CN109603812A - A kind of support type aluminum tungstate solid catalyst and its application in lactic acid is prepared in biomass - Google Patents
A kind of support type aluminum tungstate solid catalyst and its application in lactic acid is prepared in biomass Download PDFInfo
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- CN109603812A CN109603812A CN201811519970.7A CN201811519970A CN109603812A CN 109603812 A CN109603812 A CN 109603812A CN 201811519970 A CN201811519970 A CN 201811519970A CN 109603812 A CN109603812 A CN 109603812A
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Abstract
The present invention provides a kind of support type aluminum tungstate solid catalyst and its prepares the application in lactic acid in biomass.The support type aluminum tungstate solid catalyst, be prepared by following steps: by aluminum salt solution and tungsten salt solution by aluminium: tungsten molar ratio is that 0.5~2:1 is mixed to get emulsion, emulsion is heated to 100 DEG C~160 DEG C and becomes clear solution, catalyst carrier is added into clear solution and obtains mixed liquor, mixed liquor is evaporated to obtain support type aluminum tungstate solid catalyst precursor body, support type aluminum tungstate solid catalyst precursor body it is washed and calcining after to get arrive support type aluminum tungstate solid catalyst.The present invention can convert the lactic acid with high added value for the biomass resource containing cellulose being widely present in nature, and the yield of object lactic acid is higher by the preparation by support type aluminum tungstate solid catalyst applied to biomass lactic acid.
Description
Technical field:
The invention belongs to catalyst technical fields, and in particular to a kind of support type aluminum tungstate solid catalyst and its in biology
Matter prepares the application in lactic acid.
Background technique:
Multi-functional platform chemicals are prepared with biomass resource be widely present in nature, reproducible, to the mankind
The sustainable development of society is of great significance.Cellulose and hemicellulose be in the main component and the earth of biomass most
For the carbohydrate being widely present.So cellulose and hemicellulose are efficiently catalytically conveted to platform chemicals, go forward side by side
And liquid fuel, high molecular material and various downstream chemical product are converted into, have to the higher value application of biomass resource important
Meaning.
Lactic acid is a kind of important industrial chemicals, is widely used in the fields such as food, chemical industry, medicine, cosmetics.Lactic acid
It can be used as the raw material of synthesizing polylactic acid (PLA), PLA can be recycled by biodegrade, reduce the dirt to natural environment
Dye.Lactic acid industrial at present is mainly prepared using glucose as raw material using biological fermentation process, and there are cost of material for this method
The disadvantages of height, production cycle length, severe reaction conditions.In contrast, raw with the lignocellulose being widely present in nature
Physical resources (such as stalk, timber, bagasse etc.) are raw material, produce lactic acid using chemical catalysis transformation technology, then can be real
The resource utilization of existing biomass, and have many advantages, such as that the time is short, high-efficient.
Chemical catalysis conversion of biomass generates lactic acid and is related to following fundamental reactions: (1) cellulosic component in biomass
It is hydrolyzed to glucose；(2) glucose is converted into fructose through isomerization reaction；(3) fructose is converted through retrograde aldol condensation condensation reaction
Glyceraldehyde and dihydroxyacetone (DHA)；(4) glyceraldehyde and dihydroxyacetone (DHA), which occur to be dehydrated, is converted into pyroracemic aldehyde；(5) pyroracemic aldehyde hydration weight
Row is lactic acid.It is more as preparing reaction step involved in lactic acid using the cellulose in biomass, so exploitation is efficiently, inexpensively
And the catalyst easily recycled, it is that catalysis biomass prepares the industrialized core of lactic acid technology realization.
In early-stage study, it has been found that aluminum tungstate, which is converted into lactic acid to the cellulosic component in biomass, to be had preferably
Catalytic action.However, aluminum tungstate specific surface area is smaller, catalyst is caused to contact with biomass material more difficult.If by wolframic acid
In on the biggish carrier of surface area, then the catalytic active site for being on the one hand capable of increasing aluminum tungstate contacts aluminium uniform load with biomass
Chance, another aspect carrier may prepare fundamental reaction involved in lactic acid with aluminum tungstate concerted catalysis cellulose, thus
Preferably play the catalytic action that aluminum tungstate is converted into this process of lactic acid to biomass.But aluminum tungstate is insoluble in water
Solid will lead to wolframic acid alumina particles and be difficult to be evenly arranged on carrier surface if directly directly mixed aluminum tungstate with carrier；If
Impregnate the method for aluminium salt again using first dipping tungstates, then method for preparing catalyst is complicated, and load effect is equally poor.Cause
This, urgently develop at present a kind of new support type aluminum tungstate catalyst preparation technology solve the problems, such as it is of the existing technology.
