CN114605359A - Method for preparing FDCA (fully drawn yarn) and total bio-based filler by using non-grain biomass raw material - Google Patents
Method for preparing FDCA (fully drawn yarn) and total bio-based filler by using non-grain biomass raw material Download PDFInfo
- Publication number
- CN114605359A CN114605359A CN202210223966.6A CN202210223966A CN114605359A CN 114605359 A CN114605359 A CN 114605359A CN 202210223966 A CN202210223966 A CN 202210223966A CN 114605359 A CN114605359 A CN 114605359A
- Authority
- CN
- China
- Prior art keywords
- grain
- solvent
- fdca
- parts
- weight
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- 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
- C07D307/56—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 with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- 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
- C07D307/38—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 with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
Abstract
The invention provides a method for preparing FDCA and full bio-based filler by using non-grain biomass raw materials, which comprises the following steps: s1: drying the non-grain fiber and then crushing to obtain non-grain fiber powder; s2: reacting non-grain fiber powder, a solvent A and a catalyst, and filtering to obtain filter residue and filtrate; s3: distilling the filtrate obtained in the step S2 to recover the solvent, so as to obtain 5-hydroxymethylfurfural; s4: reacting 5-hydroxymethylfurfural, cobalt acetate tetrahydrate, manganese acetate tetrahydrate, sodium bromide, a fourth component metal salt and a solvent B, filtering, washing and drying to obtain FDCA powder; s5: and bleaching the filter residue obtained in the step S2, washing, drying and crushing to obtain the superfine biomass filler. The invention uses the FDCA to prepare the residual residue to prepare the ultrafine powder through simple working sections such as bleaching, drying and the like, can replace calcium carbonate and the like to be used as the filler of degradable plastics, solves the problem that the biomass raw material is difficult to be ground, and realizes the full utilization of the biomass raw material.
Description
Technical Field
The invention relates to a method for preparing FDCA and a full bio-based filler by using a non-grain biomass raw material, belonging to the technical field of organic synthesis and polymer synthesis.
Background
At present, the raw materials of polylactic acid, PLA and the like of the bio-based degradable plastics are grains such as corn, wheat and the like, and a dispute of 'competing for grains with people' exists, so that research on preparing the bio-based degradable plastics by taking non-grain biomass such as straws and the like as the raw materials is always a hot point of research. However, the preparation of various chemicals by using non-grain fibers such as straws and the like as raw materials has the problems of low conversion rate, more byproducts, large pollution and the like, so that the realization of the full utilization of the non-grain cellulose raw materials is very important.
The biological platform molecule 2, 5-furandicarboxylic acid (FDCA) as a biological-based polymer aromatic ring monomer with a 'rigid' planar structure can be polymerized with monomers such as diol, diamine and the like to prepare a novel biological-based polymer synthetic material with excellent performance.
Patent CN108997278A also provides a method for preparing 2, 5-furyl polyester, which comprises: A) taking non-grain biomass as a raw material to prepare furfural; B) oxidizing furfural to obtain furoic acid; C) performing addition reaction on furoic acid and carbon dioxide under the action of a catalyst to obtain 2, 5-furandicarboxylic acid; the catalyst is one or more of potassium carbonate, sodium oxalate, sodium nitrate, potassium nitrate, sodium nitrite, potassium acetate, sodium acetate, potassium formate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide and potassium hydroxide; D) the 2, 5-furan dicarboxylic acid and dihydric alcohol are polymerized under the action of a catalyst to obtain the furyl polyester. The invention takes non-grain biomass as raw materials to prepare furfural, the cost of the raw materials is low, the furoic acid and carbon dioxide react in a specific catalyst to obtain the 2, 5-furandicarboxylic acid, the price of the catalyst is low, the adoption of the carbon dioxide is favorable for environmental protection, and the yield of the finally prepared 2, 5-furyl polyester is high. Meanwhile, the prepared furyl polyester has high specific viscosity and molecular weight.
The traditional FDCA preparation method is characterized in that strong acids such as sulfuric acid, hydrochloric acid and phosphoric acid are used for catalyzing fructose to dehydrate to prepare HMF, the HMF product is purified and then is subjected to catalytic oxidation under a strong alkaline condition, after the oxidation is finished, the pH value is adjusted to be less than 1 by the strong acid, the FDCA product is very low in solubility under the strong acid and then is separated out, and the FDCA product is obtained through working sections such as washing and drying. The production process repeatedly uses a large amount of strong acid and strong base, pollutes the environment, has strict equipment requirements and increases the production cost. Although some researchers try to perform neutral reaction, the method has problems of extremely low reaction concentration, high catalyst cost, difficulty in recycling reaction solvent and the like.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for preparing FDCA and a full bio-based filler by using a non-grain biomass raw material.
In order to achieve the purpose, the invention is realized by the following technical scheme: a method for preparing FDCA and full bio-based filler by using non-grain biomass raw materials comprises the following steps:
s1: drying the non-grain fiber and then crushing to obtain non-grain fiber powder;
s2: reacting non-grain fiber powder, a solvent A and a catalyst, and filtering to obtain filter residue and filtrate;
s3: distilling the filtrate obtained in the step S2 to recover the solvent, so as to obtain 5-hydroxymethylfurfural;
s4: reacting 5-hydroxymethylfurfural, cobalt acetate tetrahydrate, manganese acetate tetrahydrate, sodium bromide, a fourth component metal salt and a solvent B, filtering, washing and drying to obtain FDCA powder;
s5: and bleaching the filter residue obtained in the step S2, washing, drying and crushing to obtain the superfine biomass filler.
