achieved through the following technical solutions：
A kind of immobilized ionic-liquid catalyst (acidic catalyst) for preparing 5 hydroxymethyl furfural, be by acid work(
Ionic liquid supported can be changed obtain in the carrier, wherein load capacity of the ionic liquid on carrier is 5%～30%.
The carrier is molecular sieve or multi-walled carbon nano-tubes, the molecular sieve be SBA-15, NaY, MCM-41, MCM-22 or
In ZSM-5 more than one, the multi-walled carbon nano-tubes for carboxylated multi-walled carbon nano-tubes.
The functionalized acidic ionic liquid is made up of cation and anion, and the cation carries sulfonic group for side chain
Or the imidazole salt cation of carboxylic acid group.
The anion is anion hydrogen sulphate or chlorion.
The preparation method for preparing the immobilized ionic-liquid catalyst of 5 hydroxymethyl furfural, including following three kinds
Method：
Method a is：(a-1) with organic solvent as reaction medium, by glyoxaline compound and haloalkylalkoxysilan
Reacted, revolving, obtained presoma I；
(a-2) with organic solvent 1 as reaction medium, presoma I is reacted with alkylcarboxylic acid, revolving, is obtained
Ionic liquid a；In organic solvent 2, carrier is carried out heating stirring with ionic liquid a, filter, washing, dry, obtain immobilized
Change ionic-liquid catalyst.
Method b is：(b-1) with organic solvent as reaction medium, by glyoxaline compound and haloalkylalkoxysilan
Reacted, revolving, obtained presoma I；
(b-2) presoma I is reacted with sultones, revolving, is obtained presoma II；
(b-3) presoma II, the concentrated sulfuric acid and carrier are reacted, is obtained immobilized ionic-liquid catalyst.
Method c is：(c-1) in organic solvent, glyoxaline compound and carrier are stirred mixing, add in sulfonic acid
Ester is reacted, and is filtered, and washing obtains crude product；
(c-2) crude product is dissolved in organic solvent, the addition concentrated sulfuric acid, heating response, filtration washing, dries, obtain
Immobilized ionic-liquid catalyst；
In methods described a, b and c glyoxaline compound be imidazoles, N- methylimidazole, N- ethyl imidazol(e), in N- propyl imidazole
More than one；
In methods described b and c sultones be in 1,3- propane sultone or 1,4- butane sultones more than one.
In methods described a and b, haloalkylalkoxysilan is 3- chloropropyl triethoxysilane or 3- chloropropyl front three
In TMOS more than one.
In methods described a alkylcarboxylic acid be in monoxone or chloropropionic acid more than one.
Glyoxaline compound in methods described a and method b：The mol ratio of haloalkylalkoxysilan is 1：(1～
1.2)；
Glyoxaline compound in methods described a：The mol ratio of alkylcarboxylic acid is 1：(1～1.2)；In methods described a
The mole dosage of glyoxaline compound is (0.01～0.7) mol with carrier quality ratio：(1～5) g.
Glyoxaline compound in methods described b：Sultones：The mol ratio of sulfuric acid is 1：(1～1.2)：(1～1.2)；Institute
It is (0.01～0.7) mol with carrier quality ratio to state the mole dosage of glyoxaline compound in method b：(1～5) g.
In methods described c, glyoxaline compound is 1 with the mol ratio of sultones：(1～2.2)；The imidazoles chemical combination
Thing is 1 with the mol ratio of sulfuric acid：(1～1.2)；The mole dosage of the glyoxaline compound and carrier quality ratio for (0.01～
0.7)mol：(1～5) g.
Organic solvent described in methods described a is conventional organic solvent, preferably ethanol；Organic solvent 1 has for conventional
Machine solvent, preferably ethanol or acetonitrile；Organic solvent 2 is conventional organic solvent, preferably in toluene or ethanol more than one.
Organic solvent described in methods described b is conventional organic solvent, preferably ethanol.
In the step of methods described c (c-1), organic solvent is conventional organic solvent, preferably in ethanol Step (a-2)
Organic solvent is conventional organic solvent, preferably dichloromethane.
It is anti-at 50～65 DEG C to add the reaction condition reacted by sultones in the step of methods described c (c-1)
Answer 8～12h.