Summary of the invention:
It is prepared in lactic acid the object of the present invention is to provide a kind of support type aluminum tungstate solid catalyst and its in biomass
Using the method for preparing catalyst is simple, and raw material is easy to get, at low cost, Yi Huishou, and will efficiently can deposit extensively in nature
The biomass resource containing cellulose be converted into the lactic acid with high added value.
The object of the present invention is to provide a kind of support type aluminum tungstate solid catalysts, are prepared: being pressed by following steps
Aluminium: tungsten molar ratio is that aluminum salt solution and tungsten salt solution are mixed to get emulsion by 0.5~2:1, by emulsion be heated to 100 DEG C~
160 DEG C become clear solution, and catalyst carrier is added into clear solution and obtains mixed liquor, mixed liquor is evaporated and is born
Load type aluminum tungstate solid catalyst precursor body, to get arriving after support type aluminum tungstate solid catalyst precursor body is washed and calcining
Support type aluminum tungstate solid catalyst.
Method for preparing catalyst step proposed by the present invention is simple, raw material is easy to get, is at low cost, and catalyst hydrothermal stability
It is good, Yi Huishou.
Preferably, the aluminium salt is selected from one or more of aluminium chloride, aluminum sulfate and aluminum nitrate, and the tungsten salt is selected from
One or more of tungstate lithium, sodium tungstate, potassium tungstate and ammonium tungstate, the catalyst carrier are selected from active carbon, graphite oxide
One or more of alkene, silica, aluminium oxide, zirconium oxide, niobium oxide and Si-Al molecular sieve, the aluminum tungstate load capacity are to urge
The 2%~50% of agent gross mass.Further preferably, aluminum tungstate load capacity is the 5%~30% of catalyst gross mass.
Preferably, mixed liquor is evaporated to obtain the specific steps of support type aluminum tungstate solid catalyst precursor body are as follows: will mix
Liquid is closed to be evaporated to obtain support type aluminum tungstate solid catalyst precursor body under conditions of temperature is 140 DEG C~160 DEG C.
Preferably, the washed specific steps with calcining of the support type aluminum tungstate solid catalyst precursor body are as follows: institute
Removing soluble-salt is washed with water in the support type aluminum tungstate solid catalyst precursor body stated, then 600 DEG C in protective atmosphere
~800 DEG C of 1~12h of calcining.
Further, the protective atmosphere is nitrogen, argon gas, helium or deoxidation flue gas.
Another object of the present invention is to provide support type aluminum tungstate solid catalysts to prepare in lactic acid in biomass
Using.
Preferably, the support type aluminum tungstate solid catalyst prepares the application in lactic acid in biomass, including as follows
Step: the support type aluminum tungstate solid catalyst and biomass are added in deionized water and obtain reaction mass, will be reacted
Material is warming up to 180 DEG C~240 DEG C 5~600min of reaction to get lactic acid.Further, by reaction mass be warming up to 220 DEG C~
230 DEG C of 120~180min of reaction, the yield of lactic acid are up to 46%.
Preferably, the support type aluminum tungstate solid catalyst and the mass ratio of biomass are 0.1~0.5:1, biology
The mass ratio of matter and deionized water is 0.05~0.3:1.Further preferably, the support type aluminum tungstate solid catalyst and life
The mass ratio of substance is 0.1~0.3:1, and the mass ratio of biomass and deionized water is 0.05~0.15:1.
Preferably, the biomass is the biomass that content of cellulose is more than or equal to 20%.
Compared with prior art, the invention has the following advantages that
(1) present invention can be dissolved in the salting liquid more than 100 DEG C using fresh wolframic acid aluminum precipitation and form aluminum tungstate
This property of solution, and add carrier to high temperature wolframic acid aluminum solutions, then aluminum tungstate can be distributed evenly on carrier, and negative
Wolframic acid Al catalysts after load are converted into lactic acid with preferable catalytic action to biomass；
(2) support type aluminum tungstate solid catalyst preparation method step proposed by the present invention is simple, raw material is easy to get, cost
It is low, and catalyst good hydrothermal stability, Yi Huishou；
(3) lactic acid is prepared by the way that support type aluminum tungstate solid catalyst is applied to biomass catalyzing conversion, can incites somebody to action oneself
The biomass resource containing cellulose being widely present in right boundary is converted into the lactic acid with high added value, and object lactic acid
Yield is higher.
