CN106861747A - The preparation method and tin-based catalyst of a kind of tin-based catalyst and application - Google Patents
The preparation method and tin-based catalyst of a kind of tin-based catalyst and application Download PDFInfo
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- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- 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
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
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- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
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- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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Abstract
The invention provides the preparation and its application in carbohydrate catalyzed conversion of a kind of tin-based catalyst.The method prepares tin-based catalyst using the method for ion exchange, and it is applied to the isomerization of carbohydrate and during catalyzed conversion prepares the reaction of lactate, by a step catalytic conversion process at 80-210 DEG C, realize efficient carbohydrate, high selectivity, prepare fructose or lactate in high yield.The remarkable advantage that reaction provided by the present invention is renewable resource with raw material, Atom economy is high.Meanwhile, catalyst preparation process haves the advantages that simple and easy to do, with low cost.Additionally, with others with biomass as compared with the technology of raw material fructose or lactate, this process has the advantages that course of reaction is simple, space-time yield is high, be easy to industrialized production.
Description
Technical field
The invention belongs to the catalytic field in biomass conversion, more particularly to a kind of system of tin-based catalyst
The standby and its application in carbohydrate catalyzed conversion, specifically carbohydrate is urged in tinbase
Isomerization and carbohydrate catalyzed conversion are prepared as lactate reacts under agent.
Background technology
Supported tin-based catalyst has unique Lewis acid, is showed in many catalytic reactions
Go out the reactivity of uniqueness, thus cause the common concern of researcher.At present, tinbase molecular sieve catalytic
The preparation of agent still suffer from preparation time it is long the characteristics of.(Nature, 2001,412 such as Avelino Corma:
424-425) using tetraethyl orthosilicate, SnCl4·H2O is that raw material is obtained by after hydrolysis, crystallization
Stanniferous Sn-Beta molecular sieves, it is acid with Lewis well, but this method needs the preparation grown very much
Cycle is more long, up to 40 days.(Angew.Chem.Int.Ed., 2012,51 such as Ive Hermans:
11736-11739) by tin presoma and dealuminzation molecular sieve together ball milling, by introducing tin after roasting, this
Catalyst shows catalysis activity higher, but molecular sieve is easily chipping in mechanical milling process,
Cause the change of specific surface and crystal formation.In addition, the B acid that above-mentioned catalyst surface can have residual is living
Property position, so as to cause the generation of side reaction.
Fructose is a kind of important carbohydrate, and its content in nature is relatively low, but it is in food
The fields such as product, chemical industry have a wide range of applications, and its price is the nearly twice of glucose.Therefore, Portugal
Grape sugar is isomerized to fructose as a new study hotspot.Isomerization method main at present has alkalescence
Isomerization, but it is unstable to deposit fructose in the basic conditions, easily decomposes, reset, and generation is a large amount of secondary
The shortcoming of product, the yield of fructose is relatively low.The method of another isomerization is heterogeneous acidic, main
The acid effect of framework of molecular sieve tin is utilized, but has that the system with molecular sieve for preparing standby difficult, cycle is long, choosing
The shortcomings of selecting property is relatively low (Green Chem., 2013,15,2777-2785).
Esben Taarning et al. use Sn-Beta molecular sieves, realize glucose, fructose and directly convert
Lactate (Science, 2010,602-605) is prepared, but this catalyst preparation process is complicated, it is difficult to
Realize application.In the research in later stage, Bert F.Sels et al. use Beta molecular sieves dealuminzations and then above tin
Method, in introducing tin into framework of molecular sieve (ACS Catal., 2015,5,928-940), but the method
Dealumination process is uncontrollable, haves the shortcomings that dealuminzation is incomplete, there is a certain amount of B acid, therefore in carbon water
A certain amount of accessory substance can be generated in compound conversion.
The method for preparing catalyst that the present invention is provided, it is presoma to use single siliceous molecular sieve, is realized
The controllable introducing of tin, has the advantages that catalyst preparation is simple, is easily worked, different in carbohydrate
Structure and carbohydrate degradation show catalysis activity higher in preparing the reaction of lactate.This is anti-
Answer process not only simple to operate, catalyst preparation is simple and easy to apply, it is with low cost, and also transformation efficiency is high,
The space-time yield of product is high and there is operability height, be easy to industrialized advantage.
