CN106749130A - A kind of method that 5 hydroxymethylfurfural prepares 2,5 furandicarboxylic acids - Google Patents
A kind of method that 5 hydroxymethylfurfural prepares 2,5 furandicarboxylic acids Download PDFInfo
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- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
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Abstract
The present invention relates to a kind of method that 5 hydroxymethylfurfural prepares 2,5 furandicarboxylic acids, comprise the following steps：1) catalyst carrier is added in organic solvent and is disperseed, be applied on quartz plate, heating removes organic solvent, is deposited in catalyst carrier platinum source using atomic layer deposition method, obtains platinum supported catalyst；2) by step 1) obtain platinum supported catalyst, 5 hydroxymethylfurfurals and aqueous solvent and be added in reactor, under oxygen atmosphere, 20~100 DEG C of 2~12h of reaction obtain 2,5 furandicarboxylic acids.Platinum supported catalyst is prepared by ALD atomic layer deposition methods in the preparation method, there is preferable catalytic performance in the reaction system of water phase, 2 in high yield can be obtained, 5 furandicarboxylic acids, and the catalyst stability prepared than tradition is preferably, with preferable water repelling property, not easy in inactivation.
Description
Technical field
The present invention relates to the preparation field of FDCA, and in particular to a kind of 5 hydroxymethyl furfural prepares 2,5- furans
Mutter the method for dioctyl phthalate.
Background technology
5 hydroxymethyl furfural be it is saccharide converted in important platform chemicals, can be by acid catalysis fructose, glucose and fibre
The carbohydrate dehydration such as dimension element is obtained.Its derivative such as 2,5- furandicarboxylic acids, 2,5- diformyls furans and acetyl
Propionic acid etc. suffers from extensive to apply in the fields such as medicine, plastics, fuel.Wherein, FDCA can be by 5-
Hydroxymethylfurfural selective oxidation is obtained, and is important organic compound intermediate, raw in being classified as 12 by USDOE 2004
One of thing based platform compound.
FDCA is considered as the preferable bio-based substitute of terephthalic acid (TPA), due to FDCA
With furan ring structure, it is easier degraded than the terephthalic acid (TPA) containing benzene ring structure.Additionally, the polyester material prepared by it
With more superior performance.Such as the new polyester material poly terephthalic acid second that Avantium companies of Holland are conducting vigorous propaganda
Diol ester (PET), the plastic bottle produced with this is to H2O、CO2And O2Barrier property be better than prepared by traditional PET material
Product.
Therefore, FDCA synthesis technique of the exploitation with industrial prospect and production environmental protection, will be current life
One of thing base polyester material industry key issue most urgently to be resolved hurrily.Current research is concentrated mainly on noble metal catalyst,
And to add some alkali during the course of the reaction, just can guarantee that yield higher, but product exist in a salt form, it is necessary to by
Series of steps can just obtain FDCA, and process is relatively complicated.Corma etc. (O.Casanova, S.Iborra,
A.Corma,Biomass into Chemicals:Aerobic Oxidation of 5-Hydroxymethyl-2-
furfural into 2,5-Furandicarboxylic Acid with Gold Nanoparticle Catalysts,
Chemsuschem, 2 (2009) 1138-1144.) report Au/CeO2And Au/TiO2Catalyst is in 65~130 DEG C, air pressure
10bar and highly basic (NaOH/5-HMF=4:1) the 2,5- furandicarboxylic acids yield obtained under the conditions of is up to 99%.
Davis seminars (S.E.Davis, L.R.Houk, E.C.Tamargo, A.K.Datye, R.J.Davis,
Oxidation of 5-hydroxymethylfurfural over supported Pt,Pd and Au catalysts,
Catal.Today, 160 (2011) 55-60) compare Pt, Pd and Au base catalyst 5-HMF catalysis prepare urging for 2,5-FDCA
Change activity, the primary product for as a result showing (23 DEG C, strong basicity) Pt/C and Pd/C catalyst under the same reaction conditions is 2,5-
FDCA, and Au/C and Au/TiO2The primary product of catalyst is 6- methylol -2- furancarboxylic acids, is illustrated in low-temperature alkali condition
Lower Pt, Pd are more beneficial for the generation of 2,5-FDCA than Au.