Specific embodiment:
The following examples are further illustrations of the invention, rather than limiting the invention.
Embodiment 1:
(1) activated carbon supported wolframic acid Al catalysts 2%Al2(WO4)3The preparation of/AC
0.015mol sodium tungstate, 0.015mol aluminum sulfate are dissolved separately in 40mL deionized water, it is then molten by two kinds
Liquid mixing, mixed emulsion is placed in 100 DEG C of baking ovens and is kept the temperature, and after emulsion becomes clear solution completely, is added
138.6g absorbent charcoal carrier is evaporated mixed liquor at 140 DEG C；The solid being evaporated is washed with 2L deionized water, 100 DEG C of dryings,
In 800 DEG C of calcining 5h in nitrogen atmosphere, the solid catalyst Al that aluminum tungstate load capacity is 2% is obtained2(WO4)3/AC。
(2) activated carbon supported wolframic acid Al catalysts 2%Al2(WO4)3/ AC catalytic cellulose prepares lactic acid
By 0.3g step (1) solid catalyst Al obtained2(WO4)3/ AC, 1g corn stover and 20mL deionized water add
Enter into 50mL stirred autoclave, hydrothermal degradation 600min then is carried out to mixed liquor at 180 DEG C, obtaining lactate yield is
15% (relative to the content of cellulose in raw material).
Embodiment 2:
(1) graphene oxide-loaded wolframic acid Al catalysts 50%Al2(WO4)3The preparation of/GO
0.02mol tungstate lithium, 0.01mol aluminum nitrate are dissolved separately in 40mL deionized water, then by two kinds of solution
Mixing, mixed emulsion is placed in 140 DEG C of baking ovens and is kept the temperature, and after emulsion becomes clear solution completely, is added
2.828g graphene oxide, continuation are evaporated mixed liquor at 140 DEG C；The solid being evaporated is washed with 2L deionized water, 100 DEG C dry
It is dry, in 600 DEG C of calcining 12h in argon atmosphere, obtain the solid catalyst Al that aluminum tungstate load capacity is 50%2(WO4)3/GO。
(2) solid catalyst 50%Al2(WO4)3/ GO catalytic cellulose prepares lactic acid
By 0.2g step (1) solid catalyst Al obtained2(WO4)3/ GO, 2g corncob and 20mL deionized water are added
Into 50mL stirred autoclave, hydrothermal degradation 300min then is carried out to mixed liquor at 200 DEG C, obtaining lactate yield is 33%
(relative to the content of cellulose in raw material).
Embodiment 3:
(1) silicon dioxide carried wolframic acid Al catalysts 5%Al2(WO4)3/SiO2Preparation
0.015mol potassium tungstate, 0.01mol aluminium chloride are dissolved separately in 20mL deionized water, then by two kinds of solution
Mixing, mixed emulsion is placed in 130 DEG C of baking ovens and is kept the temperature, and after emulsion becomes clear solution completely, is added
53.7g silica supports are evaporated mixed liquor at 140 DEG C；The solid being evaporated is washed with 2L deionized water, 100 DEG C of dryings,
In 800 DEG C of calcining 1h in helium atmosphere, the solid catalyst Al that aluminum tungstate load capacity is 5% is obtained2(WO4)3/SiO2。
(2) solid catalyst 5%Al2(WO4)3/SiO2Catalytic cellulose prepares lactic acid
By 0.1g step (1) solid catalyst Al obtained2(WO4)3/SiO2, 1g broomcorn straw and 20mL deionized water
It is added in 50mL stirred autoclave, hydrothermal degradation 180min then is carried out to mixed liquor at 220 DEG C, obtaining lactate yield is
31% (relative to the content of cellulose in raw material).
