CN118373726B - Method for preparing dulcitol crystals from xylose mother liquor - Google Patents
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- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
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- B01J29/00—Catalysts comprising molecular sieves
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- 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
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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Abstract
The invention provides a method for preparing dulcitol crystals from xylose mother liquor, which comprises the following steps: s1: diluting xylose mother liquor to a mass concentration of 20% -40%, decolorizing, filtering, ion-exchanging, and performing chromatographic separation to obtain raw material liquid and waste liquid; s2: the mass concentration of the raw material liquid is adjusted to be 20-50%, sulfate and alkali liquor are added, and the pH value of the raw material liquid is adjusted to be 7-10; s3: adding a modified Raney nickel catalyst into the raw material liquid obtained in the step S2 to perform a catalytic hydrogenation reaction to obtain a mixed liquid containing dulcitol and arabitol; s4: and (3) decoloring, filtering, ion-exchanging, concentrating and crystallizing the mixed solution obtained in the step (S3) to obtain the dulcitol crystal. The method improves the yield of the dulcitol crystal, and the purity can reach more than 99 percent.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a method for preparing dulcitol crystals from xylose mother liquor.
Background
Dulcitol (C 6H14O6) is also known as galactitol, dulcitol, or hexitol. English name: dulcitol. Dulcitol is an active ingredient in Chinese herbal medicines such as euonymus fortunei and plants, and is also one of the products of D-galactose metabolism in organisms. Dulcitol is a polyhydric sugar alcohol that can be synthesized by hydrogenation reduction of D-galactose. The current research shows that the dulcitol has therapeutic effects on rheumatoid arthritis, leukemia and cancer. In addition, dulcitol is also a raw material for tagatose production. In seventies, the American scientist found dulcitol from the maytansinol plant of the african tooth leaves and extracted the dulcitol from the plant of the dulcitaceae after a few years, but the application of the dulcitol is limited in the field of reagents, the dosage is small, the yield is low, the price is relatively high, and the dulcitol cannot be popularized and applied due to the influence of the low preparation yield.
In the prior art, for example, CN 107954836A discloses a method for obtaining a dulcitol crystal by using xylitol mother liquor as a raw material through steps of purification, concentration, rectification, dilution and gradient cooling crystallization, and the method can reduce potential safety hazard of reaction, but the technical problem of low yield also exists in terms of results.
Disclosure of Invention
In view of the above, the present invention aims to overcome the defects in the prior art, and proposes a method for preparing dulcitol crystals from xylose mother liquor.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
a method for preparing dulcitol crystals from xylose mother liquor, comprising the steps of:
s1: diluting xylose mother liquor to a mass concentration of 20% -40%, decolorizing, filtering, ion-exchanging, and performing chromatographic separation to obtain raw material liquid and waste liquid;
s2: the mass concentration of the raw material liquid is adjusted to be 20-50%, sulfate and alkali liquor are added, and the pH value of the raw material liquid is adjusted to be 7-10;
S3: adding a modified Raney nickel catalyst into the raw material liquid obtained in the step S2 to perform a catalytic hydrogenation reaction to obtain a mixed liquid containing dulcitol and arabitol;
s4: and (3) decoloring, filtering, ion-exchanging, concentrating and crystallizing the mixed solution obtained in the step (S3) to obtain the dulcitol crystal.
Preferably, the addition amount of the sulfate in the step S2 is 0.1% -1% of the mass of the raw material liquid.
Preferably, the sulfate in the step S2 is one or more of sodium sulfate, sodium bisulfate, potassium sulfate and potassium bisulfate.
Preferably, the preparation method of the modified Raney nickel catalyst comprises the following steps:
a. uniformly mixing nickel powder, aluminum powder and auxiliary metal powder to obtain a metal powder mixture;
b. Placing a sulfur source, a mesoporous molecular sieve and a metal powder mixture into different temperature areas in a high-temperature tube furnace with at least three heating temperature areas, wherein the high-temperature tube furnace comprises a first temperature area, a second temperature area and a third temperature area according to the gas route from the upstream to the downstream, the sulfur source is positioned in the first temperature area, the metal powder mixture is positioned in the second temperature area, and the mesoporous molecular sieve is positioned in the third temperature area;
c. Setting the heating temperature of the first temperature zone to be 160-250 ℃, setting the heating temperature of the second temperature zone to be 1500-2000 ℃, setting the heating temperature of the third temperature zone to be 450-600 ℃, starting a high-temperature tube furnace for heating, introducing protective gas, reacting for 2-4 hours, and cooling to room temperature;
d. taking out all materials in the high-temperature tube furnace, and grinding uniformly to obtain a precursor;
e. and (3) putting the precursor into a sodium hydroxide solution or a potassium hydroxide solution for activation, and cleaning to neutrality after the activation is finished to obtain the modified Raney nickel catalyst.
