CN108212207B - Solid acid catalyst for preparing methyl lactate by catalytic conversion of glucose and preparation method thereof - Google Patents
Solid acid catalyst for preparing methyl lactate by catalytic conversion of glucose and preparation method thereof Download PDFInfo
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- 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
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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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7057—Zeolite Beta
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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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
- B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
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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
- 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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- 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
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a solid acid catalyst for preparing methyl lactate by catalytic conversion of glucose and a preparation method thereof, wherein the solid acid catalyst takes a dealuminized beta molecular sieve as a carrier, Sn as a first active component, any one of Fe, In, Mg and Ni as a second active component, the mass of the catalyst is 100%, the loading amount of the first active component is 1.5-3%, and the molar ratio of the first active component to the second active component is 1: 1-2.5. The catalyst adopts a two-step hydrothermal synthesis method, active components are doped in a beta molecular sieve framework, the preparation method is simple, the period is short, the stability is good, the corrosion to equipment is small, the catalytic activity for preparing methyl lactate by catalytically converting glucose is good, the yield is high, the methyl lactate is easy to separate and recover from reactants, the methyl lactate can be recycled and has good recycling stability, glucose can be completely catalytically converted, and the yield of methyl lactate reaches 67 percent at most.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a solid acid catalyst for preparing methyl lactate by catalytically converting glucose and a preparation method thereof.
Background
With the gradual decrease of petrochemical fuel resources and the increasingly prominent ecological environment problems, the development and utilization of renewable and environment-friendly biomass resources to replace fossil energy has become a hot spot concerned by researchers at home and abroad. From biomass resources, a plurality of chemical products can be prepared, wherein methyl lactate is an important platform compound.
Methyl lactate, also known as methyl 2-hydroxypropionate, is readily soluble in water, ethanol and most organic solvents, has a relative density of 1.09 and a boiling point of 144-145 ℃, and contains an ester group, a hydroxyl group and an alpha-H in the molecular formula, so that the methyl lactate has high reaction activity and can be subjected to hydrolysis, addition, reduction, substitution, condensation and other reactions. Methyl lactate is mainly used as a synthetic spice and a herbicide, and is an important industrial solvent, so that the methyl lactate is widely used in the food industries of medicines, resin coatings, adhesives, cleaning agents, dry cleaning liquids, printing inks, cosmetics, cigarettes, wines, beverages, ice creams and the like.
Methyl lactate is used as an important chemical product, and is prepared by esterification of lactic acid and methanol mainly by using sulfuric acid as a catalyst in the industry. Wherein the sulfuric acid is easy to corrode equipment, the lactic acid is easy to generate side reaction, and the product yield is low. The solid acid catalyst is considered as an environment-friendly catalyst and widely applied to organic chemical reaction, and has the advantages of easy separation from reactants, simple process equipment, low corrosivity, low environmental pollution, reusability and the like. However, in the current reports on the preparation of methyl lactate by using solid acid catalyst to catalyze the alcoholysis of biomass, the yield of methyl lactate is relatively low. Therefore, there is a great need to find a more efficient, more stable and environmentally friendly solid acid catalyst.
Disclosure of Invention
The invention aims to solve the technical problems of the prior art for preparing methyl lactate and provides a solid acid catalyst for preparing methyl lactate by catalytic conversion of glucose, which has the advantages of simple preparation method, high catalytic activity, high selectivity, good stability, easy separation and recovery, environmental friendliness and no pollution.
The solid acid catalyst used for solving the technical problems is a solid acid catalyst which takes a dealuminized beta molecular sieve as a carrier, takes Sn as a first active component, takes any one of Fe, In, Mg and Ni as a second active component, and takes the mass of the carrier as 100%, the loading amount of the first active component is 1.5-3%, and the molar ratio of the first active component to the second active component is 1: 1-2.5.
When the second active component is Fe, the molar ratio of the first active component to the second active component is preferably 1: 1; when the second active component is any one of In, Mg and Ni, the molar ratio of the first active component to the second active component is preferably 1: 1.5.