Preferably, the particle size of the non-grain fiber powder in the step S1 is 200-400 meshes.
By adopting the technical scheme, the non-grain fiber is subjected to pretreatment and crushing operation, so that the particle size of the non-grain fiber is 200-400 meshes, the contact area between the non-grain fiber and the reagent is increased, the non-grain fiber and the reagent are completely reacted, and the subsequent yield of HMF and FDCA is further increased.
Preferably, in step S2, the non-grain fiber powder is 0.1 to 20 parts by weight, the solvent a is 100 parts by weight, and the catalyst is 0.01 to 5 parts by weight.
Preferably, the reaction conditions of the non-grain fiber powder, the solvent a and the catalyst in the step S2 are as follows: introducing nitrogen into the reaction kettle at 0.5MPa and at 140-190 ℃ for reaction for 0.5-8h, and cooling in an ice water bath after the reaction is finished.
Preferably, the solvent a in step S2 is a low-boiling point solvent, specifically, one or more of tetrahydrofuran, ethanol, and isopropanol; the catalyst is one or more of inorganic acid, organic acid and solid acid, the inorganic acid is hydrochloric acid or sulfuric acid, the organic acid is FDCA or acetic acid, and the solid acid is carbon-based solid acid.
By adopting the technical scheme, cellulose is degraded under an acidic condition to generate oligosaccharide such as monosaccharide, disaccharide and the like, and the saccharide compounds are further dehydrated to generate 5-hydroxymethylfurfural by adjusting the reaction temperature and the reaction time under the conditions of the solvent A and the catalyst.
Preferably, the non-grain cellulose is one or more of grass fiber and wood fiber; the grass fiber is one or more of wheat straw and corn straw; the wood fiber is one or more of coniferous wood and broadleaf wood.
Preferably, in step S4, the amount of 5-hydroxymethylfurfural is 0.1 to 20 parts by weight, the amount of cobalt acetate tetrahydrate is 0.1 to 10 parts by weight, the amount of manganese acetate tetrahydrate is 0.1 to 10 parts by weight, the amount of sodium bromide is 0.1 to 10 parts by weight, the amount of the fourth component metal salt is 0.1 to 10 parts by weight, and the amount of the solvent B is 100 parts by weight.
Preferably, the reaction conditions of the 5-hydroxymethylfurfural, the cobalt acetate tetrahydrate, the manganese acetate tetrahydrate, the sodium bromide, the fourth component metal salt and the solvent B in the step S4 are as follows: introduction of O2Or air 0.5-4MPa, and reacting at 80-150 deg.C for 0.5-8 h.
Preferably, the solvent B is acetic acid or water; the fourth component metal salt is one or more of zirconium acetate, copper acetate, magnesium acetate, calcium acetate, lead acetate, titanium tetrachloride, cerium chloride and chromium chloride.
In the prior art, a strong acid or a strong base is usually added for reaction in step S4, and by adopting the above technical scheme, 5-hydroxymethylfurfural prepared in S2 is purified to be a raw material in step S4, and a free radical oxidation reaction occurs in a Co/Mn/Br catalytic system, and a hydroxymethyl group and an aldehyde group of the 5-hydroxymethylfurfural are oxidized to a carboxyl group, so that 2, 5-furandicarboxylic acid is generated. The use of strong acid and strong base is eliminated in the step, and the catalyst and the solvent B are convenient to recover, so that green production is realized.
Preferably, the bleaching process in step S5 is specifically: 5-30 parts of filter residue, 100 parts of water and 0.5-5 parts of hydrogen peroxide by weight are taken and bleached for 1-9 hours at 40-120 ℃, and after the reaction is finished, the mixture is washed, filtered, dried and crushed to obtain the superfine biomass filler, wherein the particle size of the superfine biomass filler is not less than 800 meshes.
The invention has the beneficial effects that:
(1) the invention uses non-grain fiber such as straw and the like as raw materials, solves the problem of 'competing for grain with people', effectively solves the problems of using a large amount of acid and alkali, polluting environment and the like, realizes self-separation of products, and solves the problems of difficult product separation, incapability of continuously using a solvent and the like.
(2) The invention adopts non-noble metal as the catalyst to prepare the FDCA, thereby avoiding the problem that the traditional FDCA preparation method usually uses noble metal catalyst and reducing the production cost.
(3) The invention uses the FDCA to prepare the residual residue to prepare the ultrafine powder through simple working sections such as bleaching, drying and the like, can replace calcium carbonate and the like to be used as the filler of degradable plastics, solves the problem that the biomass raw material is difficult to be ground, and realizes the full utilization of the biomass raw material.
(4) The biomass is difficult to refine when being crushed to more than 400 meshes due to high toughness, so that the biomass raw material is difficult to be used as a plastic filler generally.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
Example 1
S1: drying wheat straws, and then crushing the dried wheat straws into 200 meshes to obtain wheat straw powder;
s2: placing 15g of wheat straw powder, 100g of tetrahydrofuran and 0.8g of hydrochloric acid in a reaction kettle, introducing nitrogen at 0.5MPa, reacting for 8 hours at 140 ℃, cooling in ice-water bath after the reaction is finished, and filtering to obtain filter residue and filtrate;
s3: distilling the filtrate obtained in the step S2 to recover the solvent to obtain 5-Hydroxymethylfurfural (HMF);
s4: 1.2g of HMF, 0.4g of cobalt acetate tetrahydrate, 0.4g of manganese acetate tetrahydrate, 0.35g of sodium