The content of the invention
It is an object of the invention to provide a kind of preparation of tin-based catalyst and its in carbohydrate catalysis
Application in conversion.Tin-based catalyst is prepared using the method for ion exchange, and applies it to carbon
Hydrate isomerization and catalyzed conversion are prepared in the reaction of lactate.
To achieve the above object, the technical scheme taken of the present invention is：Catalyst is using ion exchange
Prepared by mode, the mass concentration of the tin element of tin precursor solution is 0.1%-30%, ion exchange process
Middle solution of tin is more than 1 with the mass ratio of carrier, and ion-exchange time is 0.5-48 hours；
Prepared catalyst is used for carbohydrate isomerization and directly prepared by conversion in alcoholic solution
Methyl lactate, reaction is carried out in enclosed high pressure reactor or continuous tubular reactor, in course of reaction
Inert gas, 80 DEG C -210 DEG C of reaction temperature, during reaction are full of in reactor or continuous tubular reactor
Between more than 1 hour be less than 48 hours.
Tin-based catalyst is prepared using ion-exchange, specially：
1) prepare the precursor solution of tin, the preferred concentration of solution is 0.5%-10%, solvent be methyl alcohol,
Ethanol, isopropanol, butanol one or more；
2) carrier is added in the precursor solution of tin, preferably swap time is 1-12 hours, is stirred
Speed is mixed for 300-1200rpm, temperature is 10-50 DEG C, carrier be MCM-41, SBA-15, SBA-1,
One or more in KIT-1, Ludox, silica；
3) carrier after exchange filtered, cleaned with coordinative solvent, then dried and at 400-800 DEG C
Lower roasting 1-24 hours.
Solution replacement temperature is 15-35 DEG C, and preferably sintering temperature is 500-600 DEG C, when being preferably calcined
Between be 2-5 hours
Prepare tin-based catalyst Xi Yuan for butter of tin, stannous chloride, stannous methide, dioctyl tin,
Tetraphenyltin, tributyl tin acetate, triphenyltin one or more.
Catalyst be applied to reaction dissolvent in the isomerization reaction of carbohydrate be water, methyl alcohol, ethanol,
One or more in butanol；Catalyst is applied to carbohydrate catalytic degradation and prepares lactate
Reaction in solvent be methyl alcohol, ethanol, propyl alcohol, butanol in one or more.
Reaction is carried out in enclosed high pressure reactor or continuous tubular reactor, and preferable reaction temperature is
100-180 DEG C, preferred reaction time is 5-24 hours.
Reaction raw materials carbohydrate weight ratio in a solvent is 1%-10%；The consumption of catalyst is accounted for
Between the 0.5%-3% of all materials.
Inert gas in reaction is one or more in nitrogen, argon gas, helium, initial pressure
Power is normal pressure.
Carbohydrate be starch, hemicellulose, sucrose, glucose, fructose, levulan, xylose,
One or two or more kinds in synanthrin, jerusalem artichoke, soluble oligomeric xylose.
The invention has the advantages that：
1. method for preparing catalyst is simple, catalyst activity position is single.Can be kept away using pure silicon molecular sieve
Exempt from the acid of B present in Si-Al molecular sieve position, there is the carrying out using reaction.
2., with the carbohydrate in biomass as raw material, the advantage of recyclability meets sustainable development
The requirement of exhibition.
3. the Spatial-temporal Transformation rate of carbohydrate is higher, good product selectivity, should with industrialization well
Use prospect.
Below by specific embodiment, the present invention is described in detail, but these embodiments are not to this
The Composition of contents limitation of invention.
Specific embodiment
Embodiment 1
The preparation of SBA-15：Under conditions of 40 DEG C, 16gP123 is dissolved in 120g water and 472mL
In the aqueous solution of hydrochloric acid (2M), after being completely dissolved, in the case where being stirred continuously, 36mL TEOS are added,
Continue to stir 24h, be put into 100 DEG C of crystallization 24h in water heating kettle, by filtering and washing, 100 DEG C are done
Dry, 550 DEG C of roastings obtain white powder SBA-15.
