CN107200676A - A kind of method that mesoporous tungsten oxide is catalyzed softwood pulp Material synthesis ethylene glycol - Google Patents
A kind of method that mesoporous tungsten oxide is catalyzed softwood pulp Material synthesis ethylene glycol Download PDFInfo
- Publication number
- CN107200676A CN107200676A CN201710332372.8A CN201710332372A CN107200676A CN 107200676 A CN107200676 A CN 107200676A CN 201710332372 A CN201710332372 A CN 201710332372A CN 107200676 A CN107200676 A CN 107200676A
- Authority
- CN
- China
- Prior art keywords
- softwood pulp
- tungsten oxide
- ethylene glycol
- catalyzed
- mesoporous tungsten
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method that mesoporous tungsten oxide is catalyzed softwood pulp Material synthesis ethylene glycol.The method comprising the steps of：（1）It will be transferred to after softwood pulp raw material and mixed in hydrochloric acid in condensation reflux unit, reaction be hydrolyzed under heating stirring；（2）By step（1）Reactant mixture after reaction terminates is taken out, and adds water, staticly settles, and removes supernatant, and washing is spray-dried after dilution, obtains softwood pulp fine cellulose powder；（3）Obtained softwood pulp fine cellulose powder and mesoporous tungsten oxide, ruthenium carbon and deionized water are placed in closed reactor, hydro-thermal reaction, synthesizing glycol are carried out under hydrogen atmosphere.Using the softwood pulp fine cellulose powder for preparing as raw material, the conversion ratio in the catalyst system and catalyzing of the inventive method is 95.7% 100% to the present invention, and ethylene glycol yield reaches 61.3% ~ 63.6%.
Description
Technical field
Synthesizing glycol technical field is prepared the present invention relates to biomass material, and in particular to one kind is using tungsten oxide catalysis
The method of softwood pulp Material synthesis ethylene glycol.
Background technology
Ethylene glycol is a kind of important chemicals, is widely used in the production fields such as polyester, plastics, antifreezing agent.Exist at present
In industrial production, the topmost mode of production of ethylene glycol is to use petroleum path, i.e., prepared by the ethene produced first by oil
Oxirane, then by epoxyethane water it is legal/ethylene carbonate method prepares ethylene glycol.
It is well known that the fossil energy shortage such as oil, coal has become the major issue of limitation industrial development.In order to slow
The pressure that solution fossil energy shortage is brought to industrial production, prepares high added value platform chemicals with biomass material in recent years
Biomass refining technology is gradually taken seriously and obtains quick development.
Biomass route provides new approach for green high-efficient production ethylene glycol.Lignocellulosic is that a kind of reserves are rich
Richness, wide material sources, the renewable resource of environmental protection, the W-Sn deposits catalysis microcrystalline cellulose developed in recent years prepare second two
Alcohol has shown preferable effect (Ji N, Zhang T, Zheng M, et al.Direct catalytic conversion
of cellulose into ethylene glycol using nickel-promoted tungsten carbide
catalysts[J].Angewandte Chemie International Edition,2008,47(44):8510-8513.)。
Softwood pulp is the market pulp for being widely used in paper industry, and main component is cellulose and a small amount of hemicellulose, relatively
There is cheap, abundance in the microcrystalline cellulose of high-quality.It is stable in the yield convergence of current paper industry
On the premise of, by appropriate preprocess method, degraded hemicellulose therein simultaneously retains cellulose, it is replaced as one kind
The biomass material of microcrystalline cellulose is with certain competitive advantage and development space.
Mesoporous material refers to the class material with 2-50nm apertures, and mesoporous material has well-regulated profile and greatly ratio
Surface area, highly good duct order can be kept in micro-meter scale, good hydro-thermal can be obtained by optimization processing steady
It is qualitative, it is a kind of good shape-selective catalyst, there is relatively broad application in fields such as petrochemical industry, photocatalysis.
Therefore, ethylene glycol is prepared using mesoporous tungsten oxide catalysis softwood pulp, to result in preferable changing effect,
The development process that ethylene glycol is prepared to accelerating cellulose catalytic is particularly important.
The content of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of mesoporous tungsten oxide catalysis softwood pulp Material synthesis second two
The method of alcohol.