In the step of methods described c (c-2), the condition of heating response is to react 8～24h at 50～65 DEG C；The drying
Condition is to dry 12～24h at 60～80 DEG C.
In methods described a in step (a-1) and method b the reaction condition of step (b-1) be react 12 in 60～100 DEG C～
24h.
In the step of methods described a (a-2) reaction condition reacted by presoma I and alkylcarboxylic acid be in 50～
8～24h is reacted at 65 DEG C；The carrier and ionic liquid a carry out the condition of heating stirring be at 90～120 DEG C stirring 24～
48h.
The reaction condition reacted by presoma I described in the step of methods described b (b-2) and sultones be in 40～
8～24h is reacted at 65 DEG C.
Step (b-3) is concretely comprised the following steps：Under conditions of ice bath, the concentrated sulfuric acid is added in presoma II, heat up anti-
Should, obtain ionic liquid b；In organic solvent 3, carrier is carried out heating stirring with ionic liquid b, filter, washing, dry,
Obtain immobilized ionic-liquid catalyst.
In methods described b, organic solvent 3 is conventional organic solvent, preferably in ethanol or toluene more than one；The side
The condition of temperature reaction described in the step of method b (b-3) is to react 12～24h at 50～60 DEG C.
The condition that carrier and ionic liquid b carry out heating stirring in methods described b be at 80～120 DEG C stirring 24～
48h.
Drying condition described in step (b-3) is to dry 12～24h at 60～80 DEG C.Washing described in step (b-3) is
Refer to be washed using ethanol, dichloromethane or ether.
Or step (b-3) is concretely comprised the following steps：By presoma II and carrier heating stirring, mistake in organic solvent 4
Filter, washing, obtain crude product；Crude product is dispersed in organic solvent 5, under condition of ice bath, the addition concentrated sulfuric acid, heating response,
Filter, washing, dry, obtain immobilized ionic-liquid catalyst.
The organic solvent 4 is conventional organic solvent, preferably in toluene or ethanol more than one；The organic solvent 5
For conventional organic solvent, preferably in ethanol or dichloromethane more than one.
In methods described b, the condition of heating stirring in organic solvent 4 is to stir at 90～120 DEG C to presoma II with carrier
Mix 24～48h；The condition of the heating response is to react 8～24h at 50～65 DEG C.
The drying condition of methods described b is to dry 12～24h at 60～80 DEG C.
Described in step (b-3), washing refers to be washed using ethanol, dichloromethane or ether.
The revolving condition of methods described a and method b is all 0.5～1h of revolving at 50～60 DEG C.
In methods described a and c, all of washing refers to be washed using ethanol, dichloromethane or ether.
In the preparation method, the amount of organic solvent (as ethanol, toluene and dichloromethane) need not be particularly limited to, typically
Ionic liquid cation presoma can be dissolved.
The described method for preparing HMF is：Substrate living beings, catalysts and solvents are placed in heating response in reactor,
Obtain HMF；The catalyst is above-mentioned immobilized ionic-liquid catalyst.The substrate living beings：Solvent：The consumption of catalyst
For (0.1～1.0) g：(5～15) ml：(25～100) mg, the reaction temperature are 80 DEG C～120 DEG C, and the reaction time is 0.5h
～3h.
The living beings be in glucose or fructose more than one, but not limited to this.The solvent is methyl iso-butyl ketone (MIBK)
In mixture, dimethyl sulfoxide, isopropanol with water more than one.
