Regeneration method of biomass ethylene glycol refining catalyst and biomass ethylene glycol hydrofining method

Abstract

The invention discloses a regeneration method of a biomass ethylene glycol refining catalyst and a biomass ethylene glycol hydrofining method.The regeneration method comprises the following steps that S1, the inactivated biomass ethylene glycol refining catalyst is placed in a solution containing inorganic acid, a chelating agent and a solvent to be aged, and an aged catalyst is obtained; s2, washing the aged catalyst with water, and drying in an inactive atmosphere to obtain a dried catalyst; and S3, reducing the dried catalyst to obtain the regenerated biomass ethylene glycol refining catalyst. According to the catalyst prepared by the method disclosed by the invention, the ultraviolet light transmittance of a biomass ethylene glycol product can be obviously improved, and the service life of the catalyst is obviously prolonged.

Description

Technical Field

[0001] The present application relates to a method for regenerating a biomass ethylene glycol refining catalyst and a method for hydrogenating and refining biomass ethylene glycol, and belongs to the technical field of bioenergy chemical industry. Background Art

[0002] Ethylene glycol is an important bulk chemical, mainly used in the production of synthetic polyester, polyester, polyester resin, desiccant, plasticizer, surfactant, etc., with an annual global consumption of more than 30 million tons. Traditional routes for producing ethylene glycol include the ethylene-ethylene oxide hydration method using petroleum or natural gas as raw materials and the synthesis gas-oxalate hydrogenation method using coal as raw materials. In recent years, with the proposal of the dual-carbon strategic goals of "carbon peak and carbon neutrality", the development of a route for producing ethylene glycol through selective hydrogenolysis using biomass such as straw sugar and cellulose as raw materials has shown obvious competitiveness due to its rich raw material sources and good environmental protection characteristics.

[0003] The organic components of biomass raw materials are complex. The trace unsaturated aldehydes, ketones, esters, and carboxylic acids in the crude ethylene glycol reaction liquid are difficult to be completely separated from the ethylene glycol product by traditional distillation technology. The carbon-oxygen double bond structure in these molecules causes the product to have strong absorption in the ultraviolet light region of 220 to 350nm. The insufficient ultraviolet transmittance seriously affects the gloss, chroma, coloring, strength and other indicators of downstream polyester fibers, and cannot meet the requirements of the polyester industry.

[0004] The refining of biomass ethylene glycol includes two routes: physical adsorption and chemical catalysis. The physical adsorption method uses activated carbon, ion exchange resin, zeolite and other adsorbents to selectively adsorb impurities (CN114057547, CN106946654, CN102649704, US5770777), which not only has limited adsorption capacity but also inevitably produces a large amount of solid waste. In contrast, the chemical catalytic route uses a supported or skeleton-type refined catalyst containing nickel, cobalt, ruthenium, palladium, platinum, rhodium and other active components with catalytic hydrogenation functions to hydrogenate and remove unsaturated organic matter in biomass ethylene glycol under pressurized and heated conditions to improve the ultraviolet transmittance of the product (US4647705, CN104098439, CN107973699, CN107973700, CN107285997). However, due to complex factors such as carbon deposition, metal ion deposition, and irreversible adsorption of highly polar organic matter on the catalyst surface, the hydrogenation activity of refined catalysts gradually decreases, making it difficult to use them for a long life cycle. Summary of the invention

[0005] The purpose of the present invention is to provide a regeneration method and application of a biomass ethylene glycol refining catalyst. The method has the advantages of simple operation, economical and practical, wide applicability, good regeneration effect, etc.

[0006] According to one aspect of the present application, a method for regenerating a biomass ethylene glycol refining catalyst is provided, the regeneration method comprising the following steps:

[0007] S1: placing the deactivated biomass ethylene glycol refining catalyst in a solution containing an inorganic acid, a chelating agent, and a solvent for aging to obtain an aged catalyst;

[0008] S2: washing the aged catalyst with water, and drying it in an inactive atmosphere to obtain a dried catalyst;

[0009] S3: reducing the dried catalyst to obtain a regenerated biomass ethylene glycol refining catalyst.

[0010] Optionally, in step S1, the inorganic acid is selected from at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hypophosphorous acid, and phosphorous acid.

[0011] Optionally, the chelating agent is selected from at least one of ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, tartaric acid, potassium tartrate, citric acid, oxalic acid, and ethylenediaminetetrapropionic acid.