The present invention is achieved through the following technical solutions.
A kind of method that mesoporous tungsten oxide is catalyzed softwood pulp Material synthesis ethylene glycol, comprises the following steps：
(1) pretreatment of softwood pulp：It will be transferred to after softwood pulp raw material and mixed in hydrochloric acid in condensation reflux unit, plus
Reaction is hydrolyzed under thermal agitation；Judge reaction terminate foundation be changed into light brown for softwood pulp raw material color, take sample in
Added water observation in small beaker, and fiber diameter is uniform, and reaction is stopped during no winding clustering phenomena；
(2) collection of softwood pulp fine cellulose powder：Step (1) is reacted to the reactant mixture after terminating to take out, plus
Water, is staticly settled, and removes supernatant, and washing is spray-dried after dilution, obtains softwood pulp fine cellulose powder；
(3) synthesis of ethylene glycol：By obtained softwood pulp fine cellulose powder and mesoporous tungsten oxide, ruthenium carbon and deionization
Water is placed in closed reactor, and hydro-thermal reaction, synthesizing glycol are carried out under hydrogen atmosphere.
Further, in step (1), the mass concentration of the hydrochloric acid is 18~20wt%.
Further, in step (1), the softwood pulp raw material is 1 with hydrochloric acid solid-liquid ratio:15~1：20g/mL.
Further, in step (1), the heating stirring is that 200~400r/min of first room temperature low speed stirs 5~10min,
40~50 DEG C of 800~1000r/min of high speed stirrings are warming up to again, and the reaction time is fine cellulose powder grain size material impact
The time of factor, preferably high-speed stirred is 80~120min.
Further, in step (2), after adding water, the mass ratio that reactant mixture accounts for total solution is 1:50~1:150.
Further, in step (2), the time of the standing is 3~8h.
Further, in step (2), the washing is to use the pH of deionized water cyclic washing to cleaning solution to be 6~7.
Further, in step (2), the dilution is to be diluted to material concentration for 1~5wt%.
Further, in step (2), the condition of the spray drying is：Injector temperature is 110~120 DEG C, blower fan work(
Rate is 90~100%, and wriggling pump power is 15~30%, the dry powder rate of recovery 65.5%~79.8%.
Further, in step (2), the cellulose particle diameter of the softwood pulp fine cellulose powder is distributed in 6.6~
71.4μm。
Further, in step (3), the mesoporous tungsten oxide catalyst is to be prepared using hard template method.
Further, in step (3), the template used in the hard template method includes model KIT-6, SBA-15
Or MCM-41 silica mesoporous zeolite.
Further, in step (3), the softwood pulp fine cellulose powder and mesoporous tungsten oxide, ruthenium carbon and deionization
The mass ratio of water is 20:2:1:2000.
Further, in step (3), the pressure of the hydrogen atmosphere is 6MPa, and the temperature of hydro-thermal reaction is 245 DEG C, when
Between be 60min.
Further, the yield of ethylene glycol is 61.3%~63.6%.
Compared with prior art, the invention has the advantages that and beneficial effect：
(1) softwood pulp raw material is prepared the fine fibre of softwood pulp by the present invention after hydrochloric acid hydrolysis pretreatment, spray drying
The yield of the plain powder of dimension is higher, reaches 65.5%~79.8%, and the particle diameter distribution and commodity microcrystalline cellulose of fine cellulose powder
Close, by raw material of the softwood pulp fine cellulose powder of preparation, conversion ratio is in the catalyst system and catalyzing of the inventive method
95.7%-100%, and the softwood pulp fibrous raw material that pretreatment is obtained applies also for the chemical industry related to cellulose, material
Deng field；
(2) present invention has preferable changing effect, second using mesoporous tungsten oxide to the fine cellulose by pretreatment
Glycol yield reaches 61.3%~63.6%, transformation in planta effect better than/close to commodity microcrystalline cellulose coordinate commodity nanometer
Tungsten oxide catalyst system；
(3) the inventive method is simple and easy to do, and it is the common raw material being easy to get to prepare with low cost and raw materials used and reagent
And reagent, the application field of softwood pulp is widened, with good actual application value.