The preparation of MCM-41：25g sodium metasilicate is dissolved in beaker with 30ml distilled water, 6.4g's
Cetyl trimethyl desertization presses surfactant (CTAB), heating for dissolving in the distilled water of 20ml,
Be cooled to room temperature, 10min stirred after mixing, with sulfuric acid solution (5mol/L) adjust mixture pH value to
10, continue to stir 80min, solution is changed into sticky transparent gel-form.100ml is then charged into carry
In the stainless steel water heating kettle of polytetrafluoroethylliner liner, it is placed in baking oven, the crystallization 72h at a temperature of 130 DEG C,
Suction filtration is cooled down after taking-up, is washed to neutrality, be then dried overnight at 90 DEG C, gained semi-finished product are placed in
It is to slowly warm up to the heating rate of 2 DEG C/min be calcined 5h at 550 DEG C in Muffle furnace, obtains total silicon
MCM-41 mesopore molecular sieves.
The preparation of KIT-1 molecular sieves：By sodium metasilicate, cetyl trimethylammonium bromide, ethylenediamine tetrem
Sour sodium and distilled water are in molar ratio 1:0.25:1:60 mixing, polytetrafluoroethylene (PTFE) is incorporated with after stirring
In the autoclave pressure of liner, in being cooled down after 100 DEG C of constant temperature 24h, the pH of re-adjustments mixture is 11,
Constant temperature 12h, after taking-up with distilled water cyclic washing to filtrate pH be 7, dry naturally, Ran Hou
1h is calcined in 550 DEG C of nitrogen atmospheres, 6h is calcined in air and is obtained presoma.This powder is used
0.1mol/L salpeter solutions carry out pickling, and it is 10 with the mass ratio of powder to control salpeter solution:1, room temperature
Stirring 0.5h filterings, it is the prepared KIT-1 of drying at 7,100 DEG C to be washed with distilled water to the pH of filtrate
Molecular sieve.
Embodiment 2
The preparation of tinbase molecular sieve catalyst：
By the presoma of tin:Butter of tin, stannous chloride, stannous methide, dioctyl tin, tetraphenyltin,
Tributyl tin acetate, triphenyltin one or more, be dissolved in ethanol solution.Certain
At a temperature of, pure silicon molecular sieve is added, stir 5 hours, filtering, dry and be calcined at 600 DEG C,
Obtain Sn- molecular sieve catalysts.
By the presoma of tin:Butter of tin, stannous chloride, stannous methide, dioctyl tin, tetraphenyltin,
Tributyl tin acetate, triphenyltin one or more, be dissolved in ethanol solution.Certain
At a temperature of, pure silicon molecular sieve is added, stir 12 hours, filtering, dry and be calcined at 600 DEG C,
Obtain Sn- molecular sieve catalysts.
By the presoma of tin:Butter of tin, stannous chloride, stannous methide, dioctyl tin, tetraphenyltin,
Tributyl tin acetate, triphenyltin one or more, be dissolved in aqueous isopropanol.One
Determine at temperature, add pure silicon molecular sieve, stir 0.2 hour, filtering is dried and is calcined at 500 DEG C,
Obtain Sn- molecular sieve catalysts.
The preparation of comparative catalyst：
By the concentration of 1g H-Beta molecular sieves and 50ml for the concentrated nitric acid of 10mol/L is mixed, at 80 DEG C
Lower stirring reaction 12h takes off the aluminium inside molecular sieve, filters, is washed to neutrality, and drying water removal is obtained
Obtain dealuminzation molecular sieve；Butter of tin and organic solvent are subsequently adding, 20h is stirred at 100 DEG C makes tetrachloro
Change tin to be diffused into inside dealuminzation molecular sieve, then filter, wash, be calcined, obtain containing metal center
Immobilized Lewis acid.
Embodiment 3
Isomerization experiments：By 0.5g carbohydrate, 0.15g catalyst and 5ml water or alcoholic solution add
Enter in 20ml reactors, after being passed through three gases of nitrogen displacement, temperature programming to 100-120 DEG C,
Reaction 5-200min.After reaction terminates, room temperature is down to, the supernatant fluid after centrifugation is taken, in efficient liquid
Separated on phase chromatogram calcium type ion exchange column and detected with differential refractive index detector.Product is received
The products such as fructose, HMF are calculated in rate.