Preferably, nickel steam with the concentration of 0.05-1 ppm is introduced in the heating process of the step c.
Preferably, the mass ratio of nickel powder to aluminum powder in the metal powder mixture is 1:1, the content of the auxiliary metal powder is 1-10wt% of the total mass of the nickel powder and the aluminum powder.
Preferably, the sulfur source is sulfur powder.
Preferably, the mesoporous molecular sieve is selected from one or more of SBA and MCM series molecular sieves. For example: SBA3, SBA15, MCM41 or MCM48.
Preferably, the auxiliary metal powder is one or more of Ca, mg, fe, zn, cr, mo, pt.
Preferably, the shielding gas is argon or nitrogen.
Compared with the prior art, the invention has the following advantages:
(1) According to the modified Raney nickel catalyst, raw material powder containing nickel powder and aluminum powder, a molecular sieve and a sulfur source are placed in the same high-temperature tube furnace to be heated, the sulfur source located in a first temperature zone volatilizes in the heating process to enable the sulfur source to be deposited in a nickel-aluminum alloy and on the surface of the molecular sieve, the sulfur source doped in the nickel-aluminum alloy reacts with alkali liquor in the alkali liquor activation process and is removed in the cleaning process, the specific surface area of the catalyst and the lattice defect of nickel crystals are increased, and the reactivity of the catalyst is further increased;
(2) In the process of preparing the modified Raney nickel catalyst, nickel steam can be introduced into a high-temperature tube furnace, so that metal nickel nano particles are uniformly dispersed in ordered pore channels of a mesoporous molecular sieve, and the reaction activity and stability of the catalyst in the catalytic hydrogenation reaction process are further improved;
(3) In the method, 0.1% -1% of sulfate is added in the process of adjusting the pH value of the raw material liquid, the existence of the sulfate can improve the adsorption quantity of H 2 and promote the hydrogenation reduction of the catalyst by reducing the surface alkalinity of the modified Raney nickel catalyst, but the catalytic activity of the catalyst is reduced when the addition quantity of the sulfate is more than 1%.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the inventive concepts pertain. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The high-temperature tube furnaces used in the following examples and comparative examples have three heating temperature zones, a first temperature zone, a second temperature zone, and a third temperature zone in this order from upstream to downstream in the gas route.
The invention will be described in detail with reference to examples.
Example 1
(1) Preparation of modified Raney Nickel catalysts
A. nickel powder aluminum powder and iron powder according to 1:1: uniformly mixing the materials according to the mass ratio of 0.1 to obtain a metal powder mixture;
b. Putting sulfur powder, SBA3 type molecular sieve and metal powder mixture into different temperature areas in a high-temperature tube furnace, wherein the sulfur powder is positioned in a first temperature area, the metal powder mixture is positioned in a second temperature area, and the SBA3 type molecular sieve is positioned in a third temperature area;
c. Setting the heating temperature of the first temperature zone to 160 ℃, setting the heating temperature of the second temperature zone to 1500 ℃, setting the heating temperature of the third temperature zone to 450 ℃, starting a high-temperature tube furnace to perform gradient heating, introducing argon and nickel steam with the concentration of 0.05ppm in the heating process, reacting for 4 hours, and cooling to room temperature;
d. taking out all materials in the high-temperature tube furnace, and grinding uniformly to obtain a precursor;
e. And (3) putting the precursor into a sodium hydroxide solution with the mass concentration of 30% for activation for 30min, and then cleaning to neutrality to obtain the modified Raney nickel catalyst.