Brief description of the drawings
Fig. 1 is the granularmetric analysis figure of fine cellulose powder prepared by the needle wood pulp low-kappa number of embodiment 1；
Fig. 2 is the mesoporous tungsten oxide small angle x-ray diffraction (SAXD) figure of KIT-6 types prepared by the hard template method of embodiment 1；
Fig. 3 is the SEM figures of the mesoporous tungsten oxide of SBA-15 types prepared by the hard template method of embodiment 2；
Fig. 4 is the TEM figures of the mesoporous tungsten oxide of SBA-15 types prepared by the hard template method of embodiment 2.
Embodiment
Below in conjunction with specific embodiments and the drawings, the present invention is described in detail.Procedures described below is of the invention
Preferred embodiment, but the present invention is not limited to above-mentioned detail, it is necessary to which explanation, it is conceived in the method for the present invention
It is interior to carry out the adjustment of working condition, including 18~20wt% of acid concentration that paper pulp sour water solution is used, solid-liquid ratio 1:15~1:
20g/mL, 40~50 DEG C of reaction temperature, the reaction time be 80~120min, the 1~5wt% of feed concentration being spray-dried,
110~120 DEG C of spray drying temperature.Specific method provided above is not unique embodiment, in order to avoid unnecessary
Repeat, the present invention no longer separately illustrates to other various possible conditional combinations, these simple adjustment belong to guarantor of the present invention
Within the scope of shield.
Embodiment 1
Mesoporous tungsten oxide is catalyzed softwood pulp Material synthesis ethylene glycol, specifically includes following steps：
(1) hydrochloric acid of 450ml mass concentrations 18% is added in 1000ml three-necked flask, flask is placed in water bath with thermostatic control
In pot, mouth connects electric mixer in flask, and remaining connects condenser pipe flatly, is used to feed in addition flatly；200r/min's
Under stirring at low speed, 30g over dry Folium Pini wood pulps are slowly added into flask, 5min is stirred, paper pulp gradually absorbs acid solution profit
It is swollen, after the completion of charging, charge door is closed with ground glass stopper, 45 DEG C are heated to, increase mixing speed is 800r/min, during reaction
Between be 80min, raw material is tapered in course of reaction, and color is changed into light brown, at the end of reaction closes on, and 2 drops are taken with dropper
Sample is in a small beaker, plus clear water observation, and fiber diameter is uniform, and no winding clustering phenomena stops reaction；
(2) product and hydrolyzate are transferred along into 5L large beakers by reaction after terminating, and add water to 4500ml, stand 3h,
After outwelling supernatant after material precipitation, clean 5 times repeatedly, washing to cleaning solution pH=6, in order to avoid introducing salt impurity, at this moment
Alkali neutralization is added without, a small amount of hydrochloric acid can be removed in spray drying；
(3) resulting solution is spray-dried, product dilution to 3000ml (concentration 1wt%) is led in whipping process
Cross wriggling and be pumped into spray dryer, spray drying condition：Injector temperature is 110 DEG C, and power of fan is 90%, wriggling pump work
Rate is 15%, and nozzle cleaning frequency is 2 times, finally gives softwood pulp fine cellulose powder, yield is 79.8%；Obtained fibre
The granularmetric analysis figure of the plain powder of dimension is as shown in figure 1, the particle diameter of cellulose powder is 71.4 μm；
(4) 1.0g KIT-6 are added in the ethanol solution that 50ml mass concentrations are 6% phosphotungstic acid, mix 1h,
It is put into 105 DEG C of baking ovens and dries alcohol solvent, places into 350 DEG C of calcining 4h of tube furnace；Obtained powder is added to again
50ml mass concentrations are put into 550 DEG C of calcinings of tube furnace in the ethanol solution of 2% phosphotungstic acid, to mix after 1h, drying ethanol
4h；KIT-6 molecular sieves finally are removed using 2mol/L hydrofluoric acid, the mesoporous tungsten oxide catalyst of KIT-6 types, its low-angle is obtained
XRD diffracting spectrums are shown in Fig. 2；
(5) weigh in the softwood pulp fine cellulose powder addition hydrothermal reaction kettle that 0.5g spray drying is obtained, add
The mesoporous tungsten catalysts of 0.05g, 0.025g rutheniums carbon and 50g deionized waters, capping kettle are passed through hydrogen and displace air in kettle,
The initial pressure 6MPa of hydrogen is kept, mixing speed is 1000r/min, and temperature is set to 245 DEG C and starts reaction, reaction time
60min；Reaction closes stirring and fast cooling after terminating, and opens reactor and takes out product, crosses and high performance liquid chromatography is used after film
(HPLC) analyzed, and calculate ethylene glycol yield.
