NL2024497B1 - Molybdenum-boron/sepiolite catalyst, and preparation method and application thereof - Google Patents

Molybdenum-boron/sepiolite catalyst, and preparation method and application thereof Download PDF

Info

Publication number
NL2024497B1
NL2024497B1 NL2024497A NL2024497A NL2024497B1 NL 2024497 B1 NL2024497 B1 NL 2024497B1 NL 2024497 A NL2024497 A NL 2024497A NL 2024497 A NL2024497 A NL 2024497A NL 2024497 B1 NL2024497 B1 NL 2024497B1
Authority
NL
Netherlands
Prior art keywords
sepiolite
boron
molybdenum
catalyst
lignin
Prior art date
Application number
NL2024497A
Other languages
Dutch (nl)
Inventor
Wang Yishuang
Chen Mingqiang
Yang Zhonglian
Tang Zhiyuan
Wang Chunsheng
Zhang Han
Wang Jun
Original Assignee
Univ Anhui Sci & Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Univ Anhui Sci & Technology filed Critical Univ Anhui Sci & Technology
Application granted granted Critical
Publication of NL2024497B1 publication Critical patent/NL2024497B1/en

Links

Classifications

    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • 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
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention discloses a molybdenum-boron/sepiolite catalyst, and a preparation method and application thereof. The molybdenum-boron/sepiolite catalyst includes sepiolite used as a carrier and molybdenum and boron loaded on the sepiolite and used as active ingredients. The molybdenum-boron/sepiolite catalyst provided by the present invention has the advantages that sources of a raw material of the sepiolite are wide, the cost is low, green and environment-friendly effects are achieved, depolymerization cost can be effectively reduced, and the molybdenum-boron/sepiolite catalyst is suitable for large-scale industrial application. The molybdenum-boron/sepiolite catalyst provided by the present invention cooperates with a supercritical system, and has a high depolymerized lignin conversion rate and high selectivity on substituted phenol and carboxylic acid compounds. Additionally, the catalyst can be recycled for 50 times and above.