Therefore, problems faced in the preparation process of FDCA in the prior art：It is related in course of reaction big
Amount soda acid solvent, product exists, it is necessary to can just obtain FDCA by series of steps in a salt form.
The content of the invention
The purpose of the present invention is to solve the shortcomings of the prior art, there is provided a kind of 5 hydroxymethyl furfural prepares 2,5- furans two
The method of formic acid, gives full play to the catalytic performance of platinum supported catalyst, in an aqueous medium, realizes that 5 hydroxymethyl furfural is efficiently urged
Change oxidation and prepare 2,5- furandicarboxylic acids.
Technical scheme provided by the present invention is：
A kind of method that 5 hydroxymethyl furfural prepares FDCA, comprises the following steps：
1) catalyst carrier is added in organic solvent and is disperseed, be applied on quartz plate, heating removes organic solvent, makes
Platinum source is deposited in catalyst carrier with atomic layer deposition method, obtains platinum supported catalyst；
2) by step 1) obtain platinum supported catalyst, 5 hydroxymethyl furfural and aqueous solvent and be added in reactor, in oxygen
Under atmosphere, 20~100 DEG C of 2~12h of reaction obtain FDCA.
In above-mentioned technical proposal, platinum supported catalyst is prepared by atomic layer deposition method (ALD), and by platinum supported catalyst
For preparing FDCA, in an aqueous medium, realize that 5 hydroxymethyl furfural efficiently catalyzing and oxidizing prepares 2,5- furans
Dioctyl phthalate.Platinum supported catalyst is prepared by ALD atomic layer deposition methods, and ALD is a FA catalyst preparation skill
Art, it controls the growth of metal in atomic scale, is received by controlling the pulse of precursor saturated vapor pressure to be deposited in carrier surface
The other metallic particles of meter level, the size and homogeneity of precise control active metal particles so that active metal decentralization is high, and
The composition of metal active position is single, and catalytic selectivity is high.
Preferably, the step 1) in catalyst carrier be：ZrO2、CNTs、TiO2、AC、SiO2、r-Al2O3、
Graphene、ZSM-5、MoO3Or MOFs materials.
Preferably, the step 1) in platinum source be front three butylcyclopentadiene platinum or hexafluoroacetylacetonate ketone acid platinum.
Preferably, the step 1) in atomic layer deposition method platinum source temperature be 70~80 DEG C, settling chamber's reaction temperature
It is 260~300 DEG C.
Preferably, the step 1) in atomic layer deposition method the deposition number of turns for 5~50 circle, Pt in platinum supported catalyst
Content be 0.75~6.10wt%.
Preferably, the step 2) in oxygen pressure be 0~0.6Mpa.
Preferably, the step 2) in the mass ratio of platinum supported catalyst and 5 hydroxymethyl furfural be 2:2.5~3.5.
Preferably, the step 2) in reactor heated in oil bath, 0~800r/min of rotating speed.
Compared with the existing technology, beneficial effects of the present invention are embodied in：The platinum prepared by atomic layer deposition method (ALD)
Supported catalyst, has preferable catalytic performance in the reaction system of alkali-free, can obtain 2,5- furans diformazans in high yield
Acid, and the catalyst stability prepared than tradition is preferably, with preferable water repelling property, not easy in inactivation.
Brief description of the drawings
Fig. 1 is the XRD of the catalyst for preparing in embodiment 21 (a), comparative example 1 (b) and comparative example 4 (c)；
Fig. 2 is the TEM figures of the catalyst for preparing in embodiment 21；
Fig. 3 is the TEM figures of the catalyst for preparing in comparative example 1；
Fig. 4 is the TEM figures of the catalyst for preparing in comparative example 4.
Specific embodiment
With reference to specific embodiment and Figure of description, the invention will be further described.
Embodiment 1~5
Taking during appropriate zirconium oxide adds ethanol carries out ultrasonic disperse, is evenly coated on quartz plate with dropper, infrared lamps
Remove ethanol.Quartz plate is put into settling chamber, deposition chamber temperatures are arranged on 280 DEG C, and platinum source is front three butylcyclopentadiene platinum, platinum
Source temperature is arranged on 75 DEG C, and with nitrogen as carrier gas and purified gas, ozone is presoma, deposits the different number of turns (5,10,20,30
With 50 circles) Pt, be 0.75~6.10wt% through ICP-MS detection Pt contents.