The composition analysis result of the product of the mesoporous tungsten oxide catalysis softwood pulp raw material of KIT-6 types is as shown in table 1.
The product component analysis of the mesoporous tungsten oxide catalysis softwood pulp raw material of table 1KIT-6 types
As shown in Table 1, the mesoporous tungsten trioxide prepared using KIT-6 silicon template is to acid treatment softwood pulp cellulose powder
With good catalyzed conversion effect, the conversion ratio of raw material reaches 95.7%.Ethylene glycol is primary product, yield in liquid product
For 61.3%, while generating a small amount of accessory substance 1,2-PD and sorbierite, yield is respectively 8.2% and 5.3%.
Embodiment 2
Mesoporous tungsten oxide is catalyzed softwood pulp Material synthesis ethylene glycol, specifically includes following steps：
(1) 30g over dry Folium Pinis wood pulp is added in 1000ml three-necked flask, flask is placed in thermostat water bath
In, mouth connects electric mixer in flask, and remaining connects condenser pipe flatly, is used for acid adding flatly in addition；By 540ml mass concentrations
19% hydrochloric acid is added in flask, after the completion of acid adding, is sealed a bottle with ground glass stopper, keeps 300r/min stirring at low speed
8min, paper pulp gradually absorbs acid solution swollen, is heated to 50 DEG C, increase mixing speed is 900r/min, and the reaction time is 100min,
Raw material is tapered in course of reaction, and color is changed into light brown, at the end of reaction closes on, and takes 2 drop samples small in one with dropper
In beaker, plus clear water observation, uniformly, no winding clustering phenomena stops reaction to fiber diameter；
(2) product and hydrolyzate are transferred along into 5L large beakers by reaction after terminating, and add water to 3000ml, stand 5h,
After outwelling supernatant after material precipitation, clean 5 times, washed to cleaning solution pH=6 repeatedly, add deionized water to be diluted into raw material
10min is reacted under 1000ml (concentration is 3wt%), the rotating speed using homogenizer 39000r/min；
(3) resulting solution is spray-dried, product dilution to 1500ml (concentration 2wt%) is led in whipping process
Cross wriggling and be pumped into spray dryer, spray drying condition：Injector temperature is 115 DEG C, and power of fan is 95%, wriggling pump work
Rate is 20%, and nozzle cleaning frequency is 1 time, finally gives softwood pulp fine cellulose powder, yield is 70.2%, cellulose powder
Particle diameter be 6.6 μm；
(4) 1.0g SBA-15 are added in the ethanol solution that 50ml mass concentrations are 6% phosphotungstic acid, mix 1h,
It is put into 105 DEG C of baking ovens and dries alcohol solvent, places into 350 DEG C of calcining 4h of tube furnace；Obtained powder is added to again
50ml mass concentrations are put into 550 DEG C of calcinings of tube furnace in the ethanol solution of 2% phosphotungstic acid, to mix after 1h, drying ethanol
4h；SBA-15 molecular sieves finally are removed using 2mol/L hydrofluoric acid, the mesoporous tungsten oxide catalyst of SBA-15 types is obtained, it is scanned
Electronic Speculum (SEM) picture is shown in Fig. 3, and transmission electron microscope TEM pictures are shown in Fig. 4；
(5) weigh in the softwood pulp fine cellulose powder addition hydrothermal reaction kettle that 0.5g spray drying is obtained, add
The mesoporous tungsten catalysts of 0.05g, 0.025g rutheniums carbon and 50g deionized waters, capping kettle are passed through hydrogen and displace air in kettle,
The initial pressure 6MPa of hydrogen is kept, mixing speed is 1000r/min, and temperature is set to 245 DEG C and starts reaction, reaction time
60min；Reaction closes stirring and fast cooling after terminating, and opens reactor and takes out product, is analyzed after crossing film using HPLC,
Calculate ethylene glycol yield.