Description

MOLYBDENUM-BORON/SEPIOLITE CATALYST, AND
PREPARATION METHOD AND APPLICATION THEREOF
BACKGROUND
Technical Field
The present invention relates to the technical field of catalyst and lignin depolymerization, in particular to a molybdenum-boron/sepiolite catalyst, and a preparation method and application thereof.
Related Art
Lignin is a rich-content low-price renewable resource using aromatic rings as a major structure. The lignin is a complicated macromolecular compound mainly existing in plant wooden parts, its dry weight accounts for 20% to 35% of biomass, and the contained energy reaches 40% and more, so that the energy utilization efficiency of the biomass is directly influenced by conversion and utilization of the lignin. The content of the lignin in nature is rich, the sources are wide, nearly 50 million tons of industrial lignin is extracted from cooking waste liquor in a pulp and paper industry every day, a small part is used as additives of building materials, a large part is used as cheap fuel to be burnt or is directly discharged, which causes resource waste and environmental pollution. If the lignin is used for preparing monophenol high-added-value fine chemicals and high-grade biofuel such as aromatic hydrocarbon and alkane through catalytic depolymerization, a production process using fossil fuel as a raw material can be partially replaced, and it is an important part for all-component efficient comprehensive utilization of biomass resources.
At present, lignin catalytic depolymerization methods mainly include chemical methods and biological methods. The chemical methods mainly include methods of catalytic thermal cracking, catalytic hydrogenolysis and biological enzymolysis, etc. The catalytic thermal cracking faces main problems that depolymerization products are very complicated, that distillation purification is difficult to realize, and that the products have a high oxygen content and great viscosity, and cannot be directly applied to energy terminal customers as fuel. In a catalytic hydrogenolysis process, noble metal carbon carriers are used, the cost of catalysts is high, acidic and alkaline active sites are not enough, and a depolymerization production rate is low. According to the biological method, a biological enzyme is used as a catalyst to realize lignin depolymerization, but the depolymerization speed is low, the time consumption is long, the cost of the catalysts is high, and inactivation easily occurs, so that it is difficult for the biological method to adapt to large-scale industrial application of the lignin.
SUMMARY
The technical problem to be solved by the present invention is to provide a low-cost molybdenum-boron/sepiolite catalyst capable of being used for efficient catalytic depolymerization of lignin into micromolecular compounds, and a preparation method and application thereof
In order to solve the technical problems, the present invention uses the following technical scheme that the molybdenum-boron/sepiolite catalyst includes sepiolite used as a carrier and molybdenum and boron loaded on the sepiolite and used as active ingredients.
Further, a content of the molybdenum is 5 to 20 wt.%, a content of the boron is 1 to 10 wt.%, and the balance is the sepiolite. In an implementation process of the present invention, the inventor discovers that the catalytic depolymerization efficiency of the obtained catalyst is higher if the content of the molybdenum and the content of the boron are in the above-mentioned ranges.
The preparation method of the molybdenum-boron/sepiolite catalyst includes the following steps of:
(1) sequentially performing calcination treatment, acidification treatment and roasting treatment on sepiolite clay to obtain purified sepiolite;
(2) taking and dissolving precursor salts of the molybdenum and precursor salts of the boron into deionized water to form a solution I, adding the purified sepiolite into the solution I, and forming turbid liquid II after heating stirring treatment; and (3) sequentially performing sealing aging treatment, drying treatment and calcination treatment on the turbid liquid II to prepare the molybdenum-boron/sepiolite catalyst.
Further, in Step (1), the calcination treatment should be performed at 300 to 500 °C in air atmosphere; and 5 to 10 mol/L inorganic acid is used in the acidification treatment. In the implementation process of the present invention, the inventor discovers that the use of the above-mentioned conditions is favorable for molybdenum and boron loading, and the repeated utilization rate of the obtained catalyst is higher.
Further, the inorganic acid is any one of hydrochloric acid, nitric acid or sulfuric acid.
Further, the precursor salts of the molybdenum are any one or a mixture obtained by mixing two and more of ammonium molybdate tetrahydrate, ammonium molybdate heptahydrate, calcium molybdate and sodium molybdate according to any proportion. The precursor salts of the boron are any one or a mixture obtained by mixing two and more of boric acid, sodium tetraborate, sodium metaborate, sodium perborate and zinc borate according to any proportion.
Further, the sealing aging treatment includes a concrete process of evaporating the turbid liquid II to a slurry state and then performing treatment for 48 to 72 h at a temperature of 55 to 65 °C. In the implementation process of the present invention, the inventor discovers that the use of the above-mentioned conditions is favorable for molybdenum and boron loading, and the repeated utilization rate of the obtained catalyst is higher.
Further, the drying treatment includes a concrete process of firstly putting materials in a metal bath to be dried by distillation at a temperature of 60 to 95 °C and then putting the materials into a vacuum drying box to be dried for 12 to 36 h. In the implementation process of the present invention, the inventor discovers that the use of the above-mentioned conditions is favorable for molybdenum and boron loading, and the repeated utilization rate of the obtained catalyst is higher.