5 hydroxymethyl furfural catalytic oxidation is carried out in the stainless steel cauldron of 5mL, oil bath heating, magnetic agitation,
Reaction condition is sequentially added in the stainless steel high temperature autoclave of 5mL：Catalyst 10mg, raw material 5 hydroxymethyl furfural
15mg, aqueous solvent 3mL, 100 DEG C of reaction temperature, oxygen pressure 0.4Mpa, rotating speed 600r/min and reaction time 2h, and calculating 2,
5-FDCA yields and TOF, reaction result such as table 1.
The influence of table 1, the different number of turns to reaction result
As shown in Table 1, with the increase of the deposition number of turns, the content of metal of catalyst also gradually increases, in 5-HMF catalysis
In transformation system, under the same terms, product 2, the yield of 5-FDCA also gradually increases, and is calculated by TOF, and the deposition number of turns is 5,
The 10,20,30,50 corresponding TOF of catalyst is respectively 1.70h-1,6.24h-1,6.94h-1,12.25h-1,7.61h-1, thus
Can show that the catalyst that the circle of deposition 30 is obtained is applied to TOF highests in the reaction system.
Embodiment 6~11
Taking during appropriate zirconium oxide adds ethanol carries out ultrasonic disperse, is evenly coated on quartz plate with dropper, infrared lamps
Remove ethanol.Quartz plate is put into settling chamber, deposition chamber temperatures are arranged on 280 DEG C, and platinum source is front three butylcyclopentadiene platinum, platinum
Source temperature is arranged on 75 DEG C, and with nitrogen as carrier gas and purified gas, ozone is presoma, and deposition 30 is enclosed, and ICP-MS determines platinum and contains
It is 3.23wt% to measure.
Reaction condition：Catalyst 10mg, raw material 5- methylols are sequentially added in the stainless steel high temperature autoclave of 5mL
Furfural 15mg, aqueous solvent 3mL, different reaction temperatures (20,40,60,80,100 and 120 DEG C), oxygen pressure 0.4Mpa, rotating speed
600r/min, the reaction time is 2h, reaction result such as table 2.
The influence of table 2, differential responses temperature to reaction result
As shown in Table 2, under different reaction temperatures, 5-HMF's turns the catalyst that the reaction system application is screened by table 1
The yield result of rate and 2,5-FDCA.At 20~100 DEG C with the increase of reaction temperature, the activity of catalyst is continuously increased,
Therefore the conversion ratio of 5-HMF and the yield of 2,5-FDCA are also continuously increased, when temperature increases to 120 DEG C, due to side reaction
Aggravation, 2,5-FDCA yield declines.Therefore can draw 100 DEG C be the reaction system optimal reaction temperature.
Embodiment 12~15
Taking during appropriate zirconium oxide adds ethanol carries out ultrasonic disperse, is evenly coated on quartz plate with dropper, infrared lamps
Remove ethanol.Quartz plate is put into settling chamber, deposition chamber temperatures are arranged on 280 DEG C, and platinum source is front three butylcyclopentadiene platinum, platinum
Source temperature is arranged on 75 DEG C, and with nitrogen as carrier gas and purified gas, ozone is presoma, and deposition 30 is enclosed, and ICP-MS determines platinum and contains
It is 3.23wt% to measure.
Reaction condition：Catalyst 10mg, raw material 5- methylols are sequentially added in the stainless steel high temperature autoclave of 5mL
Furfural 15mg, aqueous solvent 3mL, 100 DEG C of reaction temperature, different oxygen pressures (0,0.2,0.4 and 0.6MPa), rotating speed 600r/
Min, the reaction time is 2h, reaction result such as table 3.
The influence of table 3, different oxygen pressures to reaction result
As shown in Table 3, under the conditions of the reaction temperature that the reaction system is screened in the catalyst screened by table 1 and by table 2,
0~0.4MPa is also continuously increased with the increase of reaction pressure, 2,5-FDCA yield, when reaction pressure increases to from 0.4
During 0.6MPa, 2,5-FDCA yield keeps constant.Therefore can show that 0.4MPa is the optimum response pressure of the reaction system.