The product component analysis result of the mesoporous tungsten oxide catalysis softwood pulp raw material of SBA-15 types is as shown in table 2.
The product component analysis of the mesoporous tungsten oxide catalysis softwood pulp raw material of table 2SBA-15 types
As shown in Table 2, the mesoporous tungsten trioxide prepared using SBA-15 silicon template is to acid treatment softwood pulp cellulose
Powder has good catalyzed conversion effect, and cellulosic material is converted completely.Ethylene glycol is primary product in liquid product, and yield is
61.8%, while generating a small amount of accessory substance 1,2-PD and sorbierite, yield is respectively 8.1% and 5.5%.
Embodiment 3
Mesoporous tungsten oxide is catalyzed softwood pulp Material synthesis ethylene glycol, specifically includes following steps：
(1) 30g over dry Folium Pinis wood pulp is added in 1000ml three-necked flask, flask is placed in thermostat water bath
In, mouth connects electric mixer in flask, and remaining connects condenser pipe flatly, is used for acid adding flatly in addition；By 600ml mass concentrations
20% hydrochloric acid is added in flask, after the completion of acid adding, is sealed a bottle with ground glass stopper, keeps 400r/min stirring at low speed
10min, paper pulp gradually absorbs acid solution swollen, is heated to 40 DEG C, and increase mixing speed is 1000r/min, and the reaction time is
Raw material is tapered in 120min, course of reaction, and color is changed into light brown, at the end of reaction closes on, and 2 drop samples are taken with dropper
In a small beaker, plus clear water observation, uniformly, no winding clustering phenomena stops reaction to fiber diameter；
(2) product and hydrolyzate are transferred along into 5L large beakers by reaction after terminating, and add water to 1500ml, stand 8h,
After outwelling supernatant after material precipitation, clean 5 times repeatedly, washing to cleaning solution pH=6.
(3) resulting solution is spray-dried, product dilution to 600ml (concentration 5wt%) is passed through in whipping process
Wriggling is pumped into spray dryer, spray drying condition：Injector temperature is 120 DEG C, and power of fan is 100%, wriggling pump work
Rate is 30%, and nozzle cleaning frequency is 3 times, finally gives softwood pulp fine cellulose powder, yield is 65.5%, cellulose powder
Particle diameter be 8.1 μm；
(4) 2.0g MCM-41 are added in the ethanol solution that 20ml mass concentrations are 12% phosphotungstic acid, mixed
1h, is put into 105 DEG C of baking ovens and dries alcohol solvent, places into 350 DEG C of calcining 4h of tube furnace；The powder obtained is added to again
In ethanol solution of the 20ml mass concentrations for 4% phosphotungstic acid, it is put into 550 DEG C of tube furnace after mixing 1h, drying ethanol and forges
Burn 4h；MCM-41 molecular sieves finally are removed using 2mol/L hydrofluoric acid, the mesoporous tungsten oxide catalyst of MCM-41 types is obtained；
(5) weigh in the softwood pulp fine cellulose powder addition hydrothermal reaction kettle that 0.5g spray drying is obtained, add
The mesoporous tungsten catalysts of 0.05g, 0.025g rutheniums carbon and 50g deionized waters, capping kettle are passed through hydrogen and displace air in kettle,
The initial pressure 6MPa of hydrogen is kept, mixing speed is 1000r/min, and temperature is set to 245 DEG C and starts reaction, reaction time
60min；Reaction closes stirring and fast cooling after terminating, and opens reactor and takes out product, is analyzed after crossing film using HPLC,
Calculate ethylene glycol yield.
The product component analysis result of the mesoporous tungsten oxide catalysis softwood pulp raw material of MCM-41 types is as shown in table 3.
The product component analysis of the mesoporous tungsten oxide catalysis softwood pulp raw material of table 3MCM-41 types
As shown in Table 3, the mesoporous tungsten trioxide prepared using MCM-41 silicon template is to acid treatment softwood pulp cellulose
Powder has good catalyzed conversion effect, and cellulosic material conversion ratio is up to 97.2%.Ethylene glycol is main production in liquid product
Thing, yield is 63.6%, while generating a small amount of accessory substance 1,2-PD and sorbierite, yield is respectively 5.9% and 7.6%.