Further, in Step (3), the calcination treatment includes a concrete process of raising the temperature to 300 to 550 °C at a temperature rise speed of 0.5 to 2.5 °C/min in air atmosphere and performing treatment for 2 to 6 h. In the implementation process of the present invention, the inventor discovers that the use of the above-mentioned conditions is favorable for molybdenum and boron loading, and the repeated utilization rate of the obtained catalyst is higher.
The application of the molybdenum-boron/sepiolite catalyst provided by the present invention is application in catalytic depolymerization of the lignin. Based on the application, the present invention provides a lignin catalytic depolymerization method which includes the steps of putting the lignin and the molybdenum-boron/sepiolite catalyst into a supercritical lower alcohol system and performing a depolymerization reaction.
Lower alcohol contains 1 to 4 carbons. In the implementation process of the present invention, the inventor discovers that by using this kind of alcohol, available comprehensive effects of functions used as a solvent and a hydrogen donor are better.
The lignin is any one of or a mixture obtained by mixing two and more of alkali lignin, sulfate lignin, log lignin, lignosulfonate and bamboo lignin according to any proportion.
Further, the supercritical lower alcohol system is provided by a high-pressure reaction kettle, the pressure is 6.5 to 9.5 MPa, and the temperature is 250 to 320 °C. In the implementation process of the present invention, the inventor discovers that by using the above-mentioned conditions, the catalytic depolymerization efficiency and the energy utilization rate are higher.
Further, the catalytic depolymerization of the lignin includes concrete operations of putting the lignin and the molybdenum-boron/sepiolite catalyst into the high-pressure reaction kettle, then adding absolute ethyl alcohol into the high-pressure reaction kettle, next inflating the high-pressure reaction kettle with 0.3 to 0.8 MPa high-purity nitrogen, firstly performing uniform stirring before reaction, then raising the temperature from a normal temperature to 250 to 310 °C at a temperature rise speed of 2 to 7 °C/min, and performing a reaction for 2 to 6 h at the temperature.
The present invention has the following beneficial effects that:
1. for the molybdenum-boron/sepiolite catalyst, the sources of the raw material of the sepiolite are wide, the cost is low, green and environment-friendly effects are achieved, the depolymerization cost can be effectively reduced, and the molybdenum-boron/sepiolite catalyst is suitable for large-scale industrial application; additionally, the molybdenum-boron/sepiolite catalyst provided by the present invention cooperates with a supercritical system, has a high depolymerized lignin conversion rate and high selectivity on substituted phenol and carboxylic acid compounds; and the catalyst can be recycled for 50 times and more;
2. workpieces in the preparation method of the molybdenum-boron/sepiolite catalyst provided by the present invention are simple, the implementation is easy, and very good application prospects are realized; and
3. according to a method of depolymerizing the lignin by the supercritical system and the catalyst in a cooperative way, the lignin is depolymerized in the absolute ethyl alcohol; the reaction conditions can be easily realized; advantages of low cost, simple operation, high application performance, green and environment-friendly effects, no pollution, etc. are realized; the method is applicable to large-scale industrial application; environmental pollution problems due to discharge of a great amount of papermaking waste liquid can be reduced; the efficient comprehensive utilization of the lignin is improved; and social benefits of sustainable development are realized.
DETAILED DESCRIPTION
The present invention will be further described with reference to embodiments hereafter.
Various raw materials used in following embodiments, unless otherwise specified, are all products sold in markets and well known in this field.
Embodiment 1
Preparation of a molybdenum-boron/sepiolite catalyst, and lignin depolymerization by a supercritical system and the molybdenum-boron/sepiolite catalyst in a cooperative way
A preparation method of the molybdenum-boron/sepiolite catalyst includes the following steps of:
calcining a sepiolite raw material for 4 h at 500 °C, then, taking and adding 10 g of the sepiolite raw material subjected to calcination treatment into 5 mol/L nitric acid, stirring and mixing while performing 60 °C water bath heating, performing suction filtration after uniform mixing, washing a filter cake obtained after suction filtration to a neutral state by deionized water, and drying to obtain a solid I; putting the solid I into a tubular furnace, heating the solid I to 500 °C at a temperature rise speed of 2 °C/min, then, roasting in air atmosphere for 4 h to obtain purified sepiolite; weighing and putting 2.2990 g of (NH4)6Mo7O24 4H2O and 3.1220 g of nitric acid into a 250 mL round bottomed flask, adding 100 mL of the deionized water, and forming a solution I after complete dissolution; weighing and adding 5.00 g of the purified sepiolite into the solution I, putting the solution I into a water bath pot to be subjected to constant temperature stirring for 24 h at 60 °C to form turbid liquid II; and next, raising the temperature of the turbid liquid II to 70 °C, slowly evaporating the turbid liquid II to a slurry state by a metal bath, then, sealing an opening, next, performing still standing and sealing aging on the turbid liquid II in the slurry state for 48 h at 60 °C, next, drying the turbid liquid II subjected to the sealing aging treatment through distillation in the metal bath at 60 °C to obtain a cake-shaped solid, finally drying the cake-shaped solid for 12 h at 105 °C, then, heating the cake-shaped solid to 500 °C at a temperature rise speed of 2 °C/min in the tubular furnace after drying, grinding and sieving, roasting in the air atmosphere for 4 h, and obtaining the molybdenum-boron/sepiolite catalyst with a molybdenum content being 20wt.% and a boron content being 10 wt.%.
