CN115518656A - Lignin-PVC carbon-based solid acid and preparation method and application thereof - Google Patents
Lignin-PVC carbon-based solid acid and preparation method and application thereof Download PDFInfo
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- CN115518656A CN115518656A CN202211310648.XA CN202211310648A CN115518656A CN 115518656 A CN115518656 A CN 115518656A CN 202211310648 A CN202211310648 A CN 202211310648A CN 115518656 A CN115518656 A CN 115518656A
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- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
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Abstract
The invention discloses lignin-PVC carbon-based solid acid and a preparation method and application thereof, and belongs to the technical field of preparation of solid acid catalysts. The invention takes biomass waste lignin and white pollutant polyvinyl chloride (PVC) as raw materials, and prepares the lignin-PVC carbon-based porous material under the activation of strong alkali potassium hydroxide. The method has the advantages that sulfonation conditions are mild, compared with the traditional high-temperature sulfonation by concentrated sulfuric acid, the method is safer and more environment-friendly, the total acidity of the obtained solid acid is higher, and the method accords with the concept of green environmental protection sustainable development.
Description
Technical Field
The invention belongs to the technical field of preparation of solid acid catalysts, and particularly relates to lignin-PVC carbon-based solid acid and a preparation method and application thereof.
Background
Furfural is the only important chemical raw material which is obtained by completely depending on biomass extraction at present. At present, furfural is industrially produced mainly by a homogeneous acid hydrolysis method, which has high catalytic efficiency, but due to the use of liquid acid, the catalyst cannot be recovered, and the corrosion to equipment is serious. The heterogeneous solid acid has the advantages of stability, small pollution, high yield, reusability and the like, and can solve the technical problems of the existing method, such as greenness and environmental protection, low acid amount on the surface of the prepared solid acid, easy loss of active sites, poor catalytic activity and the like, so that the heterogeneous solid acid has great potential of application in industrial production. Therefore, the development of a carbon-based solid acid with good stability and high active functional group content is important. Lignin is the world's most abundant and renewable biomass, a waste by-product or low value product of a biorefinery. Most of industrial reactions for preparing furan compounds by converting biomass saccharides (xylose, fructose, glucose and hemicellulose) are homogeneous acid catalysts, and although the conversion rate is high and the speed is high, the yield is low due to the fact that furan products are easy to polymerize; the corrosion resistance requirement on the reactor is high, and the cost is increased; the waste acid generated in the reaction is difficult to treat and has serious environmental pollution.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a lignin-PVC carbon-based solid acid and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a preparation method of lignin-PVC carbon-based solid acid, which comprises the following steps:
s1: mixing lignin, PVC and KOH, and then carrying out carbonization treatment to obtain a carbon-based material; sequentially carrying out ultrasonic treatment, washing treatment and drying treatment on the carbon-based material to obtain a pretreated carbon-based material;
s2: and sulfonating the pretreated carbon-based material by sulfanilic acid under the condition of oil bath, washing and drying to obtain the lignin-PVC carbon-based solid acid.
Further, in S1, the weight ratio of the lignin, the PVC and the KOH is 1.0:1.0:1.0.
further, in S1, the carbonization treatment is performed in N 2 The carbonization treatment is carried out under the atmosphere, the temperature of the carbonization treatment is 400-800 ℃, and the time is 4h.
Further, in S1, the ultrasonic treatment is carried out by adopting hydrochloric acid with the mass concentration of 15-20%; and the washing treatment is to wash by adopting ultrapure water until the pH value of the washing liquid is 7-8.
Further, in S2, the sulfonation step is: mixing the pretreated carbon-based material with water, adding water, heating in oil bath, adding sulfanilic acid, reacting for 30-35 min, adding NaNO 2 And reacting for 10-12 h again, taking out the reactant, washing and filtering the reactant by using dilute hydrochloric acid, water and methanol, and drying for 12-24 h at the temperature of 80-85 ℃.
Further, the pretreated carbon-based material, water, sulfanilic acid and NaNO 2 The dosage ratio of 1: (150 to 200) mL: (4-5) g:6g.
Further, in S2, the temperature of the oil bath is 80-100 ℃.
The invention also discloses the lignin-PVC carbon-based solid acid prepared by the preparation method.