Embodiment 4
Catalyzed conversion prepares lactate：By 0.2g carbohydrate, 0.15g catalyst and 10ml first
Alcohol is added in 20ml reactors, after being passed through three gases of nitrogen displacement, temperature programming to 160 DEG C,
Reaction 20h.After reaction terminates, room temperature is down to, the supernatant fluid after centrifugation is taken, in gas-chromatography watt
Separated in peace CP-WAX58 (FFAP) CB chromatographic columns.To methyl lactate, second in product yield
The products such as acyl methyl propionate are calculated.
Embodiment 5
Different catalysts are catalyzed the result of glucose isomerization on reactor, and reaction condition is with embodiment 3
(table one).
In the different catalysts of table one, result (110 DEG C, 120min of glucose isomerization；Tin presoma is
Butter of tin；Swap time is 12 hours；Exchange solvent is ethanol；Sintering temperature is 600 DEG C)
As shown in Table 1, the addition of tin can significantly improve the activity of glucose isomerization, and pure silicon point
The species and solvent species of son sieve all have a huge impact to final product.Wherein, exist
More than 40.3%, the selectivity of fructose reaches the conversion ratio of glucose on Sn (5%)-SBA-15 catalyst
86.5%, it is not detected by HMF.
Embodiment 6
Different catalysts are catalyzed the result that synanthrin conversion prepares lactate on reactor, and reaction condition is with real
Apply example 4 (table two).
In the different catalysts of table two, synanthrin conversion prepares the result of lactate (except special instruction tin forerunner
Body is butter of tin, and exchange solvent is ethanol；Swap time is 12 hours；Sintering temperature is 600 DEG C)
As shown in Table 2, compare with carrier, the yield of notable methyl lactate is capable of in the addition of tin, and is suppressed
The generation of methyl ester levulinate, with selectivity higher.In addition, molecular sieve carrier, Xi Yuan and
Ion-exchange time also significantly affects the activity of catalyst, in-SBA-15-6 hours catalyst of Sn (5%)
On, the selectivity of methyl lactate reaches 55.6%.
Embodiment 7
Catalyzed conversion result (table three) of the various carbohydrate on reactor, reaction condition is with implementation
Example 4.
On table three Sn (5%)-SBA-15 catalyst, the result of the catalyzed conversion of various carbohydrate (is removed
Special instruction tin presoma is butter of tin, and swap time is 12 hours；Sintering temperature is 600 DEG C)
As shown in Table 3, in the catalytic process that various carbohydrate can be involved in the present invention efficiently
Be converted into methyl lactate, even if the selectivity of methyl lactate still reaches on primary jerusalem artichoke
42.6%, and the generation without methyl ester levulinate.
Embodiment 8
The catalyzed conversion result (table four) of different catalysts glucose on continuous tubular reactor, reaction
Condition is：The concentration of glucose is 10%, and temperature is 90-130 DEG C, and atmosphere is nitrogen, mass space velocity
It is 1.2h-1。
Under the different catalysts of table four and reaction condition, catalysis of the glucose on continuous tubular reactor turns
Change result (glucose concentration is 10%, and flow velocity is 0.1ml/min)
As shown in Table 4, in the catalytic process that glucose can be involved in the present invention, in different catalysis
Fructose is efficiently converted into agent.The conversion ratio of the upper glucose of Sn (5%)-SBA-15 reaches at 110 DEG C
To 32.5%, the selectivity of fructose is 88.9%
Comparative example
Results contrast (the reaction condition reality of catalyst is prepared in preferred catalysts involved in the present invention and document
Apply example 4).
The Comparative result of the present invention of table five and open source literature catalyst
Compared with the result of document catalyst, there is the catalyst in the present invention methyl lactate higher to select
Selecting property.In the preparation of catalyst, the catalyst preparation process being related in the present invention is more simple and easy to apply
(referring to embodiment 1,2, comparative catalyst's preparation process), is easy to industrialized production.