Embodiment 4:
(1) gama-alumina loads wolframic acid Al catalysts 5%Al2(WO4)3/γ-Al2O3Preparation
0.015mol wolframic acid ammonia, 0.005mol aluminum sulfate are dissolved separately in 40mL deionized water, it is then molten by two kinds
Liquid mixing, mixed emulsion is placed in 140 DEG C of baking ovens and is kept the temperature, and after emulsion becomes clear solution completely, is added
53.7g gama-alumina, continuation are evaporated mixed liquor at 140 DEG C；The solid being evaporated is washed with 2L deionized water, 100 DEG C of dryings,
In 800 DEG C of calcining 5h in deoxidation flue gas atmosphere, the solid catalyst Al that aluminum tungstate load capacity is 5% is obtained2(WO4)3/γ-
Al2O3。
(2) solid catalyst 5%Al2(WO4)3/γ-Al2O3Catalytic cellulose prepares lactic acid
By 0.3g step (1) solid catalyst Al obtained2(WO4)3/γ-Al2O3, 2g Wheat Straw and 20mL deionization
Water is added in 50mL stirred autoclave, is then carried out hydrothermal degradation 120min to mixed liquor at 230 DEG C, is obtained lactate yield
For 27% (relative to the content of cellulose in raw material).
Embodiment 5:
(1) the solid catalyst 5%Al of HZSM-5 load2(WO4)3The preparation of/HZSM-5
0.0075mol sodium tungstate, 0.0075mol ammonium tungstate and 0.005mol aluminum sulfate are dissolved separately in 40mL deionization
In water, then three kinds of solution are mixed, mixed emulsion is placed in 140 DEG C of baking ovens and is kept the temperature, is become completely to emulsion
After clear solution, 53.7g HZSM-5 carrier is added, continuation is evaporated mixed liquor at 140 DEG C；Steaming is washed with 2L deionized water
Dry solid, 100 DEG C of dryings obtain the solid catalyst Al that load capacity is 5% in 800 DEG C of calcining 5h in nitrogen atmosphere2
(WO4)3/HZSM-5。
(2) solid catalyst 5%Al2(WO4)3/ HZSM-5 catalytic cellulose prepares lactic acid
By 0.1g step (1) solid catalyst Al obtained2(WO4)3/ HZSM-5,1g straw and 20mL deionized water add
Enter into 50mL stirred autoclave, hydrothermal degradation 5min then is carried out to mixed liquor at 240 DEG C, obtaining lactate yield is 18%
(relative to the content of cellulose in raw material).
Embodiment 6:
(1) H β loads wolframic acid Al catalysts 10%Al2(WO4)3The preparation of/H β
0.0075mol sodium tungstate, 0.0075mol potassium tungstate and 0.005mol aluminum sulfate are dissolved separately in 20mL deionization
In water, then three kinds of solution are mixed, mixed emulsion is placed in 140 DEG C of baking ovens and is kept the temperature, is become completely to emulsion
After clear solution, 25.45g H β carrier is added, continuation is evaporated mixed liquor at 140 DEG C；It is washed with 2L deionized water and to be evaporated
Solid, 100 DEG C of dryings obtain the solid catalyst that load capacity is 10% in 800 DEG C of calcining 5h in nitrogen atmosphere
Al2(WO4)3/Hβ。
(2) solid catalyst 10%Al2(WO4)3/ H β catalytic cellulose prepares lactic acid
By 0.1g step (1) solid catalyst Al obtained2(WO4)3/ H β, 1g pine sawdust and 20mL deionized water are added
Into 50mL stirred autoclave, hydrothermal degradation 30min then is carried out to mixed liquor at 240 DEG C, obtaining lactate yield is 19%
(relative to the content of cellulose in raw material).
Embodiment 7:
(1) ZrO 2 solid catalyst 33.3%Al2(WO4)3/ZrO2Preparation
0.015mol sodium tungstate, 0.005mol aluminum sulfate are dissolved separately in 40mL deionized water, it is then molten by two kinds
Liquid mixing, mixed emulsion is placed in 140 DEG C of baking ovens and is kept the temperature, and after emulsion becomes clear solution completely, is added
5.66g ZrO2Carrier, continuation are evaporated mixed liquor at 140 DEG C；The solid being evaporated is washed with 2L deionized water, 100 DEG C of dryings,
In 800 DEG C of calcining 5h in nitrogen atmosphere, the solid catalyst Al that load capacity is 33.3% is obtained2(WO4)3/ZrO2。
(2) solid catalyst 33.3%Al2(WO4)3/ZrO2Catalytic cellulose prepares lactic acid
By 0.1g step (1) solid catalyst Al obtained2(WO4)3/ZrO2, 1g poplar bits and 20mL deionized water add
Enter into 50mL stirred autoclave, hydrothermal degradation 180min then is carried out to mixed liquor at 220 DEG C, obtaining lactate yield is
24% (relative to the content of cellulose in raw material).