The invention also discloses an application of the lignin-PVC carbon-based solid acid, and when the lignin-PVC carbon-based solid acid is used as a catalyst in a reaction for preparing furfural by biomass conversion, the method comprises the following steps:
adding biomass and lignin-PVC carbon-based solid acid into a pressure-resistant reaction tube according to the mass ratio of (1.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of lignin-PVC carbon-based solid acid, which is characterized in that lignin and PVC are used as carbon sources, and then a sulfanilic acid sulfonation method is adopted to prepare the carbon-based solid acid catalyst grafted with sulfonic acid groups, wherein the sulfonation condition of the method is relatively mild, and the method is safer and more environment-friendly compared with the traditional high-temperature sulfonation of concentrated sulfuric acid; meanwhile, the method takes PVC as a raw material, and makes full use of waste PVC plastics; meanwhile, chlorine is introduced into the carbon-based solid acid material through PVC, and the reaction performance is promoted to be improved by utilizing hydrogen bonds formed by the chlorine and the biomass. In addition, the carbon carrier used by the method is derived from lignin in biomass and PVC (polyvinyl chloride) which is a plastic waste in life, the method accords with the concept of green environmental protection sustainable development, and the used raw materials are low in cost, simple and convenient in synthesis path and easy to amplify production and preparation.
The invention also discloses lignin-PVC carbon-based solid acid prepared by the preparation method, since the total acidity is firstly reduced along with the rise of the calcination temperature, and since the-COOH groups are main acid sites, the-COOH groups are decomposed at high temperature to reduce the total acidity. In contrast, -SO 3 The H group content increased with increasing calcination temperature, indicating that higher temperatures favor the sulfonation process, and enhanced-SO at temperatures above 600 deg.C 3 The H acidity contributes to the increase of the total acidity, however, -SO when the calcination temperature is higher than 750 ℃ 3 The H content will decrease, which means that the temperature is too high for sulfonation, resulting in a decrease in the total acidity of the carbon-based solid acid. Thus, the lignin-PVC-750 carbon-based solid acid catalyst calcined at 750 ℃ possessed the highest acidity.
The lignin-PVC carbon-based solid acid prepared by the method has high surface acid content, hardly lost active sites and good catalytic activity.
The invention also discloses application of the lignin-PVC carbon-based solid acid as a catalyst in a reaction for preparing furfural by biomass conversion, and related experimental results prove that the total acidity of the solid acid obtained by the method is higher (0.66-1.54 mmol/g), the yield of the obtained furfural reaches 82.5%, the catalyst has an excellent catalytic effect, and the high-activity and high-selectivity catalytic conversion of biomass to prepare furfural is shown.
Drawings
FIG. 1 is an SEM image of a solid acid catalyst of the present invention;
FIG. 2 is a FT-IR diagram of a solid acid catalyst of the present invention;
fig. 3 is an XRD pattern of the solid acid catalyst of the present invention.
Wherein: a-lignin-PVC-400 carbon-based solid acid; b-lignin-PVC-600 carbon-based solid acid; c-lignin-PVC-800 carbon-based solid acid; d-lignin-PVC-750 carbon-based solid acid; e-lignin-PVC-750-PVCF; f-lignin-PVC-750-POF.
Detailed Description
To make the features and effects of the present invention comprehensible to those skilled in the art, general description and definitions are made below with reference to terms and expressions mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features defined herein as numerical ranges or percentage ranges, such as values, amounts, levels and concentrations, are provided for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.
In this document, unless otherwise specified, "comprising," "including," "having," or similar terms, shall mean "consisting of 8230; \8230, composition" and "consisting essentially of 8230; \8230, composition" such as "A comprises a" shall mean "A comprises a and the other" and "A comprises a only".
In this context, for the sake of brevity, not all possible combinations of features in the various embodiments or examples are described. Therefore, as long as there is no contradiction between combinations of these technical features, any combinations of the technical features in the respective embodiments or examples may be made, and all possible combinations should be considered as the scope of the present specification.
The patent centers on the preparation of furfural from biomass waste, develops a porous solid acid catalyst compounded from the biomass waste polyvinyl chloride (PVC) plastic, and improves the acid density and stability of the catalyst by taking sulfanilic acid as a sulfonic acid group precursor. The sulfonic acid-based solid acid catalyst prepared by pyrolysis of lignin and PVC at high temperature is used for preparing furfural by xylose hydrolysis reaction to evaluate the catalytic activity of furfural. The lignin-PVCx carbon-based solid acid catalyst prepared by the invention has the advantages of low cost of used raw materials, simple and convenient synthesis route and easy scale-up production and preparation.