The preparation method of the solid acid catalyst comprises the following steps: dispersing the H-beta molecular sieve into a nitric acid aqueous solution with the concentration of 6mol/L according to the solid-to-liquid ratio of 1g: 25-40 mL, stirring for 2-8 hours at 50-100 ℃, washing with deionized water to be neutral, and drying at 50-120 ℃ to obtain a dealuminized beta molecular sieve; based on the mass of the carrier being 100%, dispersing the dealuminized beta molecular sieve, the soluble salt of the first active component and the soluble salt of the second active component in a tetraethylammonium hydroxide aqueous solution according to the loading amount of the first active component being 1.5-3%, the molar ratio of the first active component to the second active component being 1: 1-2.5, stirring at normal temperature for 3-8 hours, adding an ammonium fluoride aqueous solution, continuously stirring for 1-3 hours, performing a hydrothermal reaction at 100-200 ℃ for 12-48 hours, cooling to normal temperature after the reaction is finished, adding hexadecyl trimethyl ammonium bromide, a tetramethyl ammonium hydroxide aqueous solution and deionized water, stirring at normal temperature for 2-6 hours, performing a hydrothermal reaction at 100-200 ℃ for 12-48 hours, performing suction filtration, washing, drying, and roasting at 500-600 ℃ for 5-8 hours to obtain the solid acid catalyst.
The above preparation method is further preferred: dispersing the H-beta molecular sieve in a nitric acid aqueous solution with the concentration of 6mol/L according to the solid-to-liquid ratio of 1g:30mL, stirring for 5-6 hours at 80-90 ℃, washing with deionized water to be neutral, and drying at 80-100 ℃ to obtain a dealuminized beta molecular sieve; based on the mass of the carrier as 100%, dispersing the dealuminized beta molecular sieve, soluble salt of the first active component and soluble salt of the second active component in tetraethylammonium hydroxide aqueous solution according to the loading amount of the first active component being 1.5-3%, the molar ratio of the first active component to the second active component being 1: 1-2.5, stirring at normal temperature for 5-6 hours, adding ammonium fluoride aqueous solution, continuing stirring for 2 hours, carrying out hydrothermal reaction at 140-160 ℃ for 24 hours, cooling to normal temperature after the reaction is finished, adding hexadecyl trimethyl ammonium bromide, tetramethyl ammonium hydroxide aqueous solution and deionized water, stirring at normal temperature for 3-4 hours, carrying out hydrothermal reaction at 130-140 ℃ for 24 hours, carrying out suction filtration after the reaction is finished, washing, drying, and roasting at 550 ℃ for 6 hours to obtain the solid acid catalyst.
In the preparation method, the mass ratio of the dealuminized beta molecular sieve to the tetraethylammonium hydroxide aqueous solution, the ammonium fluoride aqueous solution, the hexadecyltrimethylammonium bromide, the tetramethylammonium hydroxide aqueous solution and the deionized water is preferably 1: 3-4: 0.3-0.4: 1-2: 0.3-0.4: 15-20, wherein the mass fractions of the tetraethylammonium hydroxide aqueous solution and the tetramethylammonium hydroxide aqueous solution are both 25%, and the mass fraction of the ammonium fluoride aqueous solution is 30-40%.
The soluble salt of the first active component is tin chloride or tin nitrate, and the soluble salt of the second active component is any one of ferric chloride, indium chloride, magnesium chloride and nickel chloride.
The method adopts a two-step hydrothermal synthesis method, the active component is doped in the beta molecular sieve framework, the preparation method is simple, the period is short, the stability is good, the environment-friendly effect is realized, the pollution is avoided, the corrosion to equipment is low, the catalytic activity for preparing methyl lactate by catalytically converting glucose is good, the yield is high, the methyl lactate is easy to separate and recover from reactants, the methyl lactate can be recycled, the cyclic stability is good, the glucose can be completely catalytically converted, and the yield of methyl lactate is up to 67%.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to these examples.
Example 1
Dispersing 3g of H-beta molecular sieve in 90mL of 6mol/L nitric acid aqueous solution, stirring for 5 hours at 90 ℃, washing to be neutral by deionized water, and drying for 12 hours at 80 ℃ to obtain the dealuminized beta molecular sieve. Based on 100 percent of the mass of the carrier, according to the loading amount of Sn of 1.5 percent and the molar ratio of Sn to Fe of 1:1, 1.5g of dealuminated beta molecular sieve, 0.0541g (0.2mmol) of ferric chloride and 0.0700g (0.2mmol) of stannic chloride are added into 5g of tetraethylammonium hydroxide aqueous solution with the mass fraction of 25 percent, stirring for 6 hours at normal temperature, adding 0.5g of ammonium fluoride aqueous solution with the mass fraction of 35%, continuing stirring for 2 hours, then carrying out hydrothermal reaction for 24 hours at 150 ℃, cooling to normal temperature after the reaction is finished, adding 2.185g of hexadecyl trimethyl ammonium bromide, 0.485g of 25 percent tetramethyl ammonium hydroxide aqueous solution and 25g of deionized water, stirring for 3 hours at normal temperature, and carrying out hydrothermal reaction at 135 ℃ for 24 hours, carrying out suction filtration after the reaction is finished, washing with deionized water, drying at 100 ℃ for 12 hours, grinding, roasting at 550 ℃ for 6 hours, and grinding to obtain the solid acid catalyst.