Embodiment 8:
(1) niobium pentaoxide loads wolframic acid Al catalysts 10%Al2(WO4)3/Nb2O5Preparation
0.015mol sodium tungstate, 0.005mol aluminum sulfate are dissolved separately in 40mL deionized water, it is then molten by two kinds
Liquid mixing, mixed emulsion is placed in 140 DEG C of baking ovens and is kept the temperature, and after emulsion becomes clear solution completely, is added
25.5g Nb2O5Carrier, continuation are evaporated mixed liquor at 140 DEG C；The solid being evaporated is washed with 2L deionized water, 100 DEG C of dryings,
In 800 DEG C of calcining 5h in nitrogen atmosphere, the solid catalyst Al that load capacity is 10% is obtained2(WO4)3/Nb2O5。
(2) solid catalyst 10%Al2(WO4)3/Nb2O5Catalytic cellulose prepares lactic acid
By 0.1g step (1) solid catalyst Al obtained2(WO4)3/Nb2O5, 1g maple bits and 20mL deionized water add
Enter into 50mL stirred autoclave, hydrothermal degradation 120min then is carried out to mixed liquor at 220 DEG C, obtaining lactate yield is
35% (relative to the content of cellulose in raw material).
Embodiment 9:
(1) activated carbon supported wolframic acid Al catalysts 10%Al2(WO4)3The preparation of/AC
0.015mol sodium tungstate, 0.005mol aluminum sulfate are dissolved separately in 20mL deionized water, it is then molten by two kinds
Liquid mixing, mixed emulsion is placed in 140 DEG C of baking ovens and is kept the temperature, and after emulsion becomes clear solution completely, is added
25.5g absorbent charcoal carrier, continuation are evaporated mixed liquor at 140 DEG C；The solid being evaporated is washed with 2L deionized water, 100 DEG C of dryings,
In 800 DEG C of calcining 5h in nitrogen atmosphere, the solid catalyst Al that load capacity is 10% is obtained2(WO4)3/AC。
(2) activated carbon supported wolframic acid Al catalysts 10%Al2(WO4)3/ AC catalytic cellulose prepares lactic acid
By 0.3g step (1) solid catalyst Al obtained2(WO4)3/ AC, 1g corn stover and 20mL deionized water add
Enter into 50mL stirred autoclave, hydrothermal degradation 120min then is carried out to mixed liquor at 230 DEG C, obtaining lactate yield is
26% (relative to the content of cellulose in raw material).
Embodiment 10:
(1) activated carbon supported wolframic acid Al catalysts 20%Al2(WO4)3The preparation of/AC
0.015mol sodium tungstate, 0.005mol aluminum sulfate are dissolved separately in 20mL deionized water, it is then molten by two kinds
Liquid mixing, mixed emulsion is placed in 140 DEG C of baking ovens and is kept the temperature, and after emulsion becomes clear solution completely, is added
11.3g absorbent charcoal carrier, continuation are evaporated mixed liquor at 140 DEG C；The solid being evaporated is washed with 2L deionized water, 100 DEG C of dryings,
In 800 DEG C of calcining 5h in nitrogen atmosphere, the solid catalyst Al that load capacity is 20% is obtained2(WO4)3/AC。
(2) activated carbon supported wolframic acid Al catalysts 20%Al2(WO4)3/ AC catalytic cellulose prepares lactic acid
By 0.3g step (1) solid catalyst Al obtained2(WO4)3/ AC, 1g corn stover and 20mL deionized water add
Enter into 50mL stirred autoclave, hydrothermal degradation 120min then is carried out to mixed liquor at 230 DEG C, obtaining lactate yield is
34% (relative to the content of cellulose in raw material).
