CN109675538A - A kind of mixed crystal titanium dioxide R3-A2TiO2And its application in 5 hydroxymethyl furfural is prepared in catalysis glucose - Google Patents
A kind of mixed crystal titanium dioxide R3-A2TiO2And its application in 5 hydroxymethyl furfural is prepared in catalysis glucose Download PDFInfo
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- CN109675538A CN109675538A CN201811486591.2A CN201811486591A CN109675538A CN 109675538 A CN109675538 A CN 109675538A CN 201811486591 A CN201811486591 A CN 201811486591A CN 109675538 A CN109675538 A CN 109675538A
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- a2tio
- titanium dioxide
- mixed crystal
- glucose
- crystal titanium
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000013078 crystal Substances 0.000 title claims abstract description 33
- 239000008103 glucose Substances 0.000 title claims abstract description 23
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 19
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims abstract description 17
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 title claims description 21
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000012429 reaction media Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims abstract 3
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000005485 electric heating Methods 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 5
- 210000001742 aqueous humor Anatomy 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 2
- 229910002660 P25‐TiO2 Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The application in 5 hydroxymethyl furfural, the mixed crystal titanium dioxide R3-A2TiO are prepared the invention discloses a kind of mixed crystal titanium dioxide and its in catalysis glucose2It is containing rutile and two kinds of crystal forms of anatase and rutile: TiO of the anatase content than the mixing crystal form for 3:22, preparing 5 hydroxymethyl furfural includes following methods: according to the R3-A2TiO of mass ratio 1% ~ 10%2Glucose with 5% ~ 20%, is configured to mixed reaction media, and reaction medium is added in reactor, is preheated to 120 ~ 150 DEG C, reacts 240 min, natural cooling sample, and the solvent of reaction medium above-mentioned is aqueous solvent.
Description
Technical field
The present invention relates to a kind of mixed crystal titanium dioxide R3-A2TiO2And its it is prepared in 5 hydroxymethyl furfural in catalysis glucose
Application.
Background technique
A large amount of uses of fossil energy cause increasingly serious energy shortage problem.Biomass Energy Development reduces the mankind
Have become the main energy sources strategy of majority state to the dependence of fossil energy.5 hydroxymethyl furfural is to produce chemistry from biomass
The important chemical industry platform chemicals of product, can directly or indirectly be converted into a variety of products being possessed of higher values and novel high score
Sub- material.Heterogeneous catalyst have the advantages that it is environmental-friendly, be easily isolated.Reported solid acid catalyst functionalization is miscellaneous more
Acid, acidic ion liquid exchanger resin, molecular sieve and metal oxide etc..Wherein, the more difficult reality of most of solid acid catalyst
The high activity of 5 hydroxymethyl furfural process is prepared in existing aqueous solvent to glucose conversion.More solid acid catalyst not can avoid
The use of heavy metal and expensive organic solvent.Mainly there are water, organic solvent, ionic liquid using relatively broad solvent at present
And two kinds or more than mixture.Ionic liquid is although advantage is more, most of higher cost, therefore industry in the recent period
It is smaller to change application possibility.A large amount of uses of low boiling point organic solvent are caused stress to environment, and water is still most green at present
Solvent.
A kind of heterogeneous catalyst cheap and easy to get is developed, realizes biomass efficient conversion preparation 5- methylol in an aqueous medium
Furfural, having turns waste into wealth, solves environmental pollution and safeguards the significance of human kind sustainable development.
Summary of the invention
The purpose of the present invention is to provide the purpose of the present invention is to provide one kind simply by special ratios mixed crystal dioxy
Change titanium R3-A2TiO2The method that catalysis glucose prepares 5 hydroxymethyl furfural, to overcome in prior art using homogeneous catalyst
Corrosion equipment, be difficult to separate, cause serious pollution to the environment, the disadvantage that activity is low in reuse and aqueous solvent cannot be recycled.
A kind of mixed crystal titanium dioxide R3-A2TiO2, which is characterized in that preparation method includes the following: to be with titanyl sulfate
Raw material, using deionized water as solvent, 0.2 ~ 0.4 titanyl sulfate is placed in aqueous solvent, using 5% glucose as directed agents, centainly
Under the conditions of temperature, air atmosphere, with 500 ~ 1500 rpm stirring, 1 ~ 3h of reaction, then solution is filtered, collects solid simultaneously
It is dry in 60 ~ 80 DEG C of vacuum ovens, it weighs, save backup, special ratios mixed crystal titanium dioxide R3-A2TiO is made2；Institute
The mixed crystal titanium dioxide R3-A2TiO stated2The application in 5 hydroxymethyl furfural is prepared in catalysis glucose.