So far, no report is found on the research of preparing the solid acid catalyst by the high-temperature pyrolysis sulfonation of lignin-PVC. So far, no report is found on the research of preparing the solid acid catalyst by the high-temperature pyrolysis sulfonation of lignin-PVC.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Instrumentation conventional in the art is used in the following examples. Experimental procedures without specific conditions noted in the following examples, generally according to conventional conditions, or according to conditions recommended by the manufacturer. The various starting materials used in the examples which follow, unless otherwise indicated, are conventional commercial products having specifications which are conventional in the art. In the description of the present invention and the following examples, "%" represents weight percent, "parts" represents parts by weight, and proportions represent weight ratios, unless otherwise specified.
Example 1
A preparation method of lignin-PVC carbon-based solid acid comprises the following steps:
s1: placing 5.0g of lignin, 5.0g of PVC and 5.0g of KOH in a mortar, uniformly grinding, transferring to a porcelain square boat, placing in a tubular furnace, purging the tubular furnace for 5-10 min by using nitrogen, heating to 750 ℃ at the speed of 10 ℃/min, carbonizing for 4h at high temperature, naturally cooling to room temperature, and taking out to obtain a carbon-based material; then putting the carbon-based material into a mortar for grinding for 5min, putting the obtained solid powder into a dilute hydrochloric acid solution, performing ultrasonic treatment for 2h, filtering, collecting a filtrate, washing with distilled water until the pH of a washing liquid is = 7-8, then putting the washed filtrate into a drying oven, and drying at 80 ℃ for 24h to obtain a pretreated carbon-based material (lignin-PVC-750 carbon base);
s2: weighing 1.0g of lignin-PVC-750 carbon base, pouring into a three-neck bottle, adding 150mL of water, heating in oil bath to 80 ℃, adding 4.0g of sulfanilic acid, reacting for 30min, dissolving, and adding 6.0g of NaNO 2 And taking out after 10h of reaction, alternately washing and filtering by using methanol and water until the pH of a washing liquid is = 7-8, and drying at 80 ℃ for 24h to obtain the lignin-PVC carbon-based solid acid (the lignin-PVC-750 carbon-based solid acid).
The acid value of the sample is 1.54mmol/g through measurement; when the prepared lignin-PVC-750 carbon-based solid acid is applied to preparation of furfural through biomass conversion, 0.10g of xylose, 0.05g of lignin-PVC-750 carbon-based solid acid and 5mL of gamma-valerolactone are added into a 25mL pressure-resistant reaction tube, the reaction temperature is 160 ℃ under magnetic stirring, the reaction is kept for 60min, and the yield of the obtained furfural is 82.5%.
Example 2
S1: placing 5.0g of lignin, 5.0g of PVC and 5.0g of KOH in a mortar, uniformly grinding, transferring to a porcelain square boat, placing in a tubular furnace, purging the tubular furnace for 5-10 min by using nitrogen, heating to 400 ℃ at a rate of 10 ℃/min, carbonizing for 4h at a high temperature, naturally cooling to room temperature, and taking out to obtain a carbon-based material; then putting the carbon-based material into a mortar for grinding for 5min, putting the obtained solid powder into a dilute hydrochloric acid solution, performing ultrasonic treatment for 2h, filtering, collecting a filtrate, washing with distilled water until the pH of a washing liquid is = 7-8, then putting the washed filtrate into a drying oven, and drying at 80 ℃ for 24h to obtain the pretreated carbon-based material (lignin-PVC-400 carbon-based);
s2: weighing 1.0g of lignin-PVC-400 carbon base, pouring into a three-neck bottle, adding 150mL of water, heating in oil bath to 80 ℃, adding 4.0g of sulfanilic acid, reacting for 35min, dissolving, and adding 6.0g of NaNO 2 And taking out after 10 hours of reaction, alternately washing and filtering by using methanol and water until the pH of a washing liquid is = 7-8, and drying at 80 ℃ for 24 hours to obtain the lignin-PVC carbon-based solid acid (lignin-PVC-400 carbon-based solid acid).
The acid value of the sample is 1.26mmol/g through measurement; when the prepared lignin-PVC-400 carbon-based solid acid is applied to the application of biomass conversion to prepare furfural, 0.10g of xylose, 0.05g of lignin-PVC-450 carbon-based solid acid and 5mL of gamma-valerolactone are added into a 25mL pressure-resistant reaction tube, the reaction temperature is 160 ℃ under magnetic stirring, the reaction is kept for 60min, and the yield of the obtained furfural is 45.3%.