Example 2
Based on 100% by mass of the carrier, 1.5g of a dealuminated beta molecular sieve, 0.0811g (0.3mmol) of ferric chloride, and 0.0700g (0.2mmol) of tin chloride were added to 5g of an aqueous 25% by mass tetraethylammonium hydroxide solution in a molar ratio of Sn to Fe of 1:1.5, and the other steps were the same as in example 1, to obtain a solid acid catalyst.
Example 3
Based on 100% by mass of the carrier, 1.5g of a dealuminated beta molecular sieve, 0.1082g of ferric chloride and 0.0700g of tin chloride were added to 5g of an aqueous 25% by mass tetraethylammonium hydroxide solution in a molar ratio of Sn to Fe of 1:2, in accordance with the loading amount of Sn of 1.5%, and the other steps were the same as in example 1, to obtain a solid acid catalyst.
Example 4
Based on 100% by mass of the carrier, 1.5g of dealuminated beta molecular sieve, 0.0879g of indium chloride and 0.0700g of tin chloride were added to 5g of 25% by mass aqueous tetraethylammonium hydroxide solution at a molar ratio of Sn to In of 1:1.5, In accordance with the loading amount of Sn of 1.5%, and the other steps were the same as In example 1, to obtain a solid acid catalyst.
Example 5
Based on 100% by mass of the carrier, 1.5g of a dealuminated beta molecular sieve, 0.0610g of magnesium chloride and 0.0700g of tin chloride were added to 5g of an aqueous 25% by mass tetraethylammonium hydroxide solution in a molar ratio of Sn to Mg of 1:1.5, in accordance with the loading amount of Sn of 1.5%, and the other steps were the same as in example 1, to obtain a solid acid catalyst.
Example 6
Based on 100% by mass of the carrier, 1.5g of a dealuminated beta molecular sieve, 0.0713g of nickel chloride and 0.0700g of tin chloride were added to 5g of an aqueous 25% by mass tetraethylammonium hydroxide solution in a molar ratio of Sn to Ni of 1:1.5, in accordance with the loading amount of Sn of 1.5%, and the other steps were the same as in example 1, to obtain a solid acid catalyst.
In order to prove the beneficial effects of the invention, the inventor uses the solid acid catalyst prepared in the embodiment 1-6 to catalytically convert glucose to prepare methyl lactate, and the specific method comprises the following steps:
adding 0.3g of glucose, 0.15g of solid acid catalyst and 24g of methanol into a high-pressure reaction kettle, introducing nitrogen to replace air in the high-pressure reaction kettle, repeating the steps for three times, introducing 2MPa of nitrogen at room temperature, heating to 220 ℃ under the condition of stirring at 500 revolutions per minute, reacting for 6 hours at constant temperature, centrifugally separating the catalyst after the reaction is finished, filtering the reaction solution by using a 0.22-micron organic filter membrane, and measuring the yield of methyl lactate by using gas chromatography, wherein the results are shown in table 1.
TABLE 1 yield of methyl lactate from the catalytic conversion of glucose with a solid acid catalyst according to the invention
| Catalyst and process for preparing same | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Methyl lactate yield | 67.0％ | 61.9％ | 60.3％ | 61.8％ | 62.5％ | 65.7％ |
As can be seen from Table 1, the solid acid catalyst of the present invention has good catalytic activity and high yield when used for preparing methyl lactate by catalytically converting glucose.
The inventors further tested the cycle stability of the solid acid catalyst prepared in example 1 according to the above method, and the experimental results are shown in table 2.
Table 2 example 1 effect of reusing solid acid catalyst for preparing methyl lactate by catalytically converting glucose
As can be seen from Table 2, the solid acid catalyst of the present invention can be recycled and has good cycle stability.