[0012] Optionally, the solvent is selected from at least one of water, methanol, ethanol, isopropanol, acetonitrile, acetone, dioxane and tetrahydrofuran.

[0013] Optionally, the deactivated biomass ethylene glycol refining catalyst is selected from at least one of a ruthenium carbon catalyst, a Raney nickel catalyst, a nickel silicon oxide catalyst, a palladium carbon catalyst, a ruthenium aluminum oxide catalyst, a nickel carbon catalyst, a platinum carbon catalyst, an iridium carbon catalyst, a rhodium carbon catalyst, a Raney iron catalyst, a Raney copper catalyst, a ruthenium silicon oxide catalyst, and a nickel aluminum oxide catalyst.

[0014] Optionally, in the solution, the concentration of the inorganic acid is 0.2-0.7 wt %.

[0015] Optionally, in the solution, the concentration of the inorganic acid is independently selected from any value of 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt% or a range between any two of the above values.

[0016] Optionally, in the solution, the concentration of the chelating agent is 0.4-8 wt %.

[0017] Optionally, in the solution, the concentration of the chelating agent is independently selected from any value among 0.4wt%, 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt% or a range between any two of the above.

[0018] Optionally, in step S1, the aging temperature is 60-170° C., the aging pressure is 0.1-3.5 MPa, and the aging time is 0.2-72 h.

[0019] Optionally, in step S1, the aging temperature is independently selected from any value of 60°C, 80°C, 100°C, 120°C, 140°C, 160°C, 170°C or a range between any two of the above values.

[0020] Optionally, the aging pressure is independently selected from any value among 0.1 MPa, 0.5 MPa, 1 MPa, 2 MPa, 3 MPa, 3.5 MPa or a range between any two of the above values.

[0021] Optionally, the aging time is independently selected from any value among 0.2h, 0.5h, 1h, 2h, 5h, 10h, 12h, 24h, 36h, 48h, 60h, 72h or a range between any two of the above.

[0022] Optionally, in step S2, the inert atmosphere is selected from at least one of nitrogen, argon and helium.

[0023] Optionally, the drying temperature is 80-130°C.

[0024] Optionally, the drying temperature is independently selected from any value of 80°C, 90°C, 100°C, 110°C, 120°C, 130°C or a range between any two of the above values.

[0025] Optionally, in step S3, the reduction is carried out in a reducing atmosphere, and the reducing atmosphere is selected from at least one of hydrogen, methane and ethane.

[0026] Optionally, the reduction temperature is 180-260° C., the reduction pressure is 0.1-2 MPa, and the reduction time is 0.6-12 h.

[0027] Optionally, the aging temperature is 80-120° C., the aging pressure is 0.12-3 MPa, and the aging time is 0.6-24 h.

[0028] Optionally, the reduction temperature is independently selected from any value of 180°C, 200°C, 220°C, 230°C, 240°C, 250°C, 260°C or a range between any two of the above values.

[0029] Optionally, the reduction pressure is independently selected from any value among 0.1 MPa, 0.5 MPa, 0.8 MPa, 1 MPa, 1.2 MPa, 1.5 MPa, 1.8 MPa, 2 MPa or a range between any two of the above values.

[0030] Optionally, the reduction time is independently selected from any value of 0.6h, 1h, 2h, 4h, 6h, 8h, 10h, 12h or a range between any two of the above.

[0031] According to another aspect of the present application, a regenerated biomass ethylene glycol refining catalyst prepared by the above-mentioned regeneration method is provided.

[0032] According to another aspect of the present application, a method for hydrogenating and refining biomass ethylene glycol is provided, the method comprising: contacting and reacting crude biomass ethylene glycol, hydrogen and a catalyst to obtain refined ethylene glycol;

[0033] The catalyst is selected from the above-mentioned regenerated biomass ethylene glycol refining catalyst.

[0034] Optionally, the volume space velocity of the hydrogen is 6000 to 120000 h -1 The mass space velocity of the crude biomass ethylene glycol is 0.2 to 7.5 h -1 .

[0035] Optionally, the volume space velocity of the hydrogen is independently selected from 6000h -1 、8000h -1 、10000h -1 、20000h -1 、40000h -1 、60000h -1 、80000h -1 、100000h -1 、120000h -1 Any value in or a range between any two of the above.

[0036] Optionally, the volume space velocity of the hydrogen is 8000 to 100000 h -1 The mass space velocity of the crude biomass ethylene glycol is 0.4 to 4 h -1 .