Example 3
A preparation method of lignin-PVC carbon-based solid acid comprises the following steps:
s1: placing 5.0g of lignin, 5.0g of PVC and 10.0g of KOH in a mortar, grinding uniformly, transferring to a porcelain ark, placing in a tubular furnace, purging the tubular furnace by using nitrogen for 5-10 min, heating to 500 ℃ at the speed of 10 ℃/min, carbonizing at high temperature for 4h, naturally cooling to room temperature, and taking out to obtain a carbon-based material; then putting the carbon-based material into a mortar for grinding for 5min, putting the obtained solid powder into a dilute hydrochloric acid solution, performing ultrasonic treatment for 2h, filtering, collecting a filtrate, washing with distilled water until the pH of a washing liquid is = 7-8, then putting the washed filtrate into a drying oven, and drying at 80 ℃ for 24h to obtain the pretreated carbon-based material (lignin-PVC-500 carbon-based);
s2: weighing 1.0g of lignin-PVC-500 carbon base, pouring into a three-neck bottle, adding 150mL of water, heating in oil bath to 100 ℃, adding 4.0g of sulfanilic acid, reacting for 30min, dissolving, and adding 6.0g of NaNO 2 Taking out after 12h of reaction, washing and filtering with methanol and water alternately until washingAnd drying the solution at the pH of between 7 and 8 for 12 hours at the temperature of 80 ℃ to obtain the lignin-PVC carbon-based solid acid (lignin-PVC-500 carbon-based solid acid).
The acid value of the sample is 1.26mmol/g through measurement; when the prepared lignin-PVC-500 carbon-based solid acid is applied to preparation of furfural through biomass conversion, 0.10g of xylose, 0.05g of lignin-PVC-500 carbon-based solid acid and 5mL of gamma-valerolactone are added into a 25mL pressure-resistant reaction tube, the reaction temperature is 160 ℃ under magnetic stirring, the reaction is kept for 60min, and the yield of the furfural is 34.5%.
Example 4
A preparation method of lignin-PVC carbon-based solid acid comprises the following steps:
s1: placing 5.0g of lignin, 5.0g of PVC and 10.0g of KOH in a mortar, grinding uniformly, transferring to a porcelain ark, placing in a tubular furnace, purging the tubular furnace by using nitrogen for 5-10 min, heating to 600 ℃ at a speed of 10 ℃/min, carbonizing at high temperature for 4h, naturally cooling to room temperature, and taking out to obtain a carbon-based material; then putting the carbon-based material into a mortar for grinding for 5min, putting the obtained solid powder into a dilute hydrochloric acid solution, performing ultrasonic treatment for 2h, filtering, collecting a filtrate, washing with distilled water until the pH of a washing liquid is = 7-8, then putting the washed filtrate into a drying oven, and drying at 80 ℃ for 24h to obtain the pretreated carbon-based material (lignin-PVC-600 carbon-based);
s2: weighing 1.0g of lignin-PVC-600 carbon base, pouring into a three-necked bottle, adding 150mL of water, heating to 80 ℃ in an oil bath, adding 4.0g of sulfanilic acid, reacting for 30min, dissolving, and adding 6.0g of NaNO 2 And taking out after 10h of reaction, alternately washing and filtering by using methanol and water until the pH of a washing liquid is = 7-8, and drying at 80 ℃ for 24h to obtain the lignin-PVC carbon-based solid acid (the lignin-PVC-600 carbon-based solid acid).
The acid value of the sample was determined to be 0.90mmol/g; when the prepared lignin-PVC-600 carbon-based solid acid is applied to preparation of furfural through biomass conversion, 0.10g of xylose, 0.05g of lignin-PVC-600 carbon-based solid acid and 5mL of gamma-valerolactone are added into a 25mL pressure-resistant reaction tube, the reaction temperature is 160 ℃ and the reaction is kept for 60min under magnetic stirring, and the yield of the furfural is 49.4%.
Example 5
S1: placing 5.0g of lignin, 5.0g of PVC and 10.0g of KOH in a mortar, grinding uniformly, transferring to a porcelain ark, placing in a tubular furnace, purging the tubular furnace by using nitrogen for 5-10 min, heating to 700 ℃ at a speed of 10 ℃/min, carbonizing at high temperature for 4h, naturally cooling to room temperature, and taking out to obtain a carbon-based material; then, putting the carbon-based material into a mortar for grinding for 5min, putting the obtained solid powder into a dilute hydrochloric acid solution, performing ultrasonic treatment for 2h, filtering, collecting a filtrate, washing with distilled water until the pH = 7-8 of a washing liquid, then putting the washed filtrate into a drying oven, and drying at 80 ℃ for 24h to obtain the pretreated carbon-based material (lignin-PVC-700 carbon-based);
s2: weighing 1.0g of lignin-PVC-700 carbon base, pouring into a three-neck bottle, adding 200mL of water, heating in oil bath to 80 ℃, adding 4.0g of sulfanilic acid, reacting for 30min, dissolving, and adding 6.0g of NaNO 2 And taking out after 10h of reaction, alternately washing and filtering by using methanol and water until the pH of a washing liquid is = 7-8, and drying at 80 ℃ for 24h to obtain the lignin-PVC carbon-based solid acid (lignin-PVC-700 carbon-based solid acid).