Compared with prior art, the present invention has advantages below and beneficial effect：
(1) functionalized acidic ionic liquid is loaded over a molecular sieve by the present invention using in-situ synthesis, can be effectively
Improve the dispersion effect in active acidic site and catalytic efficiency and can effectively prevent the loss of functionalized ion liquid；
(2) catalyst of the present invention and solvent recovering rate height, can clean, efficiently obtain high added value platform chemicals 5-
HMF.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Embodiment 1
(1), in adding 0.10mol N- methylimidazole to 30mL ethanol, (speed of agitator is 300rpm) is being stirred vigorously
Under, add 5g ZSM-5 molecular sieve, under room temperature, stir 10h, make N- methylimidazole molecular sieve be able to fully dispersed after, then to which
The middle ethanol solution added dissolved with 0.2mol 1,3- propane sultone, stirring reaction 12h at 50 DEG C, suction filtration, is washed with ethanol
3 times, by responseless N- methylimidazole, 1,3- propane sultone, and be only attached to molecular sieve surface both
Product fully washs removing, so as to obtain crude white solid, is as loaded with 1- propane sulfonic acid base -3- methylimidazole
ZMS-5 molecular sieve；
(2) by crude white solid obtained in step (1), dispersed with stirring in the dichloromethane of 30mL, after be added dropwise over
Moderate amount of sulfuric acid (consumption of sulfuric acid is 0.11mol), at 50 DEG C, is refluxed reaction 24h.After reaction terminates, reactant liquor is entered
Row suction filtration, is washed after 3 times with dichloromethane, is placed in 70 DEG C of vacuum drying chamber and is dried overnight, that is, obtains immobilized ionic liquid A：
It is loaded with the ZSM-5 molecular sieve of 1- propane sulfonic acid base -3- methylimidazolium hydrogen sulphate salt.The load factor of ionic liquid is 20%.
Immobilized ionic liquid A, the 10ml isopropanol of fructose 0.18g, 0.025g is accurately weighed, 100 DEG C, reacts 2h, reaction
After end, cooling, the filtrate obtained after filtration are analyzed with HPLC after being settled to 100ml, and it is 85% to obtain fructose converting rate,
5-HMF yield is 59%.
Embodiment 2
(1) imidazoles for taking 0.10mol is added in the absolute ethyl alcohol of 30ml, and adds three ethoxy of 3- chloropropyl of 0.11mol
Base silane, under 100 DEG C of stirrings, (time of stirring is 24h) obtains presoma I；Add in the solution that above-mentioned reaction is obtained afterwards
0.1mol 1,3- propane sultone, stirs 24h at 40 DEG C, obtains presoma II；The SBA-15 of 3g is dispersed in 50ml toluene
In, and 1.5g presoma II obtained above is added, at 100 DEG C, stirring 24h, suction filtration, the white powder solid for obtaining, use second
Alcohol is washed 3 times, obtains having loaded the SBA-15 molecular sieve of 1- siloxanes -3-N-morpholinopropanesulfonic acid base imidazoles chloride ion liquid；
(2) the SBA-15 molecular sieve of 1- siloxanes -3-N-morpholinopropanesulfonic acid base imidazoles chloride ion liquid will have been loaded, ultrasonic disperse exists
In 50ml ethanol, after gradually drip the appropriate concentrated sulfuric acid under conditions of ice bath (concentrated sulfuric acid mass concentration be 98%, and consumption is
0.11mol), afterwards at 50 DEG C, 24h is refluxed, reaction terminates rear suction filtration, washed with dichloromethane 3 times, (dry after drying
Dry temperature is 80 DEG C, and the time is 12h) obtain final product immobilized ionic liquid B：1- siloxanes -3-N-morpholinopropanesulfonic acid base imidazole bisulfate
SBA-15 molecular sieve.The load factor of ionic liquid is 30%.
Immobilized ionic liquid B, the 10ml isopropanol of fructose 0.18g, 0.025g is accurately weighed, 100 DEG C, reacts 2h, reaction
After end, cooling, the filtrate obtained after filtration are analyzed with HPLC after being settled to 100ml, and it is 97% to obtain fructose converting rate,
5-HMF yield is 81%.
Immobilized ionic liquid B, the 10ml isopropanol of glucose 0.18g, 0.025g is accurately weighed, 140 DEG C, 2h is reacted, instead
After should terminating, cooling, the filtrate obtained after filtration are analyzed with HPLC after being settled to 100ml, and obtaining inversion rate of glucose is
67%, 5-HMF yield is 31%.