Embodiment 16~20
Take appropriate zirconium oxide and add ultrasonic disperse in ethanol, be evenly coated on quartz plate with dropper, infrared lamps are removed
Ethanol.Quartz plate is put into settling chamber, deposition chamber temperatures are arranged on 280 DEG C, and platinum source is front three butylcyclopentadiene platinum, platinum source temperature
Degree is arranged on 75 DEG C, and with nitrogen as carrier gas and purified gas, ozone is presoma, and deposition 30 is enclosed, and ICP-MS determines platinum content and is
3.23wt%.
Reaction condition：Catalyst 10mg, raw material 5- methylols are sequentially added in the stainless steel high temperature autoclave of 5mL
Furfural 15mg, aqueous solvent 3mL, 100 DEG C of reaction temperature, oxygen pressure 0.4Mpa, different rotating speed (0,200,400,600 and
800r/min), the reaction time is 2h, reaction result such as table 4.
The influence of table 4, different rotating speeds to reaction result
As shown in Table 4, what the reaction temperature and table 3 that the reaction system is screened in the catalyst screened by table 1, table 2 were screened
Under the conditions of reaction pressure, in 0~600r/min with the increase of magnetic agitation rotating speed, the conversion ratio of 5-HMF and 2,5-FDCA's
Yield is also continuously increased, and when rotating speed increases to 800r/min from 600, the conversion ratio of 5-HMF and the yield of 2,5-FDCA keep
It is constant.Therefore can show that 600r/min is the optimal magnetic stirring speed of the reaction system.
Embodiment 21~27
Take appropriate zirconium oxide and add ultrasonic disperse in ethanol, be evenly coated on quartz plate with dropper, infrared lamps are removed
Ethanol.Quartz plate is put into settling chamber, deposition chamber temperatures are arranged on 280 DEG C, and platinum source is front three butylcyclopentadiene platinum, platinum source temperature
Degree is arranged on 75 DEG C, and with nitrogen as carrier gas and purified gas, ozone is presoma, and deposition 30 is enclosed, and ICP-MS determines platinum content and is
3.23wt%.
Reaction condition：Catalyst 10mg, raw material 5- methylols are sequentially added in the stainless steel high temperature autoclave of 5mL
Furfural 15mg, aqueous solvent 3mL, 100 DEG C of reaction temperature, oxygen pressure 0.4Mpa, rotating speed 600r/min, the different reaction time are
(2,4,6,8,10,12 and 14h), reaction result such as table 5.
The influence of table 5, different rotating speeds to reaction result
As shown in Table 5, the reaction system under the optimum reaction condition screened by table 1, table 2, table 3 and table 4, react by extension
Time, when reacted between for 12h when, 2,5-FDCA yield is more than 99%, and it is constant to increase the time, therefore can draw reaction
The 12h reaction responses are complete.
Embodiment 28
Take appropriate CNT and add ultrasonic disperse in ethanol, be evenly coated on quartz plate with dropper, infrared lamps are removed
Remove ethanol.Quartz plate is put into settling chamber, deposition chamber temperatures are arranged on 280 DEG C, and platinum source is front three butylcyclopentadiene platinum, platinum source
At 75 DEG C, with nitrogen as carrier gas and purified gas, ozone is presoma to temperature setting, and deposition 30 is enclosed.
Reaction condition：Catalyst 10mg, raw material 5- methylols are sequentially added in the stainless steel high temperature autoclave of 5mL
Furfural 15mg, aqueous solvent 3mL, 100 DEG C of reaction temperature, oxygen pressure 0.4Mpa, rotating speed 600r/min, the reaction time is 12h, instead
Answer result such as table 6.
Embodiment 29
Take appropriate titanium dioxide and add ultrasonic disperse in ethanol, be evenly coated on quartz plate with dropper, infrared lamps are removed
Remove ethanol.Quartz plate is put into settling chamber, deposition chamber temperatures are arranged on 280 DEG C, and platinum source is front three butylcyclopentadiene platinum, platinum source
At 75 DEG C, with nitrogen as carrier gas and purified gas, ozone is presoma to temperature setting, and deposition 30 is enclosed.
Reaction condition：Catalyst 10mg, raw material 5- methylols are sequentially added in the stainless steel high temperature autoclave of 5mL
Furfural 15mg, aqueous solvent 3mL, 100 DEG C of reaction temperature, oxygen pressure 0.4Mpa, rotating speed 600r/min, the reaction time is 12h, instead
Answer result such as table 6.