The acid value of the sample was determined to be 1.20mmol/g; when the prepared lignin-PVC-700 carbon-based solid acid is applied to preparation of furfural through biomass conversion, 0.10g of xylose, 0.05g of lignin-PVC-700 carbon-based solid acid and 5mL of gamma-valerolactone are added into a 25mL pressure-resistant reaction tube, the reaction temperature is 160 ℃ under magnetic stirring, the reaction is kept for 60min, and the yield of the obtained furfural is 74.7%.
Example 6
S1: placing 5.0g of lignin, 5.0g of PVC and 10.0g of KOH in a mortar, grinding uniformly, transferring to a porcelain ark, placing in a tubular furnace, purging the tubular furnace by using nitrogen for 5-10 min, heating to 800 ℃ at the speed of 10 ℃/min, carbonizing at high temperature for 4h, naturally cooling to room temperature, and taking out to obtain a carbon-based material; then, putting the carbon-based material into a mortar for grinding for 5min, putting the obtained solid powder into a dilute hydrochloric acid solution, performing ultrasonic treatment for 2h, filtering, collecting a filtrate, washing with distilled water until the pH = 7-8 of a washing liquid, then putting the washed filtrate into a drying oven, and drying at 80 ℃ for 24h to obtain a pretreated carbon-based material (lignin-PVC-800 carbon base);
s2: weighing 1.0g of lignin-PVC-800 carbon base, pouring into a three-neck flask, adding 180mL of water, heating to 80 ℃ in an oil bath, adding 5.0g of sulfanilic acid, reacting for 30min, dissolving, and adding 6.0g of NaNO 2 And taking out after 10 hours of reaction, alternately washing and filtering by using methanol and water until the pH of a washing liquid is = 7-8, and drying at 80 ℃ for 24 hours to obtain the lignin-PVC carbon-based solid acid (lignin-PVC-800 carbon-based solid acid).
The acid value of the sample was determined to be 0.66mmol/g; when the prepared lignin-PVC-800 carbon-based solid acid is applied to preparation of furfural through biomass conversion, 0.10g of xylose, 0.05g of lignin-PVC-800 carbon-based solid acid and 5mL of gamma-valerolactone are added into a 25mL pressure-resistant reaction tube, the reaction temperature is 160 ℃ and the reaction is kept for 60min under magnetic stirring, and the yield of the furfural is 33.3%.
Example 7
S1: placing 5.0g of lignin, 5.0g of PVC and 10.0g of KOH in a mortar, grinding uniformly, transferring to a porcelain ark, placing in a tubular furnace, purging the tubular furnace by using nitrogen for 5-10 min, heating to 750 ℃ at the speed of 10 ℃/min, carbonizing at high temperature for 4h, naturally cooling to room temperature, and taking out to obtain a carbon-based material; then putting the carbon-based material into a mortar for grinding for 5min, putting the obtained solid powder into a dilute hydrochloric acid solution, performing ultrasonic treatment for 2h, filtering, collecting a filtrate, washing with distilled water until the pH of a washing liquid is = 7-8, then putting the washed filtrate into a drying oven, and drying at 80 ℃ for 24h to obtain a pretreated carbon-based material (lignin-PVC-750 carbon base);
s2: weighing 1.0g of lignin-PVC-750 carbon base, pouring into a three-neck bottle, adding 150mL of water, heating in oil bath to 80 ℃, adding 4.0g of sulfanilic acid, reacting for 30min, dissolving, and adding 6.0g of NaNO 2 And taking out after 10h of reaction, alternately washing and filtering by using methanol and water until the pH of a washing liquid is = 7-8, and drying at 80 ℃ for 24h to obtain the lignin-PVC carbon-based solid acid (the lignin-PVC-750 carbon-based solid acid).