(2) Preparation of dulcitol crystals
S1: diluting xylose mother liquor to a mass concentration of 20%, decolorizing, filtering, performing ion exchange, and performing chromatographic separation to obtain raw material liquid and waste liquid;
S2: the mass concentration of the raw material liquid is adjusted to be 20 percent, and 0.1 percent of sodium sulfate and a proper amount of alkali liquor are added to adjust the pH value of the raw material liquid to be 7;
S3: adding a modified Raney nickel catalyst into the raw material liquid obtained in the step S2 to perform a catalytic hydrogenation reaction to obtain a mixed liquid containing dulcitol and arabitol;
s4: and (3) decoloring, filtering, ion-exchanging, concentrating and crystallizing the mixed solution obtained in the step (S3) to obtain the dulcitol crystal.
The average yield of the dulcitol crystals of this example was found to be 8.5% and the purity was found to be 99% by HPLC.
Example 2
(1) Preparation of modified Raney Nickel catalysts
A. nickel powder aluminum powder and magnesium powder according to 1:1: uniformly mixing the materials according to the mass ratio of 0.02 to obtain a metal powder mixture;
b. nickel sulfide, SBA15 type molecular sieve and metal powder mixture are placed in different temperature areas in a high-temperature tube furnace, wherein sulfur powder is located in a first temperature area, metal powder mixture is located in a second temperature area, and SBA15 type molecular sieve is located in a third temperature area;
c. Setting the heating temperature of the first temperature zone to be 200 ℃, setting the heating temperature of the second temperature zone to be 1800 ℃, starting a high-temperature tube furnace to perform gradient heating at the heating rate of 5 ℃/min, introducing argon and nickel steam with the concentration of 1ppm in the heating process, reacting for 4 hours, and cooling to room temperature;
d. taking out all materials in the high-temperature tube furnace, and grinding uniformly to obtain a precursor;
e. And (3) putting the precursor into a sodium hydroxide solution with the mass concentration of 30% for activation for 30min, and then cleaning to neutrality to obtain the modified Raney nickel catalyst.
(2) Preparation of dulcitol crystals
S1: diluting xylose mother liquor to a mass concentration of 40%, decolorizing, filtering, performing ion exchange, and performing chromatographic separation to obtain raw material liquid and waste liquid;
s2: the mass concentration of the raw material liquid is adjusted to be 30 percent, sodium bisulfate accounting for 0.3 percent of the mass of the raw material liquid and a proper amount of alkali liquor are added, and the pH value of the raw material liquid is adjusted to be 8;
S3: adding a modified Raney nickel catalyst into the raw material liquid obtained in the step S2 to perform a catalytic hydrogenation reaction to obtain a mixed liquid containing dulcitol and arabitol;
s4: and (3) decoloring, filtering, ion-exchanging, concentrating and crystallizing the mixed solution obtained in the step (S3) to obtain the dulcitol crystal.
The average yield of the dulcitol crystals of this example was 7.9% as measured by HPLC and the purity was 99%.
Example 3
(1) Preparation of modified Raney Nickel catalysts
A. Nickel powder aluminum powder and zinc powder according to 1:1: uniformly mixing the materials according to the mass ratio of 0.16 to obtain a metal powder mixture;
b. Sulfur powder, an MCM41 type molecular sieve and a metal powder mixture are subjected to different temperature areas in a high-temperature tube furnace, wherein the sulfur powder is positioned in a first temperature area, the metal powder mixture is positioned in a second temperature area, and the MCM41 type molecular sieve is positioned in a third temperature area;
c. Setting the heating temperature of the first temperature zone to be 230 ℃, setting the heating temperature of the second temperature zone to be 1800 ℃, setting the heating temperature of the third temperature zone to be 550 ℃, starting a high-temperature tube furnace to perform gradient heating, introducing argon in the heating process at a heating rate of 5 ℃/min, and cooling to room temperature after reacting for 4 hours;
d. taking out all materials in the high-temperature tube furnace, and grinding uniformly to obtain a precursor;
e. And (3) putting the precursor into a sodium hydroxide solution with the mass concentration of 30% for activation for 30min, and then cleaning to neutrality to obtain the modified Raney nickel catalyst.
