CN108689826B - Method for separating and purifying levulinic acid from sulfuric acid hydrolysate of biomass - Google Patents
Method for separating and purifying levulinic acid from sulfuric acid hydrolysate of biomass Download PDFInfo
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Abstract
A method for separating and purifying levulinic acid from sulfuric acid hydrolysate of biomass relates to levulinic acid. Adding a neutralizing reagent into a sulfuric acid hydrolysis reaction solution of biomass, filtering, adding a precipitator into a filtrate, filtering, concentrating the obtained filtrate, and recovering low-boiling-point substances to obtain a black concentrated solution; distilling the black concentrated solution, collecting fractions, and carrying out secondary reduced pressure distillation to obtain the levulinic acid product. The method solves the very important bottleneck problem in the process of producing the levulinic acid by hydrolyzing the biomass by using the sulfuric acid as the catalyst, namely the dehydration and carbonization of the concentrated sulfuric acid during the separation and purification of the levulinic acid, removes the sulfate radicals in the hydrolysate by using a reasonable neutralizing reagent and a reasonable precipitating reagent, does not influence the subsequent separation and purification of the levulinic acid, and makes the direct extraction of the levulinic acid from the sulfuric acid hydrolysis reaction liquid of the biomass possible.
Description
Technical Field
The invention relates to levulinic acid, in particular to a method for separating and purifying levulinic acid from sulfuric acid hydrolysate of biomass.
Background
The molecule of the levulinic acid contains a carbonyl group, a carboxyl group and α -hydrogen, and the levulinic acid can be used as a carboxylic acid reaction and a ketone reaction, and can be used as an intermediate product for preparing synthetic rubber, a cold-resistant plasticizer and a surfactant, and the chlorinated levulinic acid can be used as a bacteriostatic agent for industrial circulating water.
Chinese patent CN105859545A discloses a method for preparing levulinic acid, which comprises the steps of carrying out high-temperature reaction on agricultural and forestry waste under the action of an acid catalyst in a water and organic phase system to obtain reaction liquid containing the levulinic acid, and then mixing the reaction liquid with the agricultural and forestry waste to carry out low-temperature reaction to obtain furfural and the levulinic acid. The technology does not solve the problem of separation of levulinic acid from other products in the presence of an acid catalyst.
Chinese patent CN104311411A discloses a method for preparing levulinic acid by multistage acid hydrolysis, which comprises the steps of placing straws and dilute acid solution in a reaction kettle at a mass ratio of 1: 5-10, reacting at 200-250 ℃ for 30-60 min, wherein the mass concentration of the dilute acid solution is 1-3%. And (4) obtaining the levulinic acid enrichment solution with higher concentration through multiple feeding and hydrolysis. The technology can increase the concentration of by-products such as catalyst acid, humus and the like in the hydrolysate, and brings difficulty for the subsequent separation of the levulinic acid.
U.S. Pat. No. 4, 9884834, 2 discloses a process for preparing acetopropionate by dilute sulfuric acid catalysis in a steam flowing environment
The method comprises the steps of reacting in a reactor at the temperature of 150-200 ℃ for 30-480 min, wherein the content of dilute sulfuric acid is 1-5%, the pressure is 3-14 bar, and the initial biomass feeding amount is 5-30 wt%. The levulinic acid solution with higher mass fraction can be obtained by using the technology, but the total production cost is higher.
Chinese patent CN106748711A discloses a method for preparing levulinic acid by pretreated cow dung, which comprises the steps of mixing cow dung with an alkaline compound and water, heating for reaction to obtain pretreated cow dung, extracting lignin in the cow dung, and catalyzing the pretreated cow dung by dilute acid with the mass concentration of 0.3-2.3% to prepare the levulinic acid. The use of this technique requires a pretreatment process, which increases the production cost and does not solve the problem of subsequent separation.