Comparative example 1
A preparation method of carbon-based solid acid comprises the following steps:
s1: placing 5.0g of lignin and 5.0g of PV in a mortar for even grinding, transferring to a porcelain ark, placing in a tube furnace, purging the tube furnace for 5-10 min by using nitrogen, heating to 750 ℃ at a speed of 10 ℃/min, carbonizing for 4h at high temperature, naturally cooling to room temperature, and taking out to obtain a carbon-based material; then putting the carbon-based material into a mortar for grinding for 5min, putting the obtained solid powder into a dilute hydrochloric acid solution for ultrasonic treatment for 2h, filtering, collecting filtrate, washing with distilled water until the pH of the washing liquid is between 7 and 8, then putting the washed filtrate into an oven, and drying at 80 ℃ for 24h to obtain lignin-PVC-750-POF carbon (POF stands for the Potassium oxide of free);
s2: weighing 1.0g of lignin-PVC-750-POF carbon base, pouring into a three-necked bottle, adding 150mL of water, heating to 80 ℃ in an oil bath, adding 4.0g of sulfanilic acid, reacting for 30min, dissolving, and adding 6.0g of NaNO 2 And taking out after 10h of reaction, alternately washing and filtering by using methanol and water until the pH of a washing liquid is = 7-8, and drying at 80 ℃ for 24h to obtain the lignin-PVC-750-POF carbon-based solid acid.
The acid value of the sample is 1.96mmol/g through measurement; when the prepared lignin-PVC-750-POF carbon-based solid acid is applied to the application of biomass conversion in preparing furfural, 0.10g of xylose, 0.05g of lignin-PVC-750-POF carbon-based solid acid and 5mL of gamma-valerolactone are added into a 25mL pressure-resistant reaction tube, the reaction temperature is 160 ℃ under magnetic stirring, the reaction is maintained for 60min, and the yield of the obtained furfural is 11.9%.
Comparative example 2
A preparation method of carbon-based solid acid comprises the following steps:
s1: placing 5.0g of lignin and 5.0g of KOH in a mortar for grinding uniformly, transferring to a porcelain boat, placing in a tube furnace, purging the tube furnace with nitrogen for 5-10 min, heating to 750 ℃ at a speed of 10 ℃/min, carbonizing for 4h at high temperature, naturally cooling to room temperature, and taking out to obtain a carbon-based material; then putting the carbon-based material into a mortar for grinding for 5min, putting the obtained solid powder into a dilute hydrochloric acid solution for ultrasonic treatment for 2h, filtering, collecting a filtrate, washing with distilled water until the pH of a washing liquid is = 7-8, then putting the washed filtrate into an oven, and drying at 80 ℃ for 24h to obtain lignin-750-PVCF carbon-based (PVCF stands for PVC of free);
s2: weighing 1.0g of lignin-750-PVCF carbon base, pouring the lignin-750-PVCF carbon base into a three-neck flask, adding 150mL of water, heating the oil bath to 80 ℃, adding 4.0g of sulfanilic acid, reacting for 30min, and adding 6.0g of NaNO after the dissolved carbon base is dissolved 2 And taking out after 10h of reaction, alternately washing and filtering by using methanol and water until the pH of a washing liquid is = 7-8, and drying at 80 ℃ for 24h to obtain the lignin-750-PVCF carbon-based solid acid.
The acid value of the sample was determined to be 0.54mmol/g; when 0.54mmol/g obtained by preparation is applied to the application of biomass conversion to prepare furfural, 0.10g of xylose, 0.05g of 0.54mmol/g and 5mL of gamma-valerolactone are added into a 25mL pressure-resistant reaction tube, the reaction temperature is 160 ℃ under magnetic stirring, the reaction is kept for 60min, and the yield of the furfural is 3.0%.
Comparative example 3
A preparation method of carbon-based solid acid comprises the following steps:
s1: placing 5.0g of PVC and 5.0g of KOH (without lignin) in a mortar for even grinding, transferring to a porcelain ark, placing in a tube furnace, purging the tube furnace for 5-10 min by using nitrogen, heating to 750 ℃ at the speed of 10 ℃/min, carbonizing at high temperature for 4h, naturally cooling to room temperature, and taking out to obtain a carbon-based material; then putting the carbon-based material into a mortar for grinding for 5min, putting the obtained solid powder into a dilute hydrochloric acid solution, performing ultrasonic treatment for 2h, then filtering, collecting a filtrate, washing with distilled water until the pH = 7-8 of a washing liquid, then putting the washed filtrate into a drying oven, and drying at 80 ℃ for 24h to obtain the pretreated carbon-based material which is Lignin-PVC-750-LF carbon base (LF stands for Lignin of free);
s2: weighing 1.0g of lignin-PVC-750-LF carbon base, pouring into a three-neck flask, adding 150mL of water, heating in oil bath to 80 ℃, adding 4.0g of sulfanilic acid, reacting for 30min, dissolving, and adding 6.0g of NaNO 2 Reacting for 10h, taking out, washing with methanol and water alternately, filtering until pH = 7-8, and drying at 80 deg.CAnd drying for 24h to obtain the lignin-PVC-750-LF carbon-based solid acid (the lignin-PVC-750-LF carbon-based solid acid).