(2) Preparation of dulcitol crystals
S1: diluting xylose mother liquor to a mass concentration of 40%, decolorizing, filtering, performing ion exchange, and performing chromatographic separation to obtain raw material liquid and waste liquid;
S2: the mass concentration of the raw material liquid is adjusted to 40 percent, sodium bisulfate accounting for 0.5 percent of the mass of the raw material liquid and a proper amount of alkali liquor are added, and the pH value of the raw material liquid is adjusted to 9;
S3: adding a modified Raney nickel catalyst into the raw material liquid obtained in the step S2 to perform a catalytic hydrogenation reaction to obtain a mixed liquid containing dulcitol and arabitol;
s4: and (3) decoloring, filtering, ion-exchanging, concentrating and crystallizing the mixed solution obtained in the step (S3) to obtain the dulcitol crystal.
The average yield of the dulcitol crystals of this example was found to be 8.0% and the purity was found to be 99% by HPLC.
Example 4
(1) Preparation of modified Raney Nickel catalysts
A. nickel powder aluminum powder and zinc powder according to 1:1: uniformly mixing the materials according to the mass ratio of 0.2 to obtain a metal powder mixture;
b. Placing sulfur powder, an MCM48 type molecular sieve and a metal powder mixture into different temperature areas of a high-temperature tube furnace, wherein the sulfur powder is positioned in a first temperature area, the metal powder mixture is positioned in a second temperature area, and the MCM48 type molecular sieve is positioned in a third temperature area;
c. setting the heating temperature of the first temperature zone to be 250 ℃, setting the heating temperature of the second temperature zone to be 2000 ℃, setting the heating temperature of the third temperature zone to be 600 ℃, starting a high-temperature tube furnace to perform gradient heating, introducing argon in the heating process at a heating rate of 5 ℃/min, and cooling to room temperature after reacting for 4 hours;
d. taking out all materials in the high-temperature tube furnace, and grinding uniformly to obtain a precursor;
e. And (3) putting the precursor into a sodium hydroxide solution with the mass concentration of 30% for activation for 30min, and then cleaning to neutrality to obtain the modified Raney nickel catalyst.
(2) Preparation of dulcitol crystals
S1: diluting xylose mother liquor to a mass concentration of 40%, decolorizing, filtering, performing ion exchange, and performing chromatographic separation to obtain raw material liquid and waste liquid;
S2: the mass concentration of the raw material liquid is adjusted to 50 percent, potassium bisulfate accounting for 0.1 percent of the mass of the raw material liquid and a proper amount of alkali liquor are added, and the pH value of the raw material liquid is adjusted to 10;
S3: adding a modified Raney nickel catalyst into the raw material liquid obtained in the step S2 to perform a catalytic hydrogenation reaction to obtain a mixed liquid containing dulcitol and arabitol;
s4: and (3) decoloring, filtering, ion-exchanging, concentrating and crystallizing the mixed solution obtained in the step (S3) to obtain the dulcitol crystal.
The average yield of the dulcitol crystals of this example was 7.8% as measured by HPLC and the purity reached 99%.
Comparative example 1
(1) Preparation of modified Raney Nickel catalysts
A. Nickel powder aluminum powder and zinc powder according to 1:1: uniformly mixing the materials according to the mass ratio of 0.1 to obtain a metal powder mixture;
b. placing an SBA3 type molecular sieve and a metal powder mixture into different temperature areas in a high-temperature tube furnace, wherein the metal powder mixture is positioned in a second temperature area, and the SBA3 type molecular sieve is positioned in a third temperature area;
c. Setting the heating temperature of the first temperature zone to be 180 ℃, setting the heating temperature of the second temperature zone to be 1500 ℃, setting the heating temperature of the third temperature zone to be 450 ℃, starting a high-temperature tube furnace to perform gradient heating, introducing argon in the heating process at a heating rate of 5 ℃/min, and cooling to room temperature after reacting for 4 hours;
d. taking out all materials in the high-temperature tube furnace, and grinding uniformly to obtain a precursor;
e. And (3) putting the precursor into a sodium hydroxide solution with the mass concentration of 30% for activation for 30min, and then cleaning to neutrality to obtain the modified Raney nickel catalyst.
(2) A dulcitol crystal was prepared in the same manner as in example 1.
The average yield of the dulcitol crystals of this example was 4.6% as measured by HPLC and the purity reached 99%.
Comparative example 2
(1) A modified Raney nickel catalyst was prepared in the same manner as in example 1.