Claims (10)
1. a kind of preparation method of tin-based catalyst, it is characterised in that：Catalyst uses carrier ion
Prepared by the mode of exchange, the mass concentration of the tin element of tin precursor solution is 0.1%-30%, and ion is handed over
Tin precursor solution is more than 1 with the mass ratio of carrier during changing, and ion-exchange time is that 0.5-48 is small
When.
2. according to the preparation method described in claim 1, it is characterised in that：Tin-based catalyst use from
Prepared by sub- exchange process, specially：
1) prepare the precursor solution of tin, the preferred concentration of solution is 0.5%-10%, solvent be methyl alcohol,
Ethanol, isopropanol, butanol one or more；
2) carrier is added in the precursor solution of tin, preferably swap time is 1-24 hours, is stirred
Speed is mixed for 300-1200rpm, temperature is 10-50 DEG C, carrier be MCM-41, SBA-15, SBA-1,
One or more in KIT-1, Ludox, silica；
3) carrier after exchange is filtered, with step 1) identical solvent clean, then drying,
And be calcined 1-24 hours at 400-800 DEG C.
3. according to the preparation method described in claim 2, it is characterised in that：
Ion exchanged soln temperature is 15-35 DEG C, and preferably sintering temperature is 500-600 DEG C, is preferably roasted
The burning time is 2-5 hours.
4. according to the preparation method described in claim 1 or 2, it is characterised in that：
Prepare tin-based catalyst Xi Yuan for butter of tin, stannous chloride, stannous methide, dioctyl tin,
Tetraphenyltin, tributyl tin acetate, triphenyltin one or more.
5. any prepared tin-based catalysts of a kind of claim 1-4.
6., according to the application of tin-based catalyst described in claim 5, tin-based catalyst is used in carbon water
In compound for catalysis conversion.
7. according to the application of tin-based catalyst described in claim 6, it is characterised in that：
Prepared catalyst is used for carbohydrate, and in isomerization or in alcoholic solution, directly conversion is made
Standby methyl lactate, reaction is carried out in enclosed high pressure reactor or continuous tubular reactor, course of reaction
Inert gas, 80 DEG C -210 DEG C of reaction temperature, reaction are full of in middle reactor or continuous tubular reactor
Time was less than 48 hours more than 1 hour.
8. according to the application of tin-based catalyst described in claim 7, it is characterised in that：Catalyst should
It is water, methyl alcohol, ethanol, propyl alcohol, butanol for reaction dissolvent in the isomerization reaction of carbohydrate
In one or more；Catalyst is applied to carbohydrate catalytic degradation and prepares the anti-of lactate
Should in solvent be methyl alcohol, ethanol, propyl alcohol, butanol in one or more.
9. according to the application described in claim 7, it is characterised in that：Reaction is in enclosed high pressure reaction
Carried out in kettle or continuous tubular reactor, preferable reaction temperature is 100-180 DEG C, preferred reaction time is
5-24 hours；
Reaction raw materials carbohydrate weight ratio in a solvent is 1%-10%；The consumption of catalyst is accounted for
Between the 0.5%-3% of all materials；
Inert gas in reaction is one or more in nitrogen, argon gas, helium, initial pressure
Power is normal pressure.
10. according to the application described in claim 7, it is characterised in that：The carbohydrate is shallow lake
It is powder, hemicellulose, sucrose, glucose, fructose, levulan, xylose, synanthrin, jerusalem artichoke, solvable
One or two or more kinds of property xylo-oligosaccharide.