Embodiment 3
(1) imidazoles for taking 0.10mol is added in the absolute ethyl alcohol of 30ml, and adds three ethoxy of 3- chloropropyl of 0.11mol
Base silane, under 100 DEG C of stirrings (time of stirring is 24h), obtains presoma I；Add in the solution that above-mentioned reaction is obtained afterwards
0.1mol chloropropionic acid, stirs 24h at 60 DEG C, obtains ionic liquid；
(2) MCM-22 of 3g is dispersed in 50ml toluene, and above-mentioned ionic liquid is added, at 100 DEG C, 24h is stirred,
Suction filtration, the white powder solid for obtaining, washed with ethanol 3 times, (dry temperature is 80 DEG C, and the time is 12h) is dry, is born
The MCM-22 molecular sieve of 1- siloxanes -3- acetic acid imidazoles chloride ion liquid is carried, as prepared immobilized ionic liquid C.
The load factor of ionic liquid is 15%.
Immobilized ionic liquid C, the 10ml isopropanol of fructose 0.18g, 0.025g is accurately weighed, 100 DEG C, reacts 2h, reaction
After end, cooling, the filtrate obtained after filtration are analyzed with HPLC after being settled to 100ml, and it is 86% to obtain fructose converting rate,
5-HMF yield is 61%.
It is immobilized ionic liquid C, 8ml methyl iso-butyl ketone (MIBK) (MIBK) that fructose 0.18g, 0.025g are accurately weighed, 2ml water,
, 2h is reacted, after reaction terminates, reaction result HPLC is analyzed, fructose converting rate is obtained for 89%, 5-HMF yield by 100 DEG C
For 67%.
Embodiment 4
(1) imidazoles for taking 0.10mol is added in the absolute ethyl alcohol of 30ml, and adds three ethoxy of 3- chloropropyl of 0.11mol
Base silane, under 100 DEG C of stirrings, (time of stirring is 24h) obtains presoma I；Add in the solution that above-mentioned reaction is obtained afterwards
0.1mol1,3- propane sultone, stirs 24h at 40 DEG C, obtains presoma II；Past obtained above under conditions of ice bath
The concentrated sulfuric acid (concentrated sulfuric acid mass concentration be 98%, consumption be 0.11mol) is dropwise dripped in presoma II, after dripping at 50 DEG C
Stirring 24h, revolving are washed with ether after removing ethanol 3 times, and 60 DEG C of vacuum drying (the dry time is 12h) remove ether
Afterwards, grease is obtained：1- siloxanes -3-N-morpholinopropanesulfonic acid base imidazole bisulfate ionic liquid；
(2) taking 3g functionalized multi-wall carbonnanotubes adds ultrasonic disperse in 50ml ethanol uniform, adds above-mentioned grease, it
Afterwards at 90 DEG C, 24h is refluxed, reaction terminates rear suction filtration, washed with dichloromethane 3 times, (dry temperature is 80 after drying
DEG C, the time is 12h), obtained black powder is immobilized ionic liquid D：1- siloxanes -3-N-morpholinopropanesulfonic acid base imidazoles is loaded
The multi-walled carbon nano-tubes of disulfate.The load factor of ionic liquid is 16%.
Immobilized ionic liquid D, the 10ml isopropanol of fructose 0.18g, 0.025g is accurately weighed, 100 DEG C, reacts 2h, reaction
After end, cooling, the filtrate obtained after filtration are analyzed with HPLC after being settled to 100ml, and it is 93% to obtain fructose converting rate,
5-HMF yield is 77%.
Immobilized ionic liquid B, the 10ml isopropanol of glucose 0.18g, 0.025g is accurately weighed, 140 DEG C, 2h is reacted, instead
After should terminating, cooling, the filtrate obtained after filtration are analyzed with HPLC after being settled to 100ml, and obtaining inversion rate of glucose is
69%, 5-HMF yield is 38%.
Embodiment 5
It is immobilized ionic liquid A, 10ml dimethyl sulfoxide (DMSO) that fructose 0.18g, 0.025g are accurately weighed, 100 DEG C, reaction
2h, after reaction terminates, cooling, the filtrate obtained after filtration are analyzed with HPLC after being settled to 100ml, obtain fructose converting rate
It is 67% for 88%, 5-HMF yield.
It is immobilized ionic liquid D, 10ml dimethyl sulfoxide (DMSO) that fructose 0.18g, 0.025g are accurately weighed, 100 DEG C, reaction
2h, after reaction terminates, cooling, the filtrate obtained after filtration are analyzed with HPLC after being settled to 100ml, obtain fructose converting rate
It is 79% for 96%, 5-HMF yield.