Currently, there are two main routes of levulinic acid production reported, the first synthetic route: catalytic hydrolysis of furfuryl alcohol. Pentosan is used as a raw material, firstly, the pentosan is converted into furfural through cracking, then the furfural is hydrogenated to generate furfuryl alcohol, and the furfuryl alcohol is subjected to hydrolysis, ring opening and rearrangement reaction under the catalysis of acid to generate levulinic acid. The key to this process is ring opening and rearrangement. The method has the defect that the raw material price is higher, so that the total production cost of the levulinic acid is higher. Second synthetic route: and (3) performing direct biomass hydrolysis. The method takes biomass hexose as a raw material, and prepares the levulinic acid directly by hydrolysis in the presence of an acid catalyst. The biomass is various in types, wide in distribution, low in price and easy to obtain, and the cost can be effectively reduced by directly using lignocellulose such as agricultural and forestry waste and the like to produce the levulinic acid. However, the catalyst used for directly producing levulinic acid by using biomass as a raw material is generally sulfuric acid due to economic considerations, so that in the subsequent separation process, the levulinic acid is converted by dehydration and carbonization of the sulfuric acid under a high-temperature anhydrous environment. Proper treatment of the sulfuric acid is therefore critical to the isolation of levulinic acid. Meanwhile, the components in the sulfuric acid hydrolysate of biomass are complex and comprise water, acid catalysts, small molecular acids and small molecular sugars, levulinic acid, furfural, pigments, humus and other unknown substances.
Water and small molecular acid in the hydrolysate can be recovered by concentrating the reaction solution, the operation is easy to realize, but levulinic acid is difficult to separate from the concentrated solution, the main difficulties are that ① hydrolysis is low in levulinic acid content in the hydrolysate for preparing the levulinic acid, the purification is difficult, ② reaction solution contains a large amount of pigment and humus, the color and the recovery rate of the extracted levulinic acid are influenced, when the levulinic acid is collected by ③ high-temperature distillation, the levulinic acid is converted by dehydration and carbonization of concentrated sulfuric acid, and the operation is the most important obstacle in the technical industrialization process of producing the levulinic acid by catalyzing hydrolysis reaction of biological hyaluronic acid.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for separating and purifying levulinic acid from sulfuric acid hydrolysate of biomass.
The invention comprises the following steps:
1) adding a neutralizing reagent into a sulfuric acid hydrolysis reaction solution of biomass, filtering, adding a precipitator into a filtrate, filtering, concentrating the obtained filtrate, and recovering low-boiling-point substances to obtain a black concentrated solution;
in step 1), CaO, Ca (OH) and the like can be used as the neutralizing agent2、CaCO3、Ca(HCO3)2The dosage of the neutralizing agent can be 50 to 100 percent of the sulfuric acid content in the sulfuric acid hydrolysate of the biomass according to the mass percentage; the precipitant can be BaO, Ba (OH)2、BaCl2、Ba(NO3)2The dosage of the precipitator can be 0.5 to 5 percent of the sulfuric acid hydrolysate of the biomass according to the mass percentage; the conditions for concentrating and recovering the low boiling point substances can be as follows: the distillation temperature is 50-80 ℃, and the pressure is 2000-5000 Pa; the time for concentrating and recovering the low boiling point substances can be 20-30 min, and the low boiling point substances can be water, formic acid and the like.
2) Distilling the black concentrated solution, collecting fractions, and carrying out secondary reduced pressure distillation to obtain the levulinic acid product.
In the step 2), the distillation can be carried out in a negative pressure environment; the conditions for distilling and collecting the fractions under the negative pressure environment can be as follows: the temperature is 150-180 ℃, and the pressure is 2000-5000 Pa; the conditions of the secondary reduced pressure distillation can be as follows: the temperature is 140-160 ℃, and the pressure is 2000-5000 Pa.
The invention has the advantages that: the invention solves the very important bottleneck problem in the process of producing the levulinic acid by hydrolyzing the biomass by using the sulfuric acid as the catalyst, namely the dehydration and carbonization of the concentrated sulfuric acid during the separation and purification of the levulinic acid, removes the sulfate radicals in the hydrolysate by using a reasonable neutralizing reagent and a reasonable precipitating reagent, and simultaneously does not influence the subsequent separation and purification of the levulinic acid, so that the direct extraction of the levulinic acid from the sulfuric acid hydrolysis reaction solution of the biomass becomes possible.
Drawings
FIG. 1 is an HPLC chromatogram of a sulfuric acid hydrolysate of biomass in an example of the present invention.
FIG. 2 is a GC spectrum of the levulinic acid product obtained in the example of the invention.
FIG. 3 is an MS spectrum of a levulinic acid product obtained in an example of the invention.
Detailed Description
The following examples will further describe the present invention with reference to the accompanying drawings.