Claims (10)
1. a kind of method that mesoporous tungsten oxide is catalyzed softwood pulp Material synthesis ethylene glycol, it is characterised in that comprise the following steps：
（1）The pretreatment of softwood pulp：It will be transferred to after softwood pulp raw material and mixed in hydrochloric acid in condensation reflux unit, heating is stirred
Mix down and reaction is hydrolyzed；
（2）The collection of softwood pulp fine cellulose powder：By step（1）Reactant mixture after reaction terminates takes out and added water,
Staticly settle, remove supernatant, washing is spray-dried after dilution, obtains softwood pulp fine cellulose powder；
（3）The synthesis of ethylene glycol：Obtained softwood pulp fine cellulose powder is put with mesoporous tungsten oxide, ruthenium carbon and deionized water
In closed reactor, hydro-thermal reaction, synthesizing glycol are carried out under hydrogen atmosphere.
2. the method that a kind of mesoporous tungsten oxide according to claim 1 is catalyzed softwood pulp Material synthesis ethylene glycol, it is special
Levy and be, step（1）In, the mass concentration of the hydrochloric acid is 18 ~ 20 wt%；The solid-liquid ratio of the softwood pulp raw material and hydrochloric acid
For 1:15~1:20 g/mL.
3. the method that a kind of mesoporous tungsten oxide according to claim 1 is catalyzed softwood pulp Material synthesis ethylene glycol, it is special
Levy and be, step（1）In, the heating stirring is that the first r/min of room temperature low speed 200 ~ 400 stirs 5 ~ 10 min, then is warming up to 40
~ 50 DEG C of r/min of high speed 800 ~ 1000 stir 80 ~ 120 min.
4. the method that a kind of mesoporous tungsten oxide according to claim 1 is catalyzed softwood pulp Material synthesis ethylene glycol, it is special
Levy and be, step（2）In, after adding water, reactant mixture accounts for the mass ratio 1 of total solution：50~1:150；The time of the standing is
3~8 h；The washing is to use the pH of deionized water cyclic washing to cleaning solution to be 6 ~ 7.
5. the method that a kind of mesoporous tungsten oxide according to claim 1 is catalyzed softwood pulp Material synthesis ethylene glycol, it is special
Levy and be, step（2）In, the dilution is to be diluted to material concentration for 1 ~ 5 wt%；The condition of the spray drying is：Sample introduction
Mouthful temperature is 110 ~ 120 DEG C, and power of fan is the % of 90 % ~ 100, and wriggling pump power is 15 % ~ 30 %, the % of the dry powder rate of recovery 65.5
~79.8 %。
6. the method that a kind of mesoporous tungsten oxide according to claim 1 is catalyzed softwood pulp Material synthesis ethylene glycol, it is special
Levy and be, step（2）In, the cellulose particle diameter of the softwood pulp fine cellulose powder is distributed in 6.6 ~ 71.4 μm.
7. the method that a kind of mesoporous tungsten oxide according to claim 1 is catalyzed softwood pulp Material synthesis ethylene glycol, it is special
Levy and be, step（3）In, the mesoporous tungsten oxide catalyst is to be prepared using hard template method；Adopted in the hard template method
Template includes model KIT-6, SBA-15 or MCM-41 silica mesoporous zeolite.
8. the method that a kind of mesoporous tungsten oxide according to claim 1 is catalyzed softwood pulp Material synthesis ethylene glycol, it is special
Levy and be, step（3）In, the mass ratio of the softwood pulp fine cellulose powder and mesoporous tungsten oxide, ruthenium carbon and deionized water
For 20:2:1:2000.