Claims (7)
1. A solid acid catalyst for preparing methyl lactate by catalytically converting glucose is characterized in that: the solid acid catalyst takes a dealuminized beta molecular sieve as a carrier, takes Sn as a first active component, takes any one of Fe, In, Mg and Ni as a second active component, and takes the mass of the carrier as 100%, the loading capacity of the first active component is 1.5-3%, and the molar ratio of the first active component to the second active component is 1: 1-2.5;
the preparation method of the solid acid catalyst comprises the following steps: dispersing the H-beta molecular sieve into a nitric acid aqueous solution with the concentration of 6mol/L according to the solid-to-liquid ratio of 1g: 25-40 mL, stirring for 2-8 hours at 50-100 ℃, washing with deionized water to be neutral, and drying at 50-120 ℃ to obtain a dealuminized beta molecular sieve; based on the mass of the carrier being 100%, dispersing the dealuminized beta molecular sieve, the soluble salt of the first active component and the soluble salt of the second active component in a tetraethylammonium hydroxide aqueous solution according to the loading amount of the first active component being 1.5-3%, the molar ratio of the first active component to the second active component being 1: 1-2.5, stirring at normal temperature for 3-8 hours, adding an ammonium fluoride aqueous solution, continuously stirring for 1-3 hours, performing a hydrothermal reaction at 100-200 ℃ for 12-48 hours, cooling to normal temperature after the reaction is finished, adding hexadecyl trimethyl ammonium bromide, a tetramethyl ammonium hydroxide aqueous solution and deionized water, stirring at normal temperature for 2-6 hours, performing a hydrothermal reaction at 100-200 ℃ for 12-48 hours, performing suction filtration, washing, drying, and roasting at 500-600 ℃ for 5-8 hours to obtain the solid acid catalyst.
2. The solid acid catalyst for preparing methyl lactate by catalytically converting glucose according to claim 1, wherein: the second active component is Fe, and the molar ratio of the first active component to the second active component is 1:1.
3. The solid acid catalyst for preparing methyl lactate by catalytically converting glucose according to claim 1, wherein: the second active component is any one of In, Mg and Ni, and the molar ratio of the first active component to the second active component is 1: 1.5.
4. The solid acid catalyst for preparing methyl lactate by catalytically converting glucose according to claim 1, wherein: dispersing the H-beta molecular sieve in a nitric acid aqueous solution with the concentration of 6mol/L according to the solid-to-liquid ratio of 1g:30mL, stirring for 5-6 hours at 80-90 ℃, washing with deionized water to be neutral, and drying at 80-100 ℃ to obtain a dealuminized beta molecular sieve; based on the mass of the carrier as 100%, dispersing the dealuminized beta molecular sieve, soluble salt of the first active component and soluble salt of the second active component in tetraethylammonium hydroxide aqueous solution according to the loading amount of the first active component being 1.5-3%, the molar ratio of the first active component to the second active component being 1: 1-2.5, stirring at normal temperature for 5-6 hours, adding ammonium fluoride aqueous solution, continuing stirring for 2 hours, carrying out hydrothermal reaction at 140-160 ℃ for 24 hours, cooling to normal temperature after the reaction is finished, adding hexadecyl trimethyl ammonium bromide, tetramethyl ammonium hydroxide aqueous solution and deionized water, stirring at normal temperature for 3-4 hours, carrying out hydrothermal reaction at 130-140 ℃ for 24 hours, carrying out suction filtration after the reaction is finished, washing, drying, and roasting at 550 ℃ for 6 hours to obtain the solid acid catalyst.
5. The solid acid catalyst for preparing methyl lactate by catalytically converting glucose according to claim 1, wherein: the mass ratio of the dealuminized beta molecular sieve to tetraethyl ammonium hydroxide aqueous solution, ammonium fluoride aqueous solution, hexadecyl trimethyl ammonium bromide, tetramethyl ammonium hydroxide aqueous solution and deionized water is 1: 3-4: 0.3-0.4: 1-2: 0.3-0.4: 15-20, wherein the mass fractions of the tetraethyl ammonium hydroxide aqueous solution and the tetramethyl ammonium hydroxide aqueous solution are both 25%, and the mass fraction of the ammonium fluoride aqueous solution is 30-40%.
6. The solid acid catalyst for preparing methyl lactate by catalytically converting glucose according to claim 1, wherein: the soluble salt of the first active component is tin chloride or tin nitrate.
7. The solid acid catalyst for preparing methyl lactate by catalytically converting glucose according to claim 1, wherein: the soluble salt of the second active component is any one of ferric chloride, indium chloride, magnesium chloride and nickel chloride.
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