The acid value of the sample was determined to be 0.90mmol/g; when the prepared lignin-PVC-750-LF carbon-based solid acid is applied to the application of biomass conversion in the preparation of furfural, 0.10g of xylose, 0.05g of lignin-PVC-750-LF carbon-based solid acid and 5mL of gamma-valerolactone are added into a 25mL pressure-resistant reaction tube, the reaction temperature is 160 ℃ under magnetic stirring, the reaction is maintained for 60min, and the yield of the furfural is 49.4%.
The above catalyst was subjected to cyclic studies, and the used catalyst was washed with water and ethanol alternately three times. The acid value of the sample is determined to be 0.48mmol/g after five times of circulation; when the used lignin-PVC-750 carbon-based solid acid is used again in the application of preparing furfural by biomass conversion, 0.10g of xylose, 0.05g of lignin-PVC-750 carbon-based solid acid and 5mL of gamma-valerolactone are added into a 25mL pressure-resistant reaction tube, the reaction temperature is 160 ℃ under magnetic stirring, the reaction is kept for 60min, and the yield of the obtained furfural is 56.9%.
Fig. 1 shows an SEM image of the sample. From the figure, it can be seen that lignin and PVC present a smoother irregular polygonal block structure under a scanning electron microscope. As can be seen from the figure, the carbon-based catalysts calcined at different temperatures present different morphologies, the lignin-PVC-400 carbon-based solid acid catalyst calcined at 400 ℃ is a blocky structure with a smooth surface and a part of pore channels formed inside, while the lignin-PVC-600 carbon-based solid acid is a blocky structure with a large number of pore structures on the surface and inside, and when the temperature is increased to 750 ℃, the surface of the lignin-PVC-750 carbon-based solid acid catalyst presents a lamellar structure with a large number of pores, and the surface area is greatly increased. At 800 ℃, the surface of the lignin-PVC-800 carbon-based solid acid catalyst is in a porous thin-layer sheet structure, which shows that the influence of the calcination temperature on the carbon structure is very large. Compared with the lignin-PVC-750-PVCF carbon-based solid acid catalyst and the lignin-PVC-750-POF carbon-based solid acid catalyst, the appearance structure of the carbon-based lamellar structure is more abundant after PVC is added, and the appearance structure of the lignin-PVC-750-PVCF carbon-based solid acid catalyst and the appearance structure of the lignin-PVC-750-POF carbon-based solid acid catalyst are combinedThe structure has not changed too much, which indicates that-SO is introduced 3 H has no influence on the surface structure of the carbon base.
FIG. 2 shows the FT-IR spectrum of the sample. From the figure, it can be seen that various oxygen-containing functional groups of lignin, such as 3600-3000 cm -1 2850-2930 cm which is the stretching vibration peak of O-H -1 The peak at (A) is mainly from various aliphatic groups (-CH ) 2 and-CH 3 ) About 1720cm -1 The peak at position is C = O stretching vibration peak and is 1390-1647 cm -1 A strong broad peak in the range centered at 1430cm -1 The aromatic skeleton vibrates on the left and right. The lignin is a biological macromolecule with a three-dimensional network structure, is formed by connecting 3 phenylpropane units through ether bonds and carbon-carbon bonds, and contains abundant active groups such as aromatic ring structures, aliphatic and aromatic hydroxyl groups, quinone groups and the like. From 1000 to 1390cm -1 Has strong broad peak at 1351, 1230 and 1128cm -1 Several peaks on the left and right, and 1047cm -1 Due to the complex results of C-O stretching, aromatic ring respiration, aromatic C-H deformation, C-O deformation, from 600 to 800cm -1 The peaks of (A) are C-Cl vibrational haloalkanes and aromatic rings. In addition, 1232, 1128 and 1047cm were observed -1 The relative intensity of the peak is enhanced and is-SO 3 Characteristic absorption peaks of H because S = O and O = S = O stretching vibrations are 1035, 1164 and 1260cm -1 indicates-SO 3 The H group was successfully introduced by the sulfonation process.