Embodiment 11:
(1) activated carbon supported wolframic acid Al catalysts 30%Al2(WO4)3The preparation of/AC
0.015mol sodium tungstate, 0.005mol aluminum sulfate are dissolved separately in 20mL deionized water, it is then molten by two kinds
Liquid mixing, mixed emulsion is placed in 140 DEG C of baking ovens and is kept the temperature, and after emulsion becomes clear solution completely, is added
6.6g absorbent charcoal carrier, continuation are evaporated mixed liquor at 140 DEG C；The solid being evaporated is washed with 2L deionized water, 100 DEG C of dryings,
In 800 DEG C of calcining 5h in nitrogen atmosphere, the solid catalyst Al that load capacity is 30% is obtained2(WO4)3/AC。
(2) activated carbon supported wolframic acid Al catalysts 30%Al2(WO4)3/ AC catalytic cellulose prepares lactic acid
By 0.3g step (1) solid catalyst Al obtained2(WO4)3/ AC, 1g corn stover and 20mL deionized water add
Enter into 50mL stirred autoclave, hydrothermal degradation 120min then is carried out to mixed liquor at 230 DEG C, obtaining lactate yield is
43% (relative to the content of cellulose in raw material).
Embodiment 12:
(1) activated carbon supported wolframic acid Al catalysts 40%Al2(WO4)3The preparation of/AC
0.015mol sodium tungstate, 0.005mol aluminum sulfate are dissolved separately in 20mL deionized water, it is then molten by two kinds
Liquid mixing, mixed emulsion is placed in 140 DEG C of baking ovens and is kept the temperature, and after emulsion becomes clear solution completely, is added
4.2g absorbent charcoal carrier, continuation are evaporated mixed liquor at 140 DEG C；The solid being evaporated is washed with 2L deionized water, 100 DEG C of dryings,
In 800 DEG C of calcining 5h in nitrogen atmosphere, the solid catalyst Al that load capacity is 40% is obtained2(WO4)3/AC。
(2) activated carbon supported wolframic acid Al catalysts 40%Al2(WO4)3/ AC catalytic cellulose prepares lactic acid
By 0.3g step (1) solid catalyst Al obtained2(WO4)3/ AC, 1g corn stover and 20mL deionized water add
Enter into 50mL stirred autoclave, hydrothermal degradation 120min then is carried out to mixed liquor at 230 DEG C, obtaining lactate yield is
44% (relative to the content of cellulose in raw material).
Embodiment 13:
(1) niobium pentaoxide loads wolframic acid Al catalysts 20%Al2(WO4)3/Nb2O5Preparation
0.015mol sodium tungstate, 0.005mol aluminum sulfate are dissolved separately in 40mL deionized water, it is then molten by two kinds
Liquid mixing, mixed emulsion is placed in 140 DEG C of baking ovens and is kept the temperature, and after emulsion becomes clear solution completely, is added
11.3g Nb2O5Carrier, continuation are evaporated mixed liquor at 140 DEG C；The solid being evaporated is washed with 2L deionized water, 100 DEG C of dryings,
In 800 DEG C of calcining 5h in nitrogen atmosphere, the solid catalyst Al that load capacity is 20% is obtained2(WO4)3/Nb2O5。
(2) solid catalyst 20%Al2(WO4)3/Nb2O5Catalytic cellulose prepares lactic acid
By 0.1g step (1) solid catalyst Al obtained2(WO4)3/Nb2O5, 1g maple bits and 20mL deionized water add
Enter into 50mL stirred autoclave, hydrothermal degradation 120min then is carried out to mixed liquor at 220 DEG C, obtaining lactate yield is
41% (relative to the content of cellulose in raw material).
Embodiment 14:
(1) niobium pentaoxide loads wolframic acid Al catalysts 30%Al2(WO4)3/Nb2O5Preparation
0.015mol sodium tungstate, 0.005mol aluminum sulfate are dissolved separately in 40mL deionized water, it is then molten by two kinds
Liquid mixing, mixed emulsion is placed in 140 DEG C of baking ovens and is kept the temperature, and after emulsion becomes clear solution completely, is added
6.6g Nb2O5Carrier, continuation are evaporated mixed liquor at 140 DEG C；The solid being evaporated is washed with 2L deionized water, 100 DEG C of dryings,
In 800 DEG C of calcining 5h in nitrogen atmosphere, the solid catalyst Al that load capacity is 30% is obtained2(WO4)3/Nb2O5。
(2) solid catalyst 30%Al2(WO4)3/Nb2O5Catalytic cellulose prepares lactic acid
By 0.1g step (1) solid catalyst Al obtained2(WO4)3/Nb2O5, 1g maple bits and 20mL deionized water add
Enter into 50mL stirred autoclave, hydrothermal degradation 120min then is carried out to mixed liquor at 220 DEG C, obtaining lactate yield is
46% (relative to the content of cellulose in raw material).