Example 1
Adding 17.2g CaO into 1L of sulfuric acid hydrolysate of bamboo (levulinic acid content of 7.1g/L and sulfuric acid content of 0.31mol/L) to neutralize sulfuric acid as catalyst, filtering, and adding BaCl of 5mmol2Filtering the solution, gradually concentrating under reduced pressure at 50 deg.C to remove low boiling point substances such as water and formic acid, separating low boiling point substances (40min), heating to 165 deg.C, distilling under reduced pressure, collecting dark brown fraction, and distilling the fraction at 150 deg.C under reduced pressure to obtain yellowish clear liquid (levulinic acid) 5.1g (71.8% of levulinic acid in the raw material solution).
Example 2
27.2g of Ca (OH) is added into 1L of sulfuric acid hydrolysate of straws (the content of levulinic acid is 8.7g/L, and the content of sulfuric acid is 0.37mol/L)2Neutralizing sulfuric acid as catalyst, filtering, and adding BaCl with 5mmol content2Filtering the solution, gradually concentrating under reduced pressure at 60 deg.C to remove low boiling point substances such as water and formic acid, separating low boiling point substances (34min), heating to 170 deg.C, distilling under reduced pressure, collecting dark brown fraction, and distilling the fraction at 150 deg.C under reduced pressure to obtain yellowish clear liquid (levulinic acid) 6.4g, which accounts for 73.6% of levulinic acid in the raw material solution.
Example 3
33.9g of CaCO is added into 1L of sulphuric acid hydrolysate of corn stalks (the content of levulinic acid is 8.2g/L, and the content of sulphuric acid is 0.34mol/L)3Neutralizing sulfuric acid as catalyst, filtering, adding 5mmol Ba (OH)2Filtering the solution, gradually concentrating under reduced pressure at 60 deg.C to remove low boiling point substances such as water and formic acid, separating low boiling point substances (36min), heating to 170 deg.C, distilling under reduced pressure, collecting brown yellow fraction, and purifying the fraction at 1The distillation was carried out at 50 ℃ under reduced pressure twice to obtain 6.2g of a pale yellow clear liquid (levulinic acid) which accounted for 75.6% of the levulinic acid in the raw material liquid.
Example 4
66.2g Ca (HCO) is added into 1L sulfuric acid hydrolysate (the content of levulinic acid is 5.6g/L, and the content of sulfuric acid is 0.41mol/L) of residues after the corn stalks are prepared into furfural3)2Neutralizing sulfuric acid as catalyst, filtering, and adding 5mmol Ba (NO)3)2Filtering the solution, gradually concentrating under reduced pressure at 70 deg.C to remove low boiling point substances such as water and formic acid, after low boiling point substances are separated (28min), heating to 170 deg.C, distilling under reduced pressure, collecting brown yellow fraction, and distilling the fraction at 150 deg.C under reduced pressure to obtain yellowish clear liquid (levulinic acid) 3.8g, which accounts for 67.9% of levulinic acid in the raw material solution.
Example 5
Adding 19.6g CaO into 1L sulfuric acid hydrolysate (levulinic acid content of 14.7g/L, sulfuric acid content of 0.35mol/L) of bamboo pulp prepared from bamboo to neutralize catalyst sulfuric acid, filtering, and adding 5mmol Ba (OH)2Filtering the solution, gradually concentrating under reduced pressure at 80 deg.C to remove low boiling point substances such as water and formic acid, after low boiling point substances are separated (20min), continuing heating to 170 deg.C, distilling under reduced pressure, collecting brown yellow fraction, and performing secondary distillation under reduced pressure at 150 deg.C to obtain light yellow clear liquid (levulinic acid) 11.6g, which accounts for 78.9% of levulinic acid in the raw material solution.
In the embodiment of the invention, the HPLC map of the sulfuric acid hydrolysate of the biomass is shown in figure 1, the GC map of the levulinic acid product obtained in the embodiment of the invention is shown in figure 2, and the MS map of the levulinic acid product obtained in the embodiment of the invention is shown in figure 3.
The invention solves the important problem in the process of producing the levulinic acid by using the sulfuric acid as a catalyst, avoids dehydration and carbonization of the levulinic acid caused by residual sulfuric acid in the process of reduced pressure distillation, and realizes the direct extraction of the levulinic acid from the sulfuric acid hydrolysis reaction solution of biomass.