Embodiment 6
(1) imidazoles for taking 0.10mol is added in the absolute ethyl alcohol of 30ml, and adds three ethoxy of 3- chloropropyl of 0.11mol
Base silane, under 100 DEG C of stirrings, (time of stirring is 24h) obtains presoma I；Add in the solution that above-mentioned reaction is obtained afterwards
0.1mol chloropropionic acid, stirs 24h at 60 DEG C, obtains ionic liquid；
(2) MCM-41 of 3g is dispersed in 50ml toluene, and above-mentioned ionic liquid is added, at 100 DEG C, 24h is stirred,
Suction filtration, the white powder solid for obtaining, washed with ethanol 3 times, (dry temperature is 80 DEG C, and the time is 12h) is dry, is born
The SBA-15 molecular sieve of 1- siloxanes -3- acetic acid imidazoles chloride ion liquid is carried, as prepared immobilized ionic liquid E.
The load factor of ionic liquid is 15%.
Immobilized ionic liquid E, the 10ml isopropanol of fructose 0.18g, 0.025g is accurately weighed, 110 DEG C, reacts 2h, reaction
After end, cooling, the filtrate obtained after filtration are analyzed with HPLC after being settled to 100ml, and it is 91% to obtain fructose converting rate,
5-HMF yield is 69%.
Fructose 0.18g, 0.025g immobilized ionic liquid E, 2ml water accurately weighed, 8mlMIBK, reacts 2h, instead by 120 DEG C
It is analyzed with HPLC after should terminating, it is 57% to obtain fructose converting rate for 78%, 5-HMF yield.
Embodiment 7
(1) imidazoles for taking 3mol is added in the absolute ethyl alcohol of 30ml, and adds the 3- chloropropyl triethoxy silicon of 3.3mol
Alkane, obtains presoma I under 80 DEG C of stirrings (time of stirring is 24h)；3mol 1 is added afterwards in the solution that above-mentioned reaction is obtained,
3- propane sultone, stirs 24h at 40 DEG C, obtains presoma II；Toward presoma II obtained above under conditions of ice bath
In dropwise drip the concentrated sulfuric acid (concentrated sulfuric acid mass concentration be 98%, consumption be 3.3mol), after dripping at 50 DEG C stir 24h,
Revolving (temperature of revolving is 60 DEG C, and the time is 30min) is washed with ether 3 times after removing ethanol, and 60 DEG C of vacuum drying (dry
Time be 12h) remove ether after grease：1- siloxanes -3-N-morpholinopropanesulfonic acid base imidazole bisulfate ionic liquid；
(2) 15gNaY molecular sieve is added ultrasonic disperse in 150ml ethanol uniform, adds above-mentioned grease (i.e. 1- silica
Alkane -3-N-morpholinopropanesulfonic acid base imidazole bisulfate ionic liquid), at 80 DEG C, 24h is refluxed, reaction terminates rear suction filtration, uses dichloro
Methane wash 3 times, obtained white powder is immobilized ionic liquid afterwards to dry (dry temperature is 80 DEG C, and the time is 12h)
Body F：The NaY molecular sieve of 1- siloxanes -3-N-morpholinopropanesulfonic acid base imidazole bisulfate is loaded.The load factor of ionic liquid is 21%.
Fructose 0.18g, 0.025g immobilized ionic liquid E, 10mlDMSO, 110 DEG C is accurately weighed, reacts 2h, reaction knot
Shu Hou, cooling, the filtrate obtained after filtration are analyzed with HPLC after being settled to 100ml, obtain fructose converting rate for 81%, 5-
HMF yield is 59%.
Claims (10)
1. a kind of immobilized ionic-liquid catalyst for preparing 5 hydroxymethyl furfural, it is characterised in that：Be by acid function
Change ionic liquid supported to obtain in the carrier, wherein load capacity of the ionic liquid on carrier is 5%～30%.