Preparing 5 hydroxymethyl furfural includes following methods: according to the R3-A2TiO of mass ratio 1% ~ 10%2With 5% ~ 20% Portugal
Grape sugar, is configured to mixed reaction media, reaction medium is added in reactor, be preheated to 120 ~ 150 DEG C, reaction above-mentioned
The solvent of medium is aqueous solvent.
The reactor is quartz glass pressure-resistant reaction vessel, and corresponding heating method is respectively that electric heating, oil bath add
Heat and microwave heating；Mixed crystal titanium dioxide R3-A2TiO2Recycling centrifugal rotational speed should be 3000 ~ 10000r/min, after centrifuge separation
R3-A2TiO2, it is washed with deionized 3 ~ 5 times, it is dry.
The utility model has the advantages that present invention is characterized in that 1. catalysis glucose prepare the application response in 5 hydroxymethyl furfural and exist
It is carried out under the conditions of 120 ~ 150 DEG C of temperature, temperature is lower, and energy consumption is lower；It is special ratios 2. catalyst is heterogeneous catalyst
Mixed crystal titanium dioxide R3-A2TiO2Containing rutile and two kinds of crystal forms of anatase and rutile: anatase content is than mixing for 3:2
The TiO of synthetic type2,, the raw material for preparing catalyst is cheap and easy to get, nontoxic and can be easily separated, and does not corrode equipment, repeats benefit
With.3. technological operation step is few, safe operation, there is good industrial applications prospect.
Detailed description of the invention
Fig. 1 is mixed crystal titanium dioxide R3-A2TiO2Sem figure.
Fig. 2 is mixed crystal titanium dioxide R3-A2TiO2XRD diagram.
Fig. 3 is mixed crystal titanium dioxide R3-A2TiO2TEM figure.
Fig. 4 is different TiO2The XRD diagram of sample.
Specific embodiment
Embodiment 1
0.4g titanyl sulfate is placed in aqueous solvent, using 5% glucose solution as directed agents, under the conditions of room temperature, air atmosphere,
It with 2000rpm stirring, impregnates 2 hours, then solution is filtered, collects solid drying in 60 DEG C of vacuum ovens, is claimed
It measures, save backup；Special ratios mixed crystal titanium dioxide R3-A2TiO is made2It is containing rutile and two kinds of crystal forms of anatase and gold
Red stone: TiO of the anatase content than the mixing crystal form for 3:22.Its sem figure, XRD diagram and TEM figure are respectively such as Fig. 1,2 Hes
Shown in 3.
Embodiment 2
3ml aqueous solution containing 5% glucose is added to pressure bottle, the R3-A2TiO that 0.05 g of addition is prepared2Catalyst, together
50 Mm H of Shi Tianjia+150 DEG C are heated in oil bath pan, 2000 with pressure resistant quartz glass reaction bottle as co-catalyst
Under conditions of rpm stirring, 240 min are reacted.After reaction, natural cooling sample is diluted with ultrapure water and uses efficient liquid phase
Chromatography glucose and 5 hydroxymethyl furfural content, it is 99.02% that inversion rate of glucose, which is calculated, and 5 hydroxymethyl furfural obtains
Rate is 31.38%.
Different crystal forms TiO2Crystal form ratio and its catalytic test:
Respectively by Anatase TiO2、G-TiO2Or P25-TiO2As Lewis acid, with 25 mm H2SO4Together as catalyst
It is catalyzed the conversion of aqueous humor glucose.P25-TiO2 and AnataseTiO2It is commercialization purchase.As shown in table 1, Detitanium-ore-type
TiO2HMF yield be 16.29%, illustrate Detitanium-ore-type TiO2It is a kind of effective Lewis acid for being catalyzed aqueous humor glucose conversion,
This is consistent with forefathers' conclusion.And G-TiO2HMF yield be 31.38%, show G-TiO2Than Anatase TiO2With higher
Catalytic activity.P25 TiO2HMF yield it is lower, be 6.23%.Speculate mixed crystal type TiO2Middle anatase-rutile crystal type content
Than having certain correlation to the catalytic activity of aqueous humor glucose conversion with it.P25 calcines 300 at 873 K or 973 K
Min obtains different anatases-rutile content ratio TiO2Sample, i.e. P25-873 and P25-973.According to P25-873 and
The XRD of P25-973 is composed, and calculating their anatase and the content ratio of rutile is respectively 74.36% and 25.69% (such as Fig. 4
It is shown).P25-873 or P25-973 is converted into HMF for being catalyzed glucose, and the results are shown in Table 1.The result shows that P25,
The HMF yield that P25-873 and P25-973 are provided is lower, and only G-TiO2With Anatase TiO2HMF yield it is higher, and G-
TiO2The catalytic activity highest of HMF is prepared to aqueous humor glucose conversion.