A method of depolymerizing the lignin by the supercritical system and the molybdenum-boron/sepiolite catalyst in a cooperative way includes the following steps of:
putting 1.0122 g of alkali lignin and 0.5042 g of the molybdenum-boron/sepiolite catalyst into a 100 mL high-pressure reaction kettle, then, adding 30 mL of absolute ethyl alcohol into the high-pressure reaction kettle, next, inflating 0.5 MPa of high-purity nitrogen into the high-pressure reaction kettle, firstly stirring for 15 min at 620 rpm before reaction, then, raising the temperature from a normal temperature of 24 °C to 290 °C at a temperature rise speed of 6 °C/min, performing a reaction for 3 h at 290 °C, fast putting the high-pressure kettle into an ice-water bath for shock cooling after the reaction is completed, and completing lignin depolymerization.
A viscous product in the high-pressure reaction kettle is collected. Solid-liquid separation is performed through centrifugation suction filtration. A solid-phase product is added into a tetrahydrofuran solution, 100 °C ultrasonic dissolution is performed, solid-liquid separation is performed through filtration, a solid-phase substance is a catalyst, and the tetrahydrofuran solution is treated by a rotary vacuum evaporation method to obtain residue lignin. A liquid-phase product is extracted by ethyl acetate to obtain an oil-phase part, and a depolymerized product is finally obtained through rotary vacuum evaporation, and is subjected to GC-MS and GC qualitative and quantitative analysis. Through calculation, a lignin conversion rate can reach 57% or higher, and the selectivity of substituted phenol and carboxylic acid compounds exceeds 62%, where the selectivity of 4-(3-hydroxy phenyl)-4-oxobutyric acid exceeds 48%.
Embodiment 2
Preparation of a molybdenum -boron/sepiolite catalyst, and lignin depolymerization by a supercritical system and the molybdenum-boron/sepiolite catalyst in a cooperative way
A preparation method of the molybdenum-boron/sepiolite catalyst includes the following steps of:
calcining a sepiolite raw material for 4 h at 500 °C, then, taking and adding 10 g of the sepiolite raw material subjected to calcination treatment into 5 mol/L nitric acid, stirring and mixing while performing 60 °C water bath heating, performing suction filtration after uniform mixing, washing a filter cake obtained after suction filtration to a neutral state by deionized water, and then drying to obtain a solid I; putting the solid I into a tubular furnace, heating the solid I to 500 °C at a temperature rise speed of 3 °C/min, then, roasting in air atmosphere for 4 h to obtain purified sepiolite; weighing and putting 0.4840 g of (ΝΕΕ)όΜθ7θ24 ALLO and 0.3122 g of nitric acid into a 250 mL round bottomed flask, adding 100 mL of the deionized water, and forming a solution I after complete dissolution; weighing and adding 5.00 g of the purified sepiolite into the solution I; putting the solution I into a water bath pot to be subjected to constant temperature stirring for 24 h at 60 °C to form turbid liquid II; and next, raising a temperature of the turbid liquid II to 70 °C, slowly evaporating the turbid liquid II to a slurry state by a metal bath, then, sealing an opening, next, performing still standing and sealing aging on the turbid liquid II in the slurry state for 72 h at 55 °C, next, drying the turbid liquid II subjected to the sealing aging treatment through distillation in the metal bath at 95 °C to obtain a cake-shaped solid, finally drying the cake-shaped solid for 24 h at 105 °C, then, heating the cake-shaped solid to 500 °C at a temperature rise speed of 1 °C/min in the tubular furnace after drying, grinding and sieving, roasting in the air atmosphere for 5 h, and obtaining the molybdenum-boron/sepiolite catalyst with a molybdenum content being 5 wt.% and a boron content being 1 wt.%.
A method of depolymerizing the lignin by the supercritical system and the molybdenum-boron/sepiolite catalyst in a cooperative way includes the following steps of:
putting 1.0087 g of alkali lignin and 0.5123 g of the molybdenum-boron/sepiolite catalyst into a 100 mL high-pressure reaction kettle, then, adding 30 mL of absolute ethyl alcohol into the high-pressure reaction kettle, next, inflating 0.4 MPa of high-purity nitrogen into the high-pressure reaction kettle, firstly stirring for 15 min at 600 rpm before reaction, then, raising the temperature from a normal temperature of 28 °C to 250 °C at a temperature rise speed of 5 °C/min, performing a reaction for 6 h at 250 °C, fast putting the high-pressure kettle into an ice-water bath for shock cooling after the reaction is completed, and completing lignin depolymerization.
A viscous product in the high-pressure reaction kettle is collected. Solid-liquid separation is performed through centrifugation suction filtration. A solid-phase product is added into a tetrahydrofuran solution, 100 °C ultrasonic dissolution is performed, solid-liquid separation is performed through filtration, a solid-phase substance is a catalyst, and the tetrahydrofuran solution is treated by a rotary vacuum evaporation method to obtain residue lignin. A liquid-phase product is extracted by ethyl acetate to obtain an oil-phase part, and a depolymerized product is finally obtained through rotary vacuum evaporation, and is subjected to GC-MS and GC qualitative and quantitative analysis. Through calculation, a lignin conversion rate can reach 48% or higher, and the selectivity of substituted phenol and carboxylic acid compounds exceeds 40%, where the selectivity of 4-(3-hydroxy phenyl)-4-oxobutyric acid exceeds 38%.
Embodiment 3
Preparation of a molybdenum-boron/sepiolite catalyst, and lignin depolymerization by a supercritical system and the molybdenum-boron/sepiolite catalyst in a cooperative way
A preparation method of the molybdenum-boron/sepiolite catalyst includes the following steps of:
calcining a sepiolite raw material for 4 h at 500 °C, then, taking and adding 10 g of the sepiolite raw material subjected to calcination treatment into 5 mol/L nitric acid, stirring and mixing while performing 60 °C water bath heating, performing suction filtration after uniform mixing, washing a filter cake obtained after suction filtration to a neutral state by deionized water, and then drying to obtain a solid I; putting the solid I into a tubular furnace, heating the solid I to 500 °C at a temperature rise speed of 3 °C/min, then, roasting in air atmosphere for 4 h to obtain purified sepiolite; weighing and putting 0.6921 g of (NELjóMovChj'dEEO and 2.1854 g of nitric acid into a 250 mL round bottomed flask, adding 100 mL of the deionized water, and forming a solution I after complete dissolution; weighing and adding 5.00 g of the purified sepiolite into the solution I; putting the solution I into a water bath pot to be subjected to constant temperature stirring for 24 h at 60 °C to form turbid liquid II; and next, raising a temperature of the turbid liquid II to 70 °C, slowly evaporating the turbid liquid II to a slurry state by a metal bath, then, sealing an opening, next, performing still standing and sealing aging on the turbid liquid II in the slurry state for 48 h at 65 °C, next, drying the turbid liquid II subjected to the sealing aging treatment through distillation in the metal bath at 70 °C to obtain a cake-shaped solid, finally drying the cake-shaped solid for 36 h at 105 °C, then, heating the cake-shaped solid to 550 °C at a temperature rise speed of 2.5 °C/min in the tubular furnace after drying, grinding and sieving, roasting in the air atmosphere for 5 h, and obtaining the molybdenum-boron/sepiolite catalyst with a molybdenum content being 7 wt.% and a boron content being 7 wt.%.
A method of depolymerizing the lignin by the supercritical system and the molybdenum-boron/sepiolite catalyst in a cooperative way includes the following steps of:
putting 1.0176 g of alkali lignin and 0.5102 g of the molybdenum-boron/sepiolite catalyst into a 100 mL high-pressure reaction kettle, then, adding 30 mL of absolute ethyl alcohol into the high-pressure reaction kettle, next, inflating 0.3 MPa of high-purity nitrogen into the high-pressure reaction kettle, firstly stirring for 15 min at
608 rpm before reaction, then, raising the temperature from a normal temperature of 22 °C to 310 °C at a temperature rise speed of 7 °C/min, performing a reaction for 4 h at 310 °C, fast putting the high-pressure kettle into an ice-water bath for shock cooling after the reaction is completed, and completing lignin depolymerization.
A viscous product in the high-pressure reaction kettle is collected. Solid-liquid separation is performed through centrifugation suction filtration. A solid-phase product is added into a tetrahydrofuran solution, 100 °C ultrasonic dissolution is performed, solid-liquid separation is performed through filtration, a solid-phase substance is a catalyst, and the tetrahydrofuran solution is treated by a rotary vacuum evaporation method to obtain residue lignin. A liquid-phase product is extracted by ethyl acetate to obtain an oil-phase part, and a depolymerized product is finally obtained through rotary vacuum evaporation, and is subjected to GC-MS and GC qualitative and quantitative analysis. Through calculation, a lignin conversion rate can reach 59% or higher, and the selectivity of substituted phenol and carboxylic acid compounds exceeds 60%, where the selectivity of 4-(3-hydroxy phenyl)-4-oxobutyric acid exceeds 45%.
Embodiment 4
Preparation of a molybdenum-boron/sepiolite catalyst, and lignin depolymerization by a supercritical system and the molybdenum-boron/sepiolite catalyst in a cooperative way
A preparation method of the molybdenum-boron/sepiolite catalyst includes the following steps of calcining a sepiolite raw material for 4 h at 500 °C, then, taking and adding 10 g of the sepiolite raw material subjected to calcination treatment into 5 mol/L nitric acid, stirring and mixing while performing 60 °C water bath heating, performing suction filtration after uniform mixing, washing a filter cake obtained after suction filtration to a neutral state by deionized water, and then drying to obtain a solid I; putting the solid I into a tubular furnace, heating the solid I to 600 °C at a temperature rise speed of 4 °C/min, then, roasting in air atmosphere for 6 h to obtain purified sepiolite; weighing and putting 1.6230 g of (ΝΗΟόΜογΟίί 4H2O and 2.8298 g of nitric acid into a 250 mL round bottomed flask, adding 100 mL of the deionized water, and forming a solution I after complete dissolution; weighing and adding 5.00 g of the purified sepiolite into the solution I; putting the solution I into a water bath pot to be subjected to constant temperature stirring for 24 h at 60 °C to form turbid liquid II; and next, raising a temperature of the turbid liquid II to 70 °C, slowly evaporating the turbid liquid II to a ίο slurry state by a metal bath, then, sealing an opening, next, performing still standing and sealing aging on the turbid liquid II in the slurry state for 60 h at 58 °C, next, drying the turbid liquid II subjected to the sealing aging treatment through distillation in the metal bath at 80 °C to obtain a cake-shaped solid, finally drying the cake-shaped solid for 18 h at 105 °C, then, heating the cake-shaped solid to 300 °C at a temperature rise speed of 0.5 °C7min in the tubular furnace after drying, grinding and sieving, roasting in the air atmosphere for 2 h, and obtaining the molybdenum-boron/sepiolite catalyst with a molybdenum content being 15 wt.% and a boron content being 9 wt.%.
A method of depolymerizing the lignin by the supercritical system and the molybdenum-boron/sepiolite catalyst in a cooperative way includes the following steps of:
putting 1.0326 g of alkali lignin and 0.5101 g of the molybdenum-boron/sepiolite catalyst into a 100 mL high-pressure reaction kettle, then, adding 30 mb of absolute ethyl alcohol into the high-pressure reaction kettle, next, inflating 0.8 MPa of high-purity nitrogen into the high-pressure reaction kettle, firstly stirring for 15 min at 610 rpm before reaction, then, raising the temperature from a normal temperature of 26 °C to 270 °C at a temperature rise speed of 2 °C/min, performing a reaction for 5 h at 270 °C, fast putting the high-pressure kettle into an ice-water bath for shock cooling after the reaction is completed, and completing lignin depolymerization.