Embodiment 30
Take proper amount of active carbon and add ultrasonic disperse in ethanol, be evenly coated on quartz plate with dropper, infrared lamps are removed
Ethanol.Quartz plate is put into settling chamber, deposition chamber temperatures are arranged on 280 DEG C, and platinum source is front three butylcyclopentadiene platinum, platinum source temperature
Degree is arranged on 75 DEG C, and with nitrogen as carrier gas and purified gas, ozone is presoma, and deposition 30 is enclosed.
Reaction condition：Catalyst 10mg, raw material 5- methylols are sequentially added in the stainless steel high temperature autoclave of 5mL
Furfural 15mg, aqueous solvent 3mL, 100 DEG C of reaction temperature, oxygen pressure 0.4Mpa, rotating speed 600r/min, the reaction time is 12h, instead
Answer result such as table 6.
Embodiment 31
Take appropriate silica and add ultrasonic disperse in ethanol, be evenly coated on quartz plate with dropper, infrared lamps are removed
Remove ethanol.Quartz plate is put into settling chamber, deposition chamber temperatures are arranged on 280 DEG C, and platinum source is front three butylcyclopentadiene platinum, platinum source
At 75 DEG C, with nitrogen as carrier gas and purified gas, ozone is presoma to temperature setting, and deposition 30 is enclosed.
Reaction condition：Catalyst 10mg, raw material 5- methylols are sequentially added in the stainless steel high temperature autoclave of 5mL
Furfural 15mg, aqueous solvent 3mL, 100 DEG C of reaction temperature, oxygen pressure 0.4Mpa, rotating speed 600r/min, the reaction time is 12h, instead
Answer result such as table 6.
Embodiment 32
Take appropriate r- aluminum oxide and add ultrasonic disperse in ethanol, be evenly coated on quartz plate with dropper, infrared lamps are removed
Remove ethanol.Quartz plate is put into settling chamber, deposition chamber temperatures are arranged on 280 DEG C, and platinum source is front three butylcyclopentadiene platinum, platinum source
At 75 DEG C, with nitrogen as carrier gas and purified gas, ozone is presoma to temperature setting, and deposition 30 is enclosed.
Reaction condition：Catalyst 10mg, raw material 5- methylols are sequentially added in the stainless steel high temperature autoclave of 5mL
Furfural 15mg, aqueous solvent 3mL, 100 DEG C of reaction temperature, oxygen pressure 0.4Mpa, rotating speed 600r/min, the reaction time is 12h, instead
Answer result such as table 6.
Embodiment 33
Take appropriate Graphene and add ultrasonic disperse in ethanol, be evenly coated on quartz plate with dropper, infrared lamps are removed
Remove ethanol.Quartz plate is put into settling chamber, deposition chamber temperatures are arranged on 280 DEG C, and platinum source is front three butylcyclopentadiene platinum, platinum source
At 75 DEG C, with nitrogen as carrier gas and purified gas, ozone is presoma to temperature setting, and deposition 30 is enclosed.
Reaction condition：Catalyst 10mg, raw material 5- methylols are sequentially added in the stainless steel high temperature autoclave of 5mL
Furfural 15mg, aqueous solvent 3mL, 100 DEG C of reaction temperature, oxygen pressure 0.4Mpa, rotating speed 600r/min, the reaction time is 12h, instead
Answer result such as table 6.
Embodiment 34
Take appropriate ZSM-5 and add ultrasonic disperse in ethanol, be evenly coated on quartz plate with dropper, infrared lamps remove second
Alcohol.Quartz plate is put into settling chamber, deposition chamber temperatures are arranged on 280 DEG C, and platinum source is front three butylcyclopentadiene platinum, platinum source temperature
75 DEG C are arranged on, with nitrogen as carrier gas and purified gas, ozone is presoma, deposition 30 is enclosed.
Reaction condition：Catalyst 10mg, raw material 5- methylols are sequentially added in the stainless steel high temperature autoclave of 5mL
Furfural 15mg, aqueous solvent 3mL, 100 DEG C of reaction temperature, oxygen pressure 0.4Mpa, rotating speed 600r/min, the reaction time is 12h, instead
Answer result such as table 6.