[0037] Optionally, the reaction temperature is 55-160° C.; the reaction pressure is 0.6-6.5 MPa.

[0038] Optionally, the reaction temperature is 65-120° C.; the reaction pressure is 2-5.5 MPa.

[0039] Optionally, the reaction temperature is independently selected from any value of 55°C, 60°C, 80°C, 100°C, 120°C, 140°C, 160°C or a range between any two of the above values.

[0040] Optionally, the reaction pressure is independently selected from any value among 0.6MPa, 0.8MPa, 1MPa, 1.5MPa, 2MPa, 3MPa, 4MPa, 5MPa, 6MPa, 6.5MPa or a range between any two of the above.

[0041] Optionally, the reaction is carried out in a fixed bed reactor.

[0042] As an optional implementation method, the present application is implemented through the following technical solutions:

[0043] A method for regenerating a biomass ethylene glycol refining catalyst, characterized in that it comprises the following steps:

[0044] a) placing the deactivated biomass ethylene glycol refining catalyst in a solution containing an inorganic acid and a chelating agent, and aging it for a certain time at a certain temperature and pressure;

[0045] b) washing the aged catalyst in step a) with deionized water, and then drying in an inert gas;

[0046] c) placing the catalyst dried in step b) in reducing gas at a certain temperature and pressure for a certain period of time to obtain a regenerated catalyst.

[0047] In the present application, the method for hydrogenating and refining biomass ethylene glycol, the reaction steps are:

[0048] The regenerated biomass ethylene glycol refining catalyst is filled in the middle of a fixed bed, the temperature is raised to a specified reaction temperature, hydrogen is introduced to a specified pressure, and raw material crude biomass ethylene glycol is pumped in at a certain hydrogen flow rate for hydrogenation refining reaction.

[0049] Optionally, the regenerated biomass ethylene glycol refining catalyst is tableted and granulated at a pressure of 2 to 10 MPa and a particle size of 20 to 80 meshes.

[0050] The ultraviolet transmittances of the refined ethylene glycol at 220nm, 275nm and 350nm are respectively more than 75%, 92% and 99%; the catalyst operates stably for more than 250h, and the bed pressure change is less than 0.1MPa.

[0051] The beneficial effects of this application include:

[0052] 1) The present application provides a method for regenerating a biomass ethylene glycol refining catalyst, and uses it for biomass ethylene glycol hydrogenation refining. The catalyst prepared by the method can significantly improve the ultraviolet transmittance of the biomass ethylene glycol product, and the service life of the catalyst is significantly extended.

[0053] 2) The regeneration method provided in the present application has little effect on the intrinsic structure of the catalyst, and therefore has good applicability to both precious metal / non-precious metal and supported / skeleton catalysts.

[0054] 3) The regeneration method provided in this application has simple steps and is easy to scale up. The product biomass ethylene glycol has high added value and a wide range of applications, and has good prospects for large-scale applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0055] Figure 1 The ultraviolet transmittance of the refined biomass ethylene glycol product obtained in Example 1 of the present application varies with the refining treatment time. DETAILED DESCRIPTION

[0056] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0057] Unless otherwise specified, the raw materials in the examples of this application were purchased through commercial channels.

[0058] This application uses Beijing Puxi General Instrument Tu-1901 UV spectrometer to perform UV transmittance testing.

[0059] Example 1

[0060] Weigh 150g of deactivated ruthenium carbon catalyst and place it in a closed stirred reactor, add 1.1g of phosphoric acid, 4g of disodium ethylenediaminetetraacetate, and 205g of deionized water. The closed reactor was heated to 110°C, the pressure reached 0.14MPa, and aged for 4h. The aged catalyst was rinsed with 1000mL of deionized water, then placed in an oven replaced with nitrogen, and dried at 120°C overnight. The dried catalyst was placed in a stainless steel reduction tube, hydrogen was introduced, the back pressure was 0.5MPa, the gas flow rate was 250mL / min, the temperature was raised to 180°C for 4h, and the regenerated refined catalyst was obtained after natural cooling.

[0061] The regenerated refined catalyst was granulated at a pressure of 8 MPa to a particle size of 20-40 mesh. 10 g of the granulated catalyst was placed in a fixed bed reactor, hydrogen was introduced, and the temperature was raised to 100°C after the pressure reached 3 MPa, and crude biomass ethylene glycol was pumped in for refining treatment, with an ethylene glycol space velocity of 1.5 h -1 , hydrogen volume space velocity is 10000h -1 .