Fig. 3 shows the XRD spectrum of the sample, from which it can be seen that 2 θ appears as a strong peak at 20-30 °, a weak peak at 40-50 °, corresponding to the (002) and (101) crystal planes of carbon, respectively, the peak at 20-30 ° is mainly an aromatic amorphous carbon structure, and the peak at 40-50 ° is corresponding to a graphitic carbon structure. Comparing the lignin-PVC-400 carbon-based solid acid catalyst, the lignin-PVC-600 carbon-based solid acid catalyst, the lignin-PVC-750 carbon-based solid acid catalyst and the lignin-PVC-800 carbon-based solid acid catalyst, it can be seen that the higher the calcination temperature of the catalyst carbon carrier, the stronger the peak between 40 and 50 degrees of 2 theta, and the higher the graphitization degree of the catalyst. Comparing the lignin-PVC-750-PVCF carbon-based solid acid catalyst with the lignin-PVC-750-POF carbon-based solid acid catalyst, it can be seen that the addition of PVC has no influence on the crystal structure of the lignin carbon. Comparing the lignin-PVC-750-PVCF carbon-based solid acid catalyst and the lignin-PVC-750-POF carbon-based solid acid catalyst, it can be seen that the peak of the sulfonated catalyst on the (002) crystal face of carbon is widened, which indicates that the amorphous structure of the carbon is enhanced, and the insertion of the phenylsulfonic acid group increases the disorder degree of the carbon structure.
According to the invention, lignin and PVC are used as carbon sources to prepare the carbon-based solid acid catalyst by direct carbonization and sulfonation, the preparation method is green and environment-friendly and is simple to operate, and the prepared catalyst has the advantages of high activity, high selectivity, high yield, no corrosion to reaction equipment, easiness in separation after reaction and the like; the catalyst can realize the reaction of preparing furfural by biomass one-step conversion, and has good catalytic performance.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. The preparation method of the lignin-PVC carbon-based solid acid is characterized by comprising the following steps:
s1: mixing lignin, PVC and KOH, and then carrying out carbonization treatment to obtain a carbon-based material; sequentially carrying out ultrasonic treatment, washing treatment and drying treatment on the carbon-based material to obtain a pretreated carbon-based material;
s2: and sulfonating the pretreated carbon-based material by sulfanilic acid under the condition of oil bath, and then washing and drying to obtain the lignin-PVC carbon-based solid acid.
2. The method for preparing the lignin-PVC carbon-based solid acid according to claim 1, wherein in S1, the weight ratio of the lignin to the PVC to the KOH is 1.0:1.0:1.0.
3. a lignin-PVC carbon-based solid according to claim 1The method for producing an acid is characterized in that, in S1, the carbonization treatment is performed in N 2 The carbonization treatment is carried out under the atmosphere, the temperature of the carbonization treatment is 400-800 ℃, and the time is 4h.
4. The method for preparing the lignin-PVC carbon-based solid acid according to claim 1, wherein in S1, the ultrasonic treatment is performed by using hydrochloric acid with a mass concentration of 15-20%; and the washing treatment is to wash by adopting ultrapure water until the pH value of the washing liquid is 7-8.
5. The method for preparing the lignin-PVC carbon-based solid acid according to claim 1, wherein in S2, the sulfonation step is: mixing the pretreated carbon-based material with water, adding water, heating in oil bath, adding sulfanilic acid, reacting for 30-35 min, adding NaNO 2 And reacting for 10-12 h again, taking out the reactant, washing and filtering the reactant by using dilute hydrochloric acid, water and methanol, and drying for 12-24 h at the temperature of 80-85 ℃.
6. The method for preparing lignin-PVC carbon-based solid acid according to claim 5, wherein the pretreated carbon-based material, water, sulfanilic acid and NaNO are 2 The dosage ratio of 1: (150-200) mL: (4-5) g:6g.
7. The method for preparing the lignin-PVC carbon-based solid acid according to claim 1, wherein in S2, the temperature of the oil bath is 80-100 ℃.
8. A lignin-PVC carbon-based solid acid, which is characterized in that the lignin-PVC carbon-based solid acid is prepared by the preparation method of the lignin-PVC carbon-based solid acid according to any one of claims 1 to 7.
9. The application of the lignin-PVC carbon-based solid acid as claimed in claim 8, wherein the lignin-PVC carbon-based solid acid is used as a catalyst in a reaction for preparing furfural by biomass conversion.
10. The application of the lignin-PVC carbon-based solid acid as claimed in claim 9, wherein when the lignin-PVC carbon-based solid acid is used as a catalyst in a reaction for preparing furfural by biomass conversion, the method comprises the following steps:
adding biomass and lignin-PVC carbon-based solid acid into a pressure-resistant reaction tube according to the mass ratio of (1.
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