Claims (7)
1. A method for separating and purifying levulinic acid from sulfuric acid hydrolysate of biomass is characterized by comprising the following steps:
1) adding a neutralizing reagent into a sulfuric acid hydrolysis reaction solution of biomass, filtering, adding a precipitator into a filtrate, filtering, concentrating the obtained filtrate, and recovering low-boiling-point substances to obtain a black concentrated solution; the neutralizing agent adopts CaO and Ca (OH)2、CaCO3、Ca(HCO3)2One of calcium salts; the precipitant adopts BaO and Ba (OH)2、BaCl2、Ba(NO3)2One of soluble barium salts; the dosage of the neutralization reagent is 50 to 100 percent of the amount of the sulfuric acid in the sulfuric acid hydrolysate of the biomass according to the mass percentage;
2) distilling the black concentrated solution, collecting fractions, and carrying out secondary reduced pressure distillation to obtain the levulinic acid product.
2. The method for separating and purifying levulinic acid from the sulfuric acid hydrolysate of biomass as claimed in claim 1, wherein in the step 1), the amount of the precipitant is 0.5-5% by mass of the sulfuric acid hydrolysate of biomass.
3. The method for separating and purifying levulinic acid from the sulfuric acid hydrolysate of biomass as claimed in claim 1, wherein in the step 1), the conditions for concentrating and recovering low-boiling-point substances are as follows: the distillation temperature is 50-80 ℃, and the pressure is 2000-5000 Pa.
4. The method for separating and purifying levulinic acid from the sulfuric acid hydrolysate of biomass as claimed in claim 1, wherein in the step 1), the time for concentrating and recovering low boiling point substances is 20-30 min, and the low boiling point substances are water and formic acid.
5. The method for separating and purifying levulinic acid from the sulfuric acid hydrolysate of biomass as claimed in claim 1, wherein in step 2), the distillation is carried out under negative pressure.
6. The method for separating and purifying levulinic acid from the sulfuric acid hydrolysate of biomass as claimed in claim 1, wherein in the step 2), the distillation is performed under the negative pressure environment, and the conditions for collecting the distillate are as follows: the temperature is 150-180 ℃, and the pressure is 2000-5000 Pa.
7. The method for separating and purifying levulinic acid from the sulfuric acid hydrolysate of biomass as claimed in claim 1, wherein in the step 2), the conditions of the secondary reduced pressure distillation are as follows: the temperature is 140-160 ℃, and the pressure is 2000-5000 Pa.
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| CN113149822B (en) * | 2021-01-15 | 2023-10-24 | 太原工业学院 | Method for efficiently producing levulinic acid from cellulose resources |
| CN113929571A (en) * | 2021-11-23 | 2022-01-14 | 常州大学 | Method for separating and purifying levulinic acid |
Citations (6)
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| CN101875605A (en) * | 2010-04-09 | 2010-11-03 | 长春工业大学 | Method for preparing acetylpropionic acid by using wood residues or husks |
| CN103012145A (en) * | 2013-01-10 | 2013-04-03 | 厦门大学 | Method for separating and extracting ethyl levulinate from alcoholysis solution of biomass sugar |
| CN103497105A (en) * | 2013-10-18 | 2014-01-08 | 厦门大学 | Method for preparing ethyl levulinate through ultralow acid catalysis tapioca starch |
| WO2015007602A1 (en) * | 2013-07-17 | 2015-01-22 | Dsm Ip Assets B.V. | Process for the isolation of levulinic acid |
| CN104311411A (en) * | 2014-09-15 | 2015-01-28 | 淮阴师范学院 | Method for preparing levulinic acid by multistage acid hydrolysis |
| CN106397183A (en) * | 2015-07-28 | 2017-02-15 | 易高环保能源研究院有限公司 | Method for separating levulinic acid, formic acid and furfural from acid catalysis hydrolyzates of biomass |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101875605A (en) * | 2010-04-09 | 2010-11-03 | 长春工业大学 | Method for preparing acetylpropionic acid by using wood residues or husks |
| CN103012145A (en) * | 2013-01-10 | 2013-04-03 | 厦门大学 | Method for separating and extracting ethyl levulinate from alcoholysis solution of biomass sugar |
| WO2015007602A1 (en) * | 2013-07-17 | 2015-01-22 | Dsm Ip Assets B.V. | Process for the isolation of levulinic acid |
| CN103497105A (en) * | 2013-10-18 | 2014-01-08 | 厦门大学 | Method for preparing ethyl levulinate through ultralow acid catalysis tapioca starch |
| CN104311411A (en) * | 2014-09-15 | 2015-01-28 | 淮阴师范学院 | Method for preparing levulinic acid by multistage acid hydrolysis |
| CN106397183A (en) * | 2015-07-28 | 2017-02-15 | 易高环保能源研究院有限公司 | Method for separating levulinic acid, formic acid and furfural from acid catalysis hydrolyzates of biomass |
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