[0062] Depend on Figure 1 It can be seen that the regenerated catalyst showed good stability during the 400-day long-cycle operation, and the ultraviolet transmittance of the ethylene glycol product always met the national standard for polyester grade.

[0063] Example 2

[0064] Weigh 80g of deactivated Raney nickel catalyst and place it in a closed stirred reactor, add 1.7g sulfuric acid, 8g potassium tartrate, and 350g deionized water. The closed reactor was heated to 80°C, the pressure reached 0.1MPa, and aged for 12h. The aged catalyst was rinsed with 3000mL of deionized water, then placed in an oven replaced with nitrogen, and dried at 120°C overnight. The dried catalyst was placed in a stainless steel reduction tube, hydrogen was introduced, the back pressure was 0.2MPa, the gas flow rate was 500mL / min, the temperature was raised to 200°C for 5h, and the regenerated refined catalyst was obtained after natural cooling.

[0065] The regenerated refined catalyst was granulated at a pressure of 10 MPa to a particle size of 20-40 mesh. 10 g of the granulated catalyst was placed in a fixed bed reactor, hydrogen was introduced, and the temperature was raised to 120°C after the pressure reached 5 MPa, and crude biomass ethylene glycol was pumped in for refining treatment, with an ethylene glycol space velocity of 2.5 h -1 , hydrogen volume space velocity is 15000h -1 .

[0066] Example 3

[0067] Weigh 100g of deactivated nickel silicon oxide catalyst and place it in a closed stirred reactor, add 1.0g of hydrochloric acid, 2.1g of citric acid, and 300g of ethanol. The closed reactor was heated to 80°C, the pressure reached 0.15MPa, and aged for 4.5h. The aged catalyst was rinsed with 3000mL of deionized water, then placed in an oven replaced with helium, and dried at 100°C overnight. The dried catalyst was placed in a stainless steel reduction tube, hydrogen was introduced, the back pressure was 0.1MPa, the gas flow rate was 500mL / min, the temperature was raised to 220°C for 4h, and the regenerated refined catalyst was obtained after natural cooling.

[0068] The regenerated refined catalyst was granulated at a pressure of 4 MPa to a particle size of 40 to 80 mesh. 5 g of the granulated catalyst was placed in a fixed bed reactor, hydrogen was introduced, and the temperature was raised to 140°C after the pressure reached 2 MPa, and crude biomass ethylene glycol was pumped in for refining treatment, with an ethylene glycol space velocity of 4 h -1 , hydrogen volume space velocity is 90000h -1 .

[0069] Example 4

[0070] Weigh 25g of deactivated palladium carbon catalyst and place it in a closed stirred reactor, add 2.6g of phosphorous acid, 6g of ethylenediaminetetraacetic acid, and 350g of methanol. The closed reactor is heated to 120°C, the pressure reaches 0.5MPa, and aged for 2h. The aged catalyst is rinsed with 1500mL of deionized water, then placed in an oven replaced with nitrogen, and dried at 100°C overnight. The dried catalyst is placed in a stainless steel reduction tube, hydrogen is introduced, the back pressure is 0.1MPa, the gas flow rate is 200mL / min, the temperature is raised to 190°C for 5h, and the regenerated refined catalyst is obtained after natural cooling.

[0071] The regenerated refined catalyst was granulated at a pressure of 6 MPa to a particle size of 20-40 mesh. 10 g of the granulated catalyst was placed in a fixed bed reactor, hydrogen was introduced, and the temperature was raised to 120°C after the pressure reached 1 MPa, and crude biomass ethylene glycol was pumped in for refining treatment, with an ethylene glycol space velocity of 1.5 h -1 , hydrogen volume space velocity is 11000h -1 .

[0072] Example 5

[0073] Weigh 120g of deactivated ruthenium alumina catalyst and place it in a closed stirred reactor, add 1g of phosphoric acid, 4.5g of oxalic acid, and 100g of deionized water. The closed reactor is heated to 100°C, the pressure reaches 0.1MPa, and aged for 9h. The aged catalyst is rinsed with 1500mL of deionized water, then placed in a nitrogen-substituted oven and dried at 90°C overnight. The dried catalyst is placed in a stainless steel reduction tube, hydrogen is introduced, the back pressure is 0.6MPa, the gas flow rate is 300mL / min, the temperature is raised to 200°C for 1h, and the regenerated refined catalyst is obtained after natural cooling.