A viscous product in the high-pressure reaction kettle is collected. Solid-liquid separation is performed through centrifugation suction filtration. A solid-phase product is added into a tetrahydrofuran solution, 100 °C ultrasonic dissolution is performed, solid-liquid separation is performed through filtration, a solid-phase substance is a catalyst, and the tetrahydrofuran solution is treated by a rotary vacuum evaporation method to obtain residue lignin. A liquid-phase product is extracted by ethyl acetate to obtain an oil-phase part, and a depolymerized product is finally obtained through rotary vacuum evaporation, and is subjected to GC-MS and GC qualitative and quantitative analysis. Through calculation, a lignin conversion rate can reach 53% or higher, and the selectivity of substituted phenol and carboxylic acid compounds exceeds 61%, where the selectivity of 4-(3-hydroxy phenyl)-4-oxobutyric acid exceeds 51%.
Embodiment 5
Preparation of a molybdenum-boron/sepiolite catalyst, and lignin depolymerization by a supercritical system and the molybdenum-boron/sepiolite catalyst in a cooperative way
A preparation method of the molybdenum-boron/sepiolite catalyst includes the following steps of:
calcining a sepiolite raw material for 4 h at 500 °C, then, taking and adding 10 g of the sepiolite raw material subjected to calcination treatment into 5 mol/L nitric acid, stirring and mixing while performing 60 °C water bath heating, performing suction filtration after uniform mixing, washing a filter cake obtained after suction filtration to a neutral state by deionized water, and then drying to obtain a solid I; putting the solid I into a tubular furnace, heating the solid I to 600 °C at a temperature rise speed of 1 °C/min, then, roasting in air atmosphere for 4 h to obtain purified sepiolite; weighing and putting 0.6921 g of (ΝΗΟόΜογΟιτ 4H2O and 0.9366 g of nitric acid into a 250 mL round bottomed flask, adding 100 mL of the deionized water, and forming a solution I after complete dissolution; weighing and adding 5.00 g of the purified sepiolite into the solution I; putting the solution I into a water bath pot to be subjected to constant temperature stirring for 24 h at 60 °C to form turbid liquid II; and next, raising a temperature of the turbid liquid II to 70 °C, slowly evaporating the turbid liquid II to a slurry state by a metal bath, then, sealing an opening, next, performing still standing and sealing aging on the turbid liquid II in the slurry state for 66 h at 62 °C, next, drying the turbid liquid II subjected to the sealing aging treatment through distillation in the metal bath at 90 °C to obtain a cake-shaped solid, finally drying the cake-shaped solid for 30 h at 105 °C, then, heating the cake-shaped solid to 500 °C at a temperature rise speed of 1.5 °C/min in the tubular furnace after drying, grinding and sieving, roasting in the air atmosphere for 3 h, and obtaining the molybdenum-boron/sepiolite catalyst with a molybdenum content being 7 wt.% and a boron content being 3 wt.%.
A method of depolymerizing the lignin by the supercritical system and the molybdenum-boron/sepiolite catalyst in a cooperative way includes the following steps of:
putting 1.0458 g of alkali lignin and 0.5011 g of the molybdenum-boron/sepiolite catalyst into a 100 mL high-pressure reaction kettle, then, adding 30 mL of absolute ethyl alcohol into the high-pressure reaction kettle, next, inflating 0.4 MPa of high-purity nitrogen into the high-pressure reaction kettle, firstly stirring for 15 min at 608 rpm before reaction, then, raising the temperature from a normal temperature of 20 °C to 290 °C at a temperature rise speed of 6 °C/min, performing a reaction for 2 h at 290 °C, fast putting the high-pressure kettle into an ice-water bath for shock cooling after the reaction is completed, and completing lignin depolymerization.
A viscous product in the high-pressure reaction kettle is collected. Solid-liquid separation is performed through centrifugation suction fdtration. A solid-phase product is added into a tetrahydrofuran solution, 100 °C ultrasonic dissolution is performed, solid-liquid separation is performed through filtration, a solid-phase substance is a catalyst, and the tetrahydrofuran solution is treated by a rotary vacuum evaporation method to obtain residue lignin. A liquid-phase product is extracted by ethyl acetate to obtain an oil-phase part, and a depolymerized product is finally obtained through rotary vacuum evaporation, and is subjected to GC-MS and GC qualitative and quantitative analysis. Through calculation, a lignin conversion rate can reach 58% or higher, and the selectivity of substituted phenol and carboxylic acid compounds exceeds 63%, where the selectivity of 4-(3-hydroxy phenyl)-4-oxobutyric acid exceeds 51%.
Based on the above, the depolymerized lignin conversion rate is high, and can reach 55% or higher, and the selectivity of the substituted phenol and carboxylic acid compounds exceeds 60%, where the selectivity of 4-(3-hydroxy phenyl)-4-oxobutyric acid exceeds 40%. The product can be easily separated and can partially replace fossil fuel. The environmental pollution problems due to discharge of a great amount of papermaking waste liquid can be reduced, the efficient comprehensive utilization of the lignin is improved, and social benefits of sustainable development are realized.
It should also be understood that examples and embodiments according to the present invention are only used for illustration, and are not intended to limit the present invention. Those in the art can make various modifications or changes according to the present invention. All modifications, equivalent replacement, improvement, etc. made within the spirit and the principle of the present invention shall be included in the protection scope of the present invention.