9. the method that a kind of mesoporous tungsten oxide according to claim 1 is catalyzed softwood pulp Material synthesis ethylene glycol, it is special
Levy and be, step（3）In, the pressure of the hydrogen atmosphere is 6 MPa；The temperature of the hydro-thermal reaction is 245 DEG C, and the time is 60
min。
10. the method that a kind of mesoporous tungsten oxide according to claim 1 is catalyzed softwood pulp Material synthesis ethylene glycol, it is special
Levy and be, the yield of ethylene glycol is the % of 61.3 % ~ 63.6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710332372.8A CN107200676A (en) | 2017-05-12 | 2017-05-12 | A kind of method that mesoporous tungsten oxide is catalyzed softwood pulp Material synthesis ethylene glycol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710332372.8A CN107200676A (en) | 2017-05-12 | 2017-05-12 | A kind of method that mesoporous tungsten oxide is catalyzed softwood pulp Material synthesis ethylene glycol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107200676A true CN107200676A (en) | 2017-09-26 |
Family
ID=59906231
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710332372.8A Pending CN107200676A (en) | 2017-05-12 | 2017-05-12 | A kind of method that mesoporous tungsten oxide is catalyzed softwood pulp Material synthesis ethylene glycol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107200676A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111054337A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Catalyst for preparing ethylene glycol from biomass |
-
2017
- 2017-05-12 CN CN201710332372.8A patent/CN107200676A/en active Pending
Non-Patent Citations (8)
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111054337A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Catalyst for preparing ethylene glycol from biomass |
| CN111054337B (en) * | 2018-10-16 | 2023-01-31 | 中国石油化工股份有限公司 | Catalyst for preparing ethylene glycol from biomass |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107419574B (en) | A method of it must using oil-tea camellia husks preparation Cellulose nanocrystal | |
| CN106268734A (en) | A kind of preparation method of water dispersible ternary mixed crystal nano titanium dioxide photocatalyst | |
| CN105688985B (en) | A kind of preparation method of solid-carrying type ionic-liquid catalyst | |
| CN107311194B (en) | A kind of preparation method and application of Ti-MWW molecular sieve | |
| CN107381579A (en) | A kind of preparation method of mesoporous spherical nano Sio 2 particle | |
| CN102344150A (en) | Synthetic method for mesopore titanium-silicon molecular sieve | |
| CN106185976A (en) | A kind of multi-stage porous mordenite molecular sieve and preparation method thereof | |
| CN110407255A (en) | A kind of carbon coating caesium tungsten bronze composite granule and preparation method thereof | |
| CN108043407A (en) | A kind of Co/ sepiolites catalyst and its preparation method and application | |
| CN108221438A (en) | A kind of preparation method of bleached eucalyptus pulp nano-cellulose | |
| Cao et al. | Effect of hemicellulose extraction pretreatment on sulfonated corncob biochar for catalytic biodiesel production | |
| CN107200676A (en) | A kind of method that mesoporous tungsten oxide is catalyzed softwood pulp Material synthesis ethylene glycol | |
| CN108554407A (en) | Nano-copper base catalyst and preparation method thereof | |
| CN102745712A (en) | Method for preparing titanium-silicon molecular sieve and method for preparing cyclohexanone oxime by using molecular sieve | |
| CN105948117A (en) | Hydrothermal method for preparing HfO2 nano-particles | |
| CN1807259A (en) | Mesopore titanium dioxide and its SO42-/TiO2 solid super strong acid preparation method and SO42-/TiO2 solid super strong acid | |
| CN105175342B (en) | A kind of method of ionic liquid and its homogeneous modified reed enhancing PE composite materials | |
| CN107321390A (en) | A kind of preparation method of compound bio base solid-carrying type biodiesel catalyst | |
| CN110294493A (en) | A kind of preparation method of nano flower-like structure monocline phase titanic oxide | |
| CN107459047A (en) | A kind of molecular sieve preparation method based on hemicellulose | |
| CN102604453A (en) | Special nanometer composite seal paint for woodware and preparing method thereof | |
| CN107083128A (en) | A kind of environment-friendly interior wall coating of novel high-performance vinegar third and preparation method thereof | |
| CN108467374A (en) | The method that furfural hydrogenation reaction prepares biological furans is carried out in fixed bed reactors | |
| CN104445225A (en) | Method for preparing silica aerogel from straws as raw materials by virtue of low-temperature atmospheric-pressure drying | |
| CN101618850A (en) | Preparation method of anti-ultraviolet ray zinc zirconium oxide nanocomposite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170926 |
|
| RJ01 | Rejection of invention patent application after publication |