(2) Preparation of dulcitol crystals
S1: diluting xylose mother liquor to a mass concentration of 20%, decolorizing, filtering, performing ion exchange, and performing chromatographic separation to obtain raw material liquid and waste liquid;
S2: the mass concentration of the raw material liquid is adjusted to be 20 percent, and a proper amount of alkali liquor is added to adjust the pH value of the raw material liquid to be 7;
S3: adding a modified Raney nickel catalyst into the raw material liquid obtained in the step S2 to perform a catalytic hydrogenation reaction to obtain a mixed liquid containing dulcitol and arabitol;
s4: and (3) decoloring, filtering, ion-exchanging, concentrating and crystallizing the mixed solution obtained in the step (S3) to obtain the dulcitol crystal.
The average yield of the dulcitol crystals of this example was 5.3% as measured by HPLC and the purity reached 99%.
Comparative example 3
(1) A modified Raney nickel catalyst was prepared in the same manner as in example 1.
(2) Preparation of dulcitol crystals
S1: diluting xylose mother liquor to a mass concentration of 20%, decolorizing, filtering, performing ion exchange, and performing chromatographic separation to obtain raw material liquid and waste liquid;
S2: the mass concentration of the raw material liquid is adjusted to be 20 percent, sodium bisulfate with the mass of 1.1 percent of the raw material liquid and a proper amount of alkali liquor are added, and the pH value of the raw material liquid is adjusted to be 7;
S3: adding a modified Raney nickel catalyst into the raw material liquid obtained in the step S2 to perform a catalytic hydrogenation reaction to obtain a mixed liquid containing dulcitol and arabitol;
s4: and (3) decoloring, filtering, ion-exchanging, concentrating and crystallizing the mixed solution obtained in the step (S3) to obtain the dulcitol crystal.
The average yield of the dulcitol crystals of this example was 2.8% as measured by HPLC and the purity reached 99%.
Comparative example 4
Preparation of dulcitol crystals
S1: diluting xylose mother liquor to a mass concentration of 20%, decolorizing, filtering, performing ion exchange, and performing chromatographic separation to obtain raw material liquid and waste liquid;
S2: the mass concentration of the raw material liquid is adjusted to be 20 percent, and 0.1 percent of sodium sulfate and a proper amount of alkali liquor are added to adjust the pH value of the raw material liquid to be 7;
S3: adding Raney nickel catalyst (available from Jiangsu Raney metal science and technology Co., ltd., model RCZ-80-2) into the raw material liquid obtained in the step S2 to perform catalytic hydrogenation reaction to obtain a mixed liquid containing dulcitol and arabitol;
s4: and (3) decoloring, filtering, ion-exchanging, concentrating and crystallizing the mixed solution obtained in the step (S3) to obtain the dulcitol crystal.
The average yield of the dulcitol crystals of this example was 4.5% as measured by HPLC and the purity reached 99%.
The above embodiments are merely preferred embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A method for preparing dulcitol crystals from xylose mother liquor is characterized in that: the method comprises the following steps:
s1: diluting xylose mother liquor to a mass concentration of 20% -40%, decolorizing, filtering, ion-exchanging, and performing chromatographic separation to obtain raw material liquid and waste liquid;
s2: the mass concentration of the raw material liquid is adjusted to be 20-50%, sulfate and alkali liquor are added, and the pH value of the raw material liquid is adjusted to be 7-10;
S3: adding a modified Raney nickel catalyst into the raw material liquid obtained in the step S2 to perform a catalytic hydrogenation reaction to obtain a mixed liquid containing dulcitol and arabitol;
S4: decolorizing, filtering, ion exchanging, concentrating and crystallizing the mixed solution obtained in the step S3 to obtain dulcitol crystals;
the adding amount of the sulfate in the step S2 is 0.1% -1% of the mass of the raw material liquid;
The preparation method of the modified Raney nickel catalyst comprises the following steps:
a. uniformly mixing nickel powder, aluminum powder and auxiliary metal powder to obtain a metal powder mixture;
b. Placing a sulfur source, a mesoporous molecular sieve and a metal powder mixture into different temperature areas in a high-temperature tube furnace with at least three heating temperature areas, wherein the high-temperature tube furnace comprises a first temperature area, a second temperature area and a third temperature area according to the gas route from the upstream to the downstream, the sulfur source is positioned in the first temperature area, the metal powder mixture is positioned in the second temperature area, and the mesoporous molecular sieve is positioned in the third temperature area;
c. Setting the heating temperature of the first temperature zone to be 160-250 ℃, setting the heating temperature of the second temperature zone to be 1500-2000 ℃, setting the heating temperature of the third temperature zone to be 450-600 ℃, starting a high-temperature tube furnace for heating, introducing protective gas, reacting for 2-4 hours, and cooling to room temperature;
d. taking out all materials in the high-temperature tube furnace, and grinding uniformly to obtain a precursor;
e. and (3) putting the precursor into a sodium hydroxide solution or a potassium hydroxide solution for activation, and cleaning to neutrality after the activation is finished to obtain the modified Raney nickel catalyst.