2. it is used for according to claim 1 preparing the immobilized ionic-liquid catalyst of 5 hydroxymethyl furfural, it is characterised in that：
The carrier is molecular sieve or multi-walled carbon nano-tubes, and the molecular sieve is in SBA-15, NaY, MCM-41, MCM-22 or ZSM-5
More than one, the multi-walled carbon nano-tubes is the multi-walled carbon nano-tubes of carboxylated；
The functionalized acidic ionic liquid is made up of cation and anion, and the cation is for side chain with sulfonic group or carboxylic
The imidazole salt cation of acidic group；
The anion is anion hydrogen sulphate or chlorion.
3. for preparing the immobilized ionic-liquid catalyst of 5 hydroxymethyl furfural according to any one of claim 1～2
Preparation method, it is characterised in that：Including following three kinds of methods：
Method a is：(a-1) with organic solvent as reaction medium, glyoxaline compound is carried out with haloalkylalkoxysilan
Reaction, revolving, obtain presoma I；
(a-2) with organic solvent 1 as reaction medium, presoma I is reacted with alkylcarboxylic acid, revolving, is obtained ion
Liquid a；In organic solvent 2, carrier and ionic liquid a are carried out heating stirring, filter, washing, dry, obtain immobilized from
Sub- liquid catalyst；
Method b is：(b-1) with organic solvent as reaction medium, glyoxaline compound is carried out with haloalkylalkoxysilan
Reaction, revolving, obtain presoma I；
(b-2) presoma I is reacted with sultones, revolving, is obtained presoma II；
(b-3) presoma II, the concentrated sulfuric acid and carrier are reacted, is obtained immobilized ionic-liquid catalyst；
Method c is：(c-1) in organic solvent, glyoxaline compound and carrier are stirred mixing, add sultones to enter
Row reaction, filters, and washing obtains crude product；
(c-2) crude product is dissolved in organic solvent, the addition concentrated sulfuric acid, heating response, filtration washing, dries, obtain immobilized
Change ionic-liquid catalyst.
4. according to claim 3 for preparing the preparation method of the immobilized ionic-liquid catalyst of 5 hydroxymethyl furfural,
It is characterized in that：In methods described a, method b and method c glyoxaline compound be imidazoles, N- methylimidazole, N- ethyl imidazol(e),
In N- propyl imidazole more than one；
In methods described b and method c sultones be in 1,3- propane sultone or 1,4- butane sultones more than one；
In methods described a and method b, haloalkylalkoxysilan is 3- chloropropyl triethoxysilane or 3- chloropropyl front three
In TMOS more than one；
In methods described a alkylcarboxylic acid be in monoxone or chloropropionic acid more than one；
In methods described a, organic solvent 1 is conventional organic solvent.
5. according to claim 3 for preparing the preparation method of the immobilized ionic-liquid catalyst of 5 hydroxymethyl furfural,
It is characterized in that：Add in the step of methods described c (c-1) reaction condition reacted by sultones be at 50～65 DEG C
8～12h of reaction；
In the step of methods described c (c-2), the condition of heating response is to react 8～24h at 50～65 DEG C；
In methods described a, in step (a-1) and method b, the reaction condition of step (b-1) is to react 12～24h in 60～100 DEG C；
In the step of methods described a (a-2) reaction condition reacted by presoma I and alkylcarboxylic acid be in 50～65 DEG C
8～24h of lower reaction；The condition that the carrier carries out heating stirring with ionic liquid a is to stir 24～48h at 90～120 DEG C；
The reaction condition reacted by presoma I described in the step of methods described b (b-2) and sultones be in 40～65 DEG C
8～24h of lower reaction.
6. according to claim 3 for preparing the preparation method of the immobilized ionic-liquid catalyst of 5 hydroxymethyl furfural,
It is characterized in that：Step (b-3) is concretely comprised the following steps：Under conditions of ice bath, the concentrated sulfuric acid is added in presoma II, is heated up
Reaction, obtains ionic liquid b；In organic solvent 3, carrier is carried out heating stirring with ionic liquid b, filter, washing, do
Dry, obtain immobilized ionic-liquid catalyst；
Or step (b-3) is concretely comprised the following steps：By presoma II and carrier heating stirring in organic solvent 4, filter, wash
Wash, obtain crude product；Crude product is dispersed in organic solvent 5, under condition of ice bath, the addition concentrated sulfuric acid, heating response, filters,
Washing, dries, obtains immobilized ionic-liquid catalyst.