Embodiment 15:
(1) niobium pentaoxide loads wolframic acid Al catalysts 40%Al2(WO4)3/Nb2O5Preparation
0.015mol sodium tungstate, 0.005mol aluminum sulfate are dissolved separately in 40mL deionized water, it is then molten by two kinds
Liquid mixing, mixed emulsion is placed in 140 DEG C of baking ovens and is kept the temperature, and after emulsion becomes clear solution completely, is added
4.2g Nb2O5Carrier, continuation are evaporated mixed liquor at 140 DEG C；The solid being evaporated is washed with 2L deionized water, 100 DEG C of dryings,
In 800 DEG C of calcining 5h in nitrogen atmosphere, the solid catalyst Al that load capacity is 40% is obtained2(WO4)3/Nb2O5。
(2) solid catalyst 40%Al2(WO4)3/Nb2O5Catalytic cellulose prepares lactic acid
By 0.1g step (1) solid catalyst Al obtained2(WO4)3/Nb2O5, 1g maple bits and 20mL deionized water add
Enter into 50mL stirred autoclave, hydrothermal degradation 120min then is carried out to mixed liquor at 220 DEG C, obtaining lactate yield is
43% (relative to the content of cellulose in raw material).
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention etc.
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of support type aluminum tungstate solid catalyst, which is characterized in that be prepared by following steps: by aluminum salt solution and tungsten
Salting liquid is by aluminium: tungsten molar ratio be 0.5~2:1 be mixed to get emulsion, by emulsion be heated to 100 DEG C~160 DEG C make its at
For clear solution, catalyst carrier is added into clear solution and obtains mixed liquor, mixed liquor is evaporated to obtain support type aluminum tungstate
Solid catalyst precursor body, support type aluminum tungstate solid catalyst precursor body it is washed and calcining after to get arrive support type wolframic acid
Aluminium solid catalyst.
2. support type aluminum tungstate solid catalyst according to claim 1, which is characterized in that the aluminium salt is selected from chlorination
One or more of aluminium, aluminum sulfate and aluminum nitrate, the tungsten salt is in tungstate lithium, sodium tungstate, potassium tungstate and ammonium tungstate
More than one.
3. support type aluminum tungstate solid catalyst according to claim 1, which is characterized in that the catalyst carrier choosing
It is described from one or more of active carbon, graphene oxide, silica, aluminium oxide, zirconium oxide, niobium oxide and Si-Al molecular sieve
Aluminum tungstate load capacity be catalyst gross mass 2%~50%.
4. support type aluminum tungstate solid catalyst according to claim 1, which is characterized in that be evaporated mixed liquor and born
The specific steps of load type aluminum tungstate solid catalyst precursor body are as follows: steam mixed liquor under conditions of temperature is 140 DEG C~160 DEG C
It is dry to obtain support type aluminum tungstate solid catalyst precursor body.
5. support type aluminum tungstate solid catalyst according to claim 1 or 4, which is characterized in that the support type tungsten
The washed specific steps with calcining of sour aluminium solid catalyst precursor body are as follows: the support type aluminum tungstate solid catalyst precursor
Removing soluble-salt is washed with water in body, then 600 DEG C~800 DEG C 1~12h of calcining in protective atmosphere.
6. support type aluminum tungstate solid catalyst according to claim 5, which is characterized in that the protective atmosphere is
Nitrogen, argon gas, helium or deoxidation flue gas.
7. a kind of support type aluminum tungstate solid catalyst described in claim 1 prepares the application in lactic acid in biomass.
8. support type aluminum tungstate solid catalyst according to claim 7 prepares the application in lactic acid in biomass, special
Sign is, includes the following steps: to obtain in the support type aluminum tungstate solid catalyst and biomass addition deionized water
Reaction mass is warming up to 180 DEG C~240 DEG C 5~600min of reaction to get lactic acid by reaction mass.
9. support type aluminum tungstate solid catalyst according to claim 8 prepares the application in lactic acid in biomass, special
Sign is, the mass ratio of the support type aluminum tungstate solid catalyst and biomass is 0.1~0.5:1, biomass and go from
The mass ratio of sub- water is 0.05~0.3:1.
10. support type aluminum tungstate solid catalyst according to claim 8 prepares the application in lactic acid in biomass, special
Sign is that the biomass is the biomass that content of cellulose is more than or equal to 20%.
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