Embodiment 35
Take appropriate MoO3Ultrasonic disperse in ethanol is added, is evenly coated on quartz plate with dropper, infrared lamps remove second
Alcohol.Quartz plate is put into settling chamber, deposition chamber temperatures are arranged on 280 DEG C, and platinum source is front three butylcyclopentadiene platinum, platinum source temperature
75 DEG C are arranged on, with nitrogen as carrier gas and purified gas, ozone is presoma, deposition 30 is enclosed.
Reaction condition：Catalyst 10mg, raw material 5- methylols are sequentially added in the stainless steel high temperature autoclave of 5mL
Furfural 15mg, aqueous solvent 3mL, 100 DEG C of reaction temperature, oxygen pressure 0.4Mpa, rotating speed 600r/min, the reaction time is 12h, instead
Answer result such as table 6.
Embodiment 36
Take appropriate MOFs materials and add ultrasonic disperse in ethanol, be evenly coated on quartz plate with dropper, infrared lamps are removed
Remove ethanol.Quartz plate is put into settling chamber, deposition chamber temperatures are arranged on 280 DEG C, and platinum source is front three butylcyclopentadiene platinum, platinum source
At 75 DEG C, with nitrogen as carrier gas and purified gas, ozone is presoma to temperature setting, and deposition 30 is enclosed.
Reaction condition：Catalyst 10mg, raw material 5- methylols are sequentially added in the stainless steel high temperature autoclave of 5mL
Furfural 15mg, aqueous solvent 3mL, 100 DEG C of reaction temperature, oxygen pressure 0.4Mpa, rotating speed 600r/min, the reaction time is 12h, instead
Answer result such as table 6.
The influence of table 6, different catalyst to reaction result
As shown in Table 6, under optimal reaction condition, the different carriers of catalyst are prepared by change, it can be deduced that platinum
ZrO is supported on by ALD equipment2、CNTs、TiO2, AC and Graphene, 2,5-FDCA yield can reach more than 99%；When
Carrier is SiO2、r-Al2O3、ZSM-5、MoO3During with MOFs, 2,5-FDCA yield is respectively 95%, 92%, 90%, 86%,
89%.It can be seen that influence of the carrier to reaction result.
Embodiment 37
Take appropriate zirconium oxide and add ultrasonic disperse in ethanol, be evenly coated on quartz plate with dropper, infrared lamps are removed
Ethanol.Quartz plate is put into settling chamber, deposition chamber temperatures are arranged on 280 DEG C, and platinum source is front three butylcyclopentadiene platinum, platinum source temperature
Degree is arranged on 75 DEG C, and with nitrogen as carrier gas and boosting gas, ozone is presoma, and deposition 30 is enclosed, and ICP-MS determines platinum content and is
3.23wt%.
Reaction condition：Catalyst 10mg, raw material 5- methylols are sequentially added in the stainless steel high temperature autoclave of 5mL
Furfural 15mg, aqueous solvent 3mL, 100 DEG C of reaction temperature, oxygen pressure 0.4Mpa, rotating speed 600r/min, the reaction time is 12h, is surveyed
The cycle-index of catalyst is tried to judge the stability of catalyst, reaction result such as table 7.
The influence of table 7, different cycle-indexes to reaction result
As shown in Table 7, under conditions of optimal, it will be seen that by the recycling to catalyst, 2,5-FDCA yield meeting
It is gradually reduced, but is not very big, 90.7% can also be reached when recycling for the 5th time, it can be deduced that prepared by ALD
Catalyst stability is fine.
Comparative example 1~3
Weigh 0.1543g ammonium chloroplatinates to be dissolved in 1mL water, fully 1.9354g nano zircites are added after dissolving, in room temperature
Lower ultrasonic agitation 0.5h, stands 10h, the dried overnight in 100 DEG C of baking ovens.Then, 4h is calcined at 500 DEG C with Muffle furnace, finally
500 DEG C of hydrogen reducing 2h are obtained catalyst in tube furnace.
Reaction condition：Catalyst 10mg, raw material 5- methylols are sequentially added in the stainless steel high temperature autoclave of 5mL
Furfural 15mg, aqueous solvent 3mL, 100 DEG C of reaction temperature, oxygen pressure 0.4Mpa, rotating speed 600r/min, the different reaction time are
2h, 6h and 12h, reaction result such as table 8.