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| CN111253450A (en) * | 2018-11-30 | 2020-06-09 | 中国石油化工股份有限公司 | Method for preparing fructose by catalyzing glucose |
| CN111253449A (en) * | 2018-11-30 | 2020-06-09 | 中国石油化工股份有限公司 | Method for preparing fructose |
| CN111905802A (en) * | 2020-06-15 | 2020-11-10 | 厦门大学 | Method for preparing lactate by using molybdenum-alkali metal/alkaline earth metal modified Lewis acid catalyst |
| CN112175177A (en) * | 2020-10-15 | 2021-01-05 | 贵州省材料技术创新基地 | Catalyst and preparation method thereof, and preparation method of polylactic acid |
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| CN114377720A (en) * | 2022-01-25 | 2022-04-22 | 浙江省林业科学研究院 | Tin-based catalyst and preparation method and application thereof |
| CN116272945A (en) * | 2023-01-16 | 2023-06-23 | 山东理工大学 | Preparation method and application of acid-base carbon-based catalyst |
| CN116440941A (en) * | 2023-03-17 | 2023-07-18 | 宏业生物科技股份有限公司 | Composite mesoporous molecular sieve catalyst and application thereof in preparation of arabinose |
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| CN110152648B (en) * | 2018-02-12 | 2022-01-04 | 中国石油化工股份有限公司 | Preparation method of tin catalyst, tin catalyst and application thereof |
| CN110152648A (en) * | 2018-02-12 | 2019-08-23 | 中国石油化工股份有限公司 | Preparation method, tin catalyst and its application of tin catalyst |
| CN111253250B (en) * | 2018-11-30 | 2023-03-10 | 中国石油化工股份有限公司 | Method for preparing lactate |
| CN111253450A (en) * | 2018-11-30 | 2020-06-09 | 中国石油化工股份有限公司 | Method for preparing fructose by catalyzing glucose |
| CN111253450B (en) * | 2018-11-30 | 2023-03-14 | 中国石油化工股份有限公司 | Method for preparing fructose by catalyzing glucose |
| CN111253250A (en) * | 2018-11-30 | 2020-06-09 | 中国石油化工股份有限公司 | Method for preparing lactate |
| CN111253449A (en) * | 2018-11-30 | 2020-06-09 | 中国石油化工股份有限公司 | Method for preparing fructose |
| CN111253449B (en) * | 2018-11-30 | 2023-03-10 | 中国石油化工股份有限公司 | Method for preparing fructose |
| CN112742446A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Catalyst for preparing fructose and preparation method and application thereof |
| CN113121616A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | Method for preparing fructose through glucose chemical isomerization |
| CN113121616B (en) * | 2019-12-31 | 2022-08-12 | 中国石油化工股份有限公司 | Method for preparing fructose through glucose chemical isomerization |
| CN111905802B (en) * | 2020-06-15 | 2022-01-18 | 厦门大学 | Method for preparing lactate by using molybdenum-alkali metal/alkaline earth metal modified Lewis acid catalyst |
| CN111905802A (en) * | 2020-06-15 | 2020-11-10 | 厦门大学 | Method for preparing lactate by using molybdenum-alkali metal/alkaline earth metal modified Lewis acid catalyst |
| CN113831238A (en) * | 2020-06-24 | 2021-12-24 | 中国石油化工股份有限公司 | Method for preparing methyl lactate by catalytic conversion of carbohydrate |
| CN113831238B (en) * | 2020-06-24 | 2024-05-03 | 中国石油化工股份有限公司 | Method for preparing methyl lactate by catalytic conversion of carbohydrate |
| CN112175177A (en) * | 2020-10-15 | 2021-01-05 | 贵州省材料技术创新基地 | Catalyst and preparation method thereof, and preparation method of polylactic acid |
| CN113509940A (en) * | 2021-07-08 | 2021-10-19 | 广东工业大学 | NiSn-MgAlO @ C phase transfer catalyst and preparation method and application thereof |
| CN113509940B (en) * | 2021-07-08 | 2024-04-12 | 广东工业大学 | NiSn-MgAlO@C phase transfer catalyst and preparation method and application thereof |
| CN114377720A (en) * | 2022-01-25 | 2022-04-22 | 浙江省林业科学研究院 | Tin-based catalyst and preparation method and application thereof |
| CN114377720B (en) * | 2022-01-25 | 2024-04-19 | 浙江省林业科学研究院 | Tin-based catalyst and preparation method and application thereof |
| CN116272945A (en) * | 2023-01-16 | 2023-06-23 | 山东理工大学 | Preparation method and application of acid-base carbon-based catalyst |
| CN116440941A (en) * | 2023-03-17 | 2023-07-18 | 宏业生物科技股份有限公司 | Composite mesoporous molecular sieve catalyst and application thereof in preparation of arabinose |
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