[0074] The regenerated refined catalyst was granulated at a pressure of 6 MPa to a particle size of 20-40 mesh. 10 g of the granulated catalyst was placed in a fixed bed reactor, hydrogen was introduced, and the temperature was raised to 100°C after the pressure reached 2 MPa, and crude biomass ethylene glycol was pumped in for refining treatment, with an ethylene glycol space velocity of 1 h -1 , hydrogen volume space velocity is 20000h -1 .

[0075] Test Example 1

[0076] The purified catalysts prepared in Examples 2 to 5 were tested for UV transmittance. The specific experimental results are shown in Table 1 below.

[0077] Table 1 UV transmittance of refined biomass ethylene glycol product after 50 and 100 days of operation in Example 2-5

[0078]

[0079] The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A method for regenerating a biomass ethylene glycol refining catalyst, characterized in that: The regeneration method comprises the following steps: S1: placing the deactivated biomass ethylene glycol refining catalyst in a solution containing an inorganic acid, a chelating agent, and a solvent for aging to obtain an aged catalyst; S2: washing the aged catalyst with water, and drying it in an inactive atmosphere to obtain a dried catalyst; S3: reducing the dried catalyst to obtain a regenerated biomass ethylene glycol refining catalyst.

2. The regeneration method according to claim 1, characterized in that: In step S1, the inorganic acid is selected from at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hypophosphorous acid, and phosphorous acid; Preferably, the chelating agent is selected from at least one of ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, tartaric acid, potassium tartrate, citric acid, oxalic acid, and ethylenediaminetetrapropionic acid; Preferably, the solvent is selected from at least one of water, methanol, ethanol, isopropanol, acetonitrile, acetone, dioxane, and tetrahydrofuran; Preferably, the deactivated biomass ethylene glycol refining catalyst is selected from at least one of a ruthenium carbon catalyst, a Raney nickel catalyst, a nickel silicon oxide catalyst, a palladium carbon catalyst, a ruthenium aluminum oxide catalyst, a nickel carbon catalyst, a platinum carbon catalyst, an iridium carbon catalyst, a rhodium carbon catalyst, a Raney iron catalyst, a Raney copper catalyst, a ruthenium silicon oxide catalyst, and a nickel aluminum oxide catalyst.

3. The regeneration method according to claim 1, characterized in that: In the solution, the concentration of the inorganic acid is 0.2-0.7 wt %; Preferably, in the solution, the concentration of the chelating agent is 0.4-8 wt %.

4. The regeneration method according to claim 1, characterized in that: In the step S1, the aging temperature is 60-170° C., the aging pressure is 0.1-3.5 MPa, and the aging time is 0.2-72 h; Preferably, the aging temperature is 80-120° C., the aging pressure is 0.12-3 MPa, and the aging time is 0.6-24 h.

5. The regeneration method according to claim 1, characterized in that: In step S2, the inert atmosphere is selected from at least one of nitrogen, argon and helium; Preferably, the drying temperature is 80-130°C.

6. The regeneration method according to claim 1, characterized in that: In step S3, the reduction is performed in a reducing atmosphere, and the reducing atmosphere is selected from at least one of hydrogen, methane, and ethane; Preferably, the reduction temperature is 180-260° C., the reduction pressure is 0.1-2 MPa, and the reduction time is 0.6-12 h.

7. A regenerated biomass ethylene glycol refining catalyst prepared by the regeneration method according to any one of claims 1 to 6.

8. A method for hydrogenating and refining biomass ethylene glycol, characterized in that: The method comprises: contacting and reacting crude biomass ethylene glycol, hydrogen and a catalyst to obtain refined ethylene glycol; The catalyst is selected from the regenerated biomass ethylene glycol purification catalyst described in claim 7.

9. The method according to claim 8, characterized in that The volume space velocity of the hydrogen is 6000~120000h -1 The mass space velocity of the crude biomass ethylene glycol is 0.2 to 7.5 h -1 ; Preferably, the volume space velocity of the hydrogen is 8000 to 100000 h -1 The mass space velocity of the crude biomass ethylene glycol is 0.4 to 4 h -1 .

10. The method according to claim 8, characterized in that The reaction temperature is 55-160°C; the reaction pressure is 0.6-6.5MPa; Preferably, the reaction temperature is 65-120°C; the reaction pressure is 2-5.5 MPa; Preferably, the reaction is carried out in a fixed bed reactor.

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