2. The method for preparing dulcitol crystals from xylose mother liquor as claimed in claim 1, wherein: the sulfate in the step S2 is one or more of sodium sulfate, sodium bisulfate, potassium sulfate and potassium bisulfate.
3. The method for preparing dulcitol crystals from xylose mother liquor as claimed in claim 1, wherein: and c, introducing nickel steam with the concentration of 0.05-1 ppm in the heating process of the step.
4. The method for preparing dulcitol crystals from xylose mother liquor as claimed in claim 1, wherein: the mass ratio of the nickel powder to the aluminum powder in the metal powder mixture is 1:1, the content of the auxiliary metal powder is 1-10wt% of the total mass of the nickel powder and the aluminum powder.
5. The method for preparing dulcitol crystals from xylose mother liquor as claimed in claim 1, wherein: the sulfur source is sulfur powder.
6. The method for preparing dulcitol crystals from xylose mother liquor as claimed in claim 1, wherein: the mesoporous molecular sieve is selected from one or more of SBA and MCM series molecular sieves.
7. The method for preparing dulcitol crystals from xylose mother liquor as claimed in claim 1, wherein: the auxiliary metal powder is one or more of Ca, mg, fe, zn, cr, mo, pt.
8. The method for preparing dulcitol crystals from xylose mother liquor as claimed in claim 1, wherein: the shielding gas is argon or nitrogen.
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| CN101029059A (en) * | 2006-02-28 | 2007-09-05 | 禹城福田药业有限公司 | Preparation of dulcose crystal |
| CN104707626A (en) * | 2015-03-26 | 2015-06-17 | 赛鼎工程有限公司 | Raney nickel catalyst and preparation method thereof |
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| CN101392339A (en) * | 2007-09-18 | 2009-03-25 | 汉能科技有限公司 | Renyi alloy for preparing renyi catalyst, preparation method thereof and use thereof |
| CN101254466A (en) * | 2008-03-25 | 2008-09-03 | 浙江大学 | Preparation method of supported Raney catalyst |
| CN101775413B (en) * | 2010-03-23 | 2013-03-20 | 禹城绿健生物技术有限公司 | Technique for producing xylitol and dulcitol simultaneously |
| CN103923039A (en) * | 2014-01-30 | 2014-07-16 | 天津中津药业股份有限公司 | Method for preparing dianhydrogalactitol |
| CA2945297A1 (en) * | 2014-04-10 | 2015-10-15 | Archer Daniels Midland Company | Synthesis of reduced sugar alcohols, furan derivatives |
| CN109371069B (en) * | 2018-09-30 | 2022-02-15 | 南京工业大学 | Method for preparing 5-hydroxymethylfurfural and polyalcohol from xylose mother liquor |
| CN112206769A (en) * | 2020-09-21 | 2021-01-12 | 浙江工业大学 | Multi-walled carbon nanotube supported ruthenium catalyst and preparation and application thereof |
| CN117778775A (en) * | 2023-11-10 | 2024-03-29 | 中南大学 | Method for preparing Raney nickel precursor by recycling and coupling waste nickel-based superalloy |
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| CN101029059A (en) * | 2006-02-28 | 2007-09-05 | 禹城福田药业有限公司 | Preparation of dulcose crystal |
| CN104707626A (en) * | 2015-03-26 | 2015-06-17 | 赛鼎工程有限公司 | Raney nickel catalyst and preparation method thereof |
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