7. according to claim 6 for preparing the preparation method of the immobilized ionic-liquid catalyst of 5 hydroxymethyl furfural,
It is characterized in that：The condition of temperature reaction described in step (b-3) is to react 12～24h at 50～60 DEG C；The carrier with
It is to stir 24～48h at 80～120 DEG C that ionic liquid b carries out the condition of heating stirring；
The condition of heating stirring in organic solvent 4 is to stir at 90～120 DEG C to presoma II described in step (b-3) with carrier
Mix 24～48h；The condition of the heating response is to react 8～24h at 50～65 DEG C；
The organic solvent 4 is conventional organic solvent；The organic solvent 5 is conventional organic solvent；The organic solvent 3 is normal
Rule organic solvent.
8. according to claim 3 for preparing the preparation method of the immobilized ionic-liquid catalyst of 5 hydroxymethyl furfural,
It is characterized in that：Glyoxaline compound in methods described a and method b：The mol ratio of haloalkylalkoxysilan is 1：(1～
1.2)；
Glyoxaline compound in methods described a：The mol ratio of alkylcarboxylic acid is 1：(1～1.2)；Imidazoles in methods described a
The mole dosage of class compound is (0.01～0.7) mol with carrier quality ratio：(1～5) g；
Glyoxaline compound in methods described b：Sultones：The mol ratio of sulfuric acid is 1：(1～1.2)：(1～1.2)；The side
In method b, the mole dosage of glyoxaline compound is (0.01～0.7) mol with carrier quality ratio：(1～5) g；
In methods described c, glyoxaline compound is 1 with the mol ratio of sultones：(1～2.2)；The glyoxaline compound with
The mol ratio of sulfuric acid is 1：(1～1.2)；The mole dosage of the glyoxaline compound is (0.01～0.7) with carrier quality ratio
mol：(1～5) g.
9. for preparing the immobilized ionic-liquid catalyst of 5 hydroxymethyl furfural according to any one of claim 1～2
Application, it is characterised in that：The immobilized ionic-liquid catalyst is used for preparing the method for HMF：By substrate living beings, catalysis
Agent and solvent are placed in heating response in reactor, obtain HMF；The catalyst is above-mentioned immobilized ionic-liquid catalyst.
10. apply according to claim 9, it is characterised in that：The substrate living beings：Solvent：The consumption of catalyst is
(0.1～1.0) g：(5～15) ml：(25～100) mg, the reaction temperature be 80 DEG C～120 DEG C, the reaction time be 0.5h～
3h；
The living beings be in glucose or fructose more than one, but not limited to this；The solvent is methyl iso-butyl ketone (MIBK) and water
Mixture, dimethyl sulfoxide, in isopropanol more than one.
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| CN106749122A (en) * | 2016-12-22 | 2017-05-31 | 同济大学 | Commerical grade Beta molecular sieve catalytics conversion carbohydrate is the method for 5 hydroxymethylfurfurals |
| CN108579805A (en) * | 2018-04-03 | 2018-09-28 | 胡珂 | A kind of catalyst and its preparation and application preparing Peracetic acid |
| CN110368985A (en) * | 2019-07-04 | 2019-10-25 | 浙江工业大学 | It is a kind of for 5-HMF synthesis catalyst and 5-HMF preparation method |
| CN111036195A (en) * | 2018-10-12 | 2020-04-21 | 中国石油化工股份有限公司 | Catalyst and preparation method of 2, 5-furandicarboxylic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106749122A (en) * | 2016-12-22 | 2017-05-31 | 同济大学 | Commerical grade Beta molecular sieve catalytics conversion carbohydrate is the method for 5 hydroxymethylfurfurals |
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| CN111036195A (en) * | 2018-10-12 | 2020-04-21 | 中国石油化工股份有限公司 | Catalyst and preparation method of 2, 5-furandicarboxylic acid |
| CN110368985A (en) * | 2019-07-04 | 2019-10-25 | 浙江工业大学 | It is a kind of for 5-HMF synthesis catalyst and 5-HMF preparation method |
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