1. different crystal forms TiO of table2Crystal form ratio and its catalytic result
Reaction condition: glucose solution (3 mL; 5 w/w %), 423 K, 300 min, 500 rpm; a 2.67 mg/
ML NaOH is added simultaneously; b 62.5 mM;25 mM H2SO4 are added simultaneously.
Claims (4)
1. a kind of mixed crystal titanium dioxide R3-A2TiO2, which is characterized in that the mixed crystal titanium dioxide R3-A2TiO2It is containing gold
Red stone and two kinds of crystal forms of anatase and rutile: TiO of the anatase content than the mixing crystal form for 3:22；
Preparation method includes the following: using titanyl sulfate as raw material, and using deionized water as solvent, 0.2 ~ 0.4 titanyl sulfate is placed
In aqueous solvent, using 5% glucose as directed agents, under the conditions of certain temperature, air atmosphere, with 500 ~ 1500 rpm stirring, instead
1 ~ 3h is answered, then solution is filtered, collects solid and the drying in 60 ~ 80 DEG C of vacuum ovens, weighs, save backup,
Special ratios mixed crystal titanium dioxide R3-A2TiO is made2。
2. the mixed crystal titanium dioxide R3-A2TiO as described in power 12The application in 5 hydroxymethyl furfural is prepared in catalysis glucose.
3. application according to claim 3, it is characterised in that: preparing 5 hydroxymethyl furfural includes following methods: according to matter
Amount compares 1% ~ 10% R3-A2TiO2Glucose with 5% ~ 20%, is configured to mixed reaction media, and reaction medium is added to reaction
In device, 120 ~ 150 DEG C are preheated to, reacts 240 min；
After reaction, natural cooling sample, the solvent of reaction medium above-mentioned are aqueous solvent.
4. application according to claim 3, it is characterised in that: the reactor is quartz glass pressure-resistant reaction vessel,
Corresponding heating method is respectively electric heating, oil bath heating and microwave heating；Mixed crystal titanium dioxide R3-A2TiO2Recycling centrifugation turns
Speed should be 3000 ~ 10000r/min, the R3-A2TiO after centrifuge separation2, it is washed with deionized 3 ~ 5 times, it is dry.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811486591.2A CN109675538A (en) | 2018-12-06 | 2018-12-06 | A kind of mixed crystal titanium dioxide R3-A2TiO2And its application in 5 hydroxymethyl furfural is prepared in catalysis glucose |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811486591.2A CN109675538A (en) | 2018-12-06 | 2018-12-06 | A kind of mixed crystal titanium dioxide R3-A2TiO2And its application in 5 hydroxymethyl furfural is prepared in catalysis glucose |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112263999A (en) * | 2020-10-20 | 2021-01-26 | 广州维港环保科技有限公司 | Anatase-rutile mixed phase TiO2Catalyst, preparation method and application thereof |
| CN112375052A (en) * | 2020-10-20 | 2021-02-19 | 广州维港环保科技有限公司 | Method for preparing 2, 5-diformylfuran through glucose three-step cascade reaction |
| CN113262775A (en) * | 2021-05-27 | 2021-08-17 | 南京先进生物材料与过程装备研究院有限公司 | Metal-doped titanium dioxide catalyst and application thereof in glucose cyclization reaction |
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| CN101791546A (en) * | 2010-03-04 | 2010-08-04 | 上海大学 | Method for preparing mixed-phase nano-titania hydrosol photocatalyst |
| US20140107355A1 (en) * | 2012-10-11 | 2014-04-17 | Wisconsin Alumni Research Foundation | Method to convert monosaccharides to 5-(hydroxymethyl) furfural (hmf) using biomass-derived solvents |
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| US20140107355A1 (en) * | 2012-10-11 | 2014-04-17 | Wisconsin Alumni Research Foundation | Method to convert monosaccharides to 5-(hydroxymethyl) furfural (hmf) using biomass-derived solvents |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112263999A (en) * | 2020-10-20 | 2021-01-26 | 广州维港环保科技有限公司 | Anatase-rutile mixed phase TiO2Catalyst, preparation method and application thereof |
| CN112375052A (en) * | 2020-10-20 | 2021-02-19 | 广州维港环保科技有限公司 | Method for preparing 2, 5-diformylfuran through glucose three-step cascade reaction |
| CN112375052B (en) * | 2020-10-20 | 2023-06-16 | 广州维港环保科技有限公司 | Method for preparing 2, 5-diformylfuran through glucose three-step cascade reaction |
| CN113262775A (en) * | 2021-05-27 | 2021-08-17 | 南京先进生物材料与过程装备研究院有限公司 | Metal-doped titanium dioxide catalyst and application thereof in glucose cyclization reaction |
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