Comparative example 4~6
3.6666g zirconyl nitrates and 0.1470g ammonium chloroplatinates are weighed in 100mL round-bottomed flasks and water-soluble with 30mL
Solution, magnetic agitation 1h makes to be well mixed.Then 0.5mol/L is configured-1Sodium carbonate liquor as precipitating reagent, be slowly dropped to burning
In bottle, pH value of solution >=9 are controlled.Stand 10h, the dried overnight in 100 DEG C of baking ovens.Then, 4h is calcined at 500 DEG C with Muffle furnace,
Last 500 DEG C of hydrogen reducing 2h in tube furnace are obtained catalyst.
Reaction condition：Catalyst 10mg, raw material 5- methylols are sequentially added in the stainless steel high temperature autoclave of 5mL
Furfural 15mg, aqueous solvent 3mL, 100 DEG C of reaction temperature, oxygen pressure 0.4Mpa, rotating speed 600r/min, the different reaction time are
2h, 6h and 12h, reaction result such as table 8.
The influence of table 8, different rotating speeds to reaction result
As shown in Table 8, the catalyst for being prepared by three kinds of methods, in the reaction system, under same reaction conditions, anti-
After answering 12h, catalyst prepared by ALD can make the yield of 2,5-FDCA reach more than 99%, catalyst 2 prepared by infusion process,
The yield of 5-FDCA is 9.4%, catalyst prepared by coprecipitation makes the yield of 2,5-FDCA be 3.9%.
Continue to carry out XRD and TEM signs, such as Fig. 1~4 to the catalyst of embodiment 21, comparative example 1 and the gained of comparative example 4
It is shown, it is known that catalyst prepared by ALD has metal dispersion high and metallic particles size is homogeneous, and sudden and violent to greatest extent
The active sites of active metal in dew catalyst.
Claims (8)
1. a kind of method that 5 hydroxymethyl furfural prepares FDCA, it is characterised in that comprise the following steps：
1) catalyst carrier is added in organic solvent and is disperseed, be applied on quartz plate, heating removes organic solvent, uses original
Sublayer sedimentation deposits in catalyst carrier platinum source, obtains platinum supported catalyst；
2) by step 1) obtain platinum supported catalyst, 5 hydroxymethyl furfural and aqueous solvent and be added in reactor, in oxygen atmosphere
Under, 20~100 DEG C of 2~12h of reaction obtain FDCA.
2. the method that 5 hydroxymethyl furfural according to claim 1 prepares FDCA, it is characterised in that described
Step 1) in catalyst carrier be：ZrO2、CNTs、TiO2、AC、SiO2、r-Al2O3、Graphene、ZSM-5、MoO3Or MOFs materials
Material.
3. the method that 5 hydroxymethyl furfural according to claim 1 prepares FDCA, it is characterised in that described
Step 1) in platinum source be front three butylcyclopentadiene platinum or hexafluoroacetylacetonate ketone acid platinum.
4. the method that 5 hydroxymethyl furfural according to claim 1 prepares FDCA, it is characterised in that described
Step 1) in atomic layer deposition method platinum source temperature be 70~80 DEG C, settling chamber's reaction temperature be 260~300 DEG C.
5. the method that 5 hydroxymethyl furfural according to claim 1 prepares FDCA, it is characterised in that described
Step 1) in atomic layer deposition method the deposition number of turns for 5~50 circle, in platinum supported catalyst the content of Pt be 0.75~
6.10wt%.
6. the method that 5 hydroxymethyl furfural according to claim 1 prepares FDCA, it is characterised in that described
Step 2) in oxygen pressure be 0~0.6Mpa.
7. the method that 5 hydroxymethyl furfural according to claim 1 prepares FDCA, it is characterised in that described
Step 2) in the mass ratio of platinum supported catalyst and 5 hydroxymethyl furfural be 2:2.5~3.5.
8. the method that 5 hydroxymethyl furfural according to claim 1 prepares FDCA, it is characterised in that described
Step 2) in reactor heated in oil bath, 0~800r/min of rotating speed.
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| CN111153877A (en) * | 2020-01-14 | 2020-05-15 | 浙江大学衢州研究院 | Method for continuously and environmentally synthesizing furan dicarboxylic acid by using furoic acid |
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| CN111153877A (en) * | 2020-01-14 | 2020-05-15 | 浙江大学衢州研究院 | Method for continuously and environmentally synthesizing furan dicarboxylic acid by using furoic acid |
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