Claims (2)

CONCLUSIESCONCLUSIONS 1. Een molybdenum-boor/sepioliet katalysator, omvattende sepioliet als drager, en molybdenum en boor op het sepioliet als actieve componenten.A molybdenum boron / sepiolite catalyst, comprising sepiolite as a support, and molybdenum and boron on the sepiolite as active components. 2. De molybdenum-boor/sepioliet katalysator volgens conclusie 1, met het kenmerk, dat een gehalte molybdenum 5-20 gewichtsprocent is, een gehalte boor 1 -The molybdenum boron / sepiolite catalyst according to claim 1, characterized in that a molybdenum content is 5-20% by weight, a content of boron 1 - 10 gewichtsprocent is, en de rest sepioliet is.Is 10 weight percent, and the rest is sepiolite. 3. Een werkwijze voor het vormen van de molybdenum-boor/sepioliet katalysator volgens conclusies 1 of 2, omvattende de stappen:A method of forming the molybdenum boron / sepiolite catalyst according to claims 1 or 2, comprising the steps of: (1) achtereenvolgens uitvoeren van calcinatie behandeling, aangezuring en roosteren van sepioliet klei om gezuiverd sepioliet te verkrijgen;(1) sequentially conducting calcination treatment, acidification and roasting of sepiolite clay to obtain purified sepiolite; (2) oplossen van precursor zouten van molybdenum en precursor zouten van boor in gedeïoniseerd water onder vorming van een oplossing I, toevoegen van het gezuiverde sepioliet aan de oplossing I, en vormen van een troebele vloeistof II na verwarmen en roeren, en (3) het vervolgens afgesloten rusten, drogen en calcineren van de troebele vloeistof(2) dissolving molybdenum precursor salts and boron precursor salts in deionized water to form solution I, adding the purified sepiolite to solution I, and forming a cloudy liquid II after heating and stirring, and (3) subsequently resting, drying and calcining the cloudy liquid 11 voor bereiding van de molybdenum-boor/sepioliet katalysator.11 for preparing the molybdenum boron / sepiolite catalyst. 4. De werkwijze volgens conclusie 3, waarbij de precursor zouten van molybdenum een of een mengsel van twee of meer is van ammoniummolybdaat tetrahydraat, ammoniummolybdaat heptahydraat, calciummolybdaat of natriummolybdaat, in willekeurige verhouding;The method of claim 3, wherein the precursor salts of molybdenum is one or a mixture of two or more of ammonium molybdate tetrahydrate, ammonium molybdate heptahydrate, calcium molybdate or sodium molybdate, in any proportion; de precursor zouten van boor een of een mengsel van twee of meer is van boorzuur, natriumtetraboraat, natriummetaboraat, natriumperboraat of zinkboraat, in willekeurige verhouding.the precursor salts of boron is one or a mixture of two or more of boric acid, sodium tetraborate, sodium metaborate, sodium perborate or zinc borate, in any proportion. 5. De werkwijze volgens conclusie 3, waarbij het afgesloten rusten een proces omvat van verdampen van de troebele vloeistof II tot een slurry en daarna behandelen bij 55 - 65°C gedurende 48-72 uur.The method of claim 3, wherein the sealed rest comprises a process of evaporating the cloudy liquid II into a slurry and then treating at 55-65 ° C for 48-72 hours. 6. De werkwijze volgens conclusie 3, waarbij het droogproces een proces omvat van het eerst in een metaalbad brengen van materialen voor drogen door destillatie bij een temperatuur van 60 - 95°C en de materialen daarna gedurende 12 - 36 uur in een vacuüm droogoven brengen voor drogen.The method of claim 3, wherein the drying process comprises a process of first bringing metal materials for drying by distillation at a temperature of 60 - 95 ° C into a metal bath and then placing the materials in a vacuum drying oven for 12 - 36 hours. for drying. 7. De werkwijze volgens conclusie 3, waarbij in stap (3) het calcineren een proces omvat van verhogen van de temperatuur tot 300 - 550°C bij een temperatuurstijging van The method of claim 3, wherein in step (3) the calcination comprises a process of raising the temperature to 300-550 ° C at a temperature rise of 0,5 - 2,5°C /min in een lucht atmosfeer en het uitvoeren van behandeling gedurende 2 6 uur.0.5 - 2.5 ° C / min in an air atmosphere and carry out treatment for 2 6 hours. 8. Toepassing van de molybdaat-boor/sepioliet katalysator volgens conclusie 1 of 2, voor het katalytisch depolymeriseren van lignine.Use of the molybdate boron / sepiolite catalyst according to claim 1 or 2 for the catalytic depolymerization of lignin. 5 9. Een werkwijze voor het katalytisch depolymeriseren van lignine, omvattende de volgende stappen: het brengen van lignine en de molybdenum-boor/sepioliet katalysator volgens conclusie 1 of 2 in een superkritisch lager alcohol systeem en uitvoeren van de depolymerisatie reactie.9. A method of catalytic depolymerizing lignin, comprising the following steps: introducing lignin and the molybdenum boron / sepiolite catalyst of claim 1 or 2 into a supercritical lower alcohol system and performing the depolymerization reaction. 10. De werkwijze voor het katalytisch depolymeriseren van lignine volgens 10 conclusie 9, waarbij het superkritisch lager alcohol systeem verschaft middels een hoge-druk reactievat, de druk 6,5 - 9,5MPa is en de temperatuur 250 - 320°C is.The method of catalytic depolymerization of lignin according to claim 9, wherein the supercritical lower alcohol system is provided by a high pressure reaction vessel, the pressure is 6.5-9.5MPa and the temperature is 250-320 ° C.
NL2024497A 2018-12-21 2019-12-18 Molybdenum-boron/sepiolite catalyst, and preparation method and application thereof NL2024497B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811570730.XA CN109675550B (en) 2018-12-21 2018-12-21 Molybdenum-boron/sepiolite catalyst and preparation method and application thereof

Publications (1)

Publication Number Publication Date
NL2024497B1 true NL2024497B1 (en) 2020-05-07

Family

ID=66188755

Family Applications (1)

Application Number Title Priority Date Filing Date
NL2024497A NL2024497B1 (en) 2018-12-21 2019-12-18 Molybdenum-boron/sepiolite catalyst, and preparation method and application thereof

Country Status (2)

Country Link
CN (1) CN109675550B (en)
NL (1) NL2024497B1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112191254B (en) * 2020-08-27 2022-12-02 安徽理工大学 Catalyst and method for preparing 2-ethoxyphenol by catalytic depolymerization of lignin
CN113004122B (en) * 2021-03-16 2023-05-09 安徽理工大学 Method for preparing 2, 5-dimethylphenol by lignin selective catalytic conversion
CN115318287B (en) * 2021-12-16 2024-03-19 中国科学院大连化学物理研究所 Catalyst for preparing styrene by toluene side chain alkylation and preparation method and application thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2008281299B2 (en) * 2007-07-27 2013-09-19 Ignite Resources Pty Limited Process and apparatus for converting organic matter into a product
CN106699517A (en) * 2016-11-17 2017-05-24 浙江理工大学 Method for preparing bio-based monophenol chemical product from alkali lignin and subcritical/supercritical ethanol
CN107597097B (en) * 2017-09-04 2020-07-24 北京林业大学 Preparation method and application of supported molybdenum oxide catalyst
CN108043407A (en) * 2017-12-19 2018-05-18 安徽理工大学 A kind of Co/ sepiolites catalyst and its preparation method and application

Also Published As

Publication number Publication date
CN109675550A (en) 2019-04-26
CN109675550B (en) 2021-10-26

Similar Documents

Publication Publication Date Title
NL2024497B1 (en) Molybdenum-boron/sepiolite catalyst, and preparation method and application thereof
CN107099314B (en) A method of long chain fatty acids and nitrating carbon are prepared using agriculture and forestry organic waste material
CN103910903B (en) Application of the catalyst with base of molybdenum in organic chemicals are produced by lignin
CN105461758B (en) A method of improving lignite humic acid extract content
JP2021524869A (en) Comprehensive usage for fiber-based biomass
CN107840783B (en) Method for catalytic depolymerization of biomass by molybdenum oxide catalyst
CN108043407A (en) A kind of Co/ sepiolites catalyst and its preparation method and application
CN110586131A (en) Preparation method of sulfonated coconut shell activated carbon solid acid catalyst
CN102417937A (en) Method for preparing reducing sugar by catalytically hydrolyzing cellulose
CN114272932B (en) Nickel-cerium biochar catalyst and preparation method and application thereof
CN103484158B (en) Method for preparing chemicals containing phenols and aromatic hydrocarbons from bio-oil pyrolysis lignin through catalysis
CN107286006B (en) Method for preparing vanillone and acetosyringone by catalytic alcoholysis of lignin
CN107090303B (en) Prepared by overcritical mixed solvent liquefaction lignin is rich in aromatic compound bio oil method
CN112899067A (en) Method for increasing sugar content in biological oil
CN108085039A (en) A kind of method that biomass by hydro-thermal liquefaction bio oil is modified
CN105622419A (en) Method for preparing from glycolic acid ester from carbohydrate
CN109628128B (en) CO (carbon monoxide)2Method for preparing furfural by hydrothermal liquefaction of agricultural and forestry waste under atmosphere
CN116283846A (en) Method for high-valued agricultural residues by ternary deep eutectic solvent system
CN104829072A (en) Method for preparing energy gas through direct catalysis gasification of sludge by metal-based catalyst in supercritical water
CN115106111B (en) Molybdenum carbide particle size dependent nitrogen-doped carbon material catalyst and preparation method and application thereof
CN113308265A (en) Method for preparing biological crude oil by catalytic conversion method
CN104327875A (en) Method for efficiently preparing biological oil by liquefying with water-hydrogen donor mixed solvent
CN115282957B (en) Hydrogenation reaction method for catalytic levulinic acid by using alkali lignin-based carbon loaded ruthenium
CN115466627B (en) Method for alcoholysis hydrogenation treatment of papermaking black liquor lignin
CN113831372B (en) Method for quickly extracting waste biomass lignin and recycling waste biomass lignin by microwave method

Legal Events

Date Code Title Description
MM Lapsed because of non-payment of the annual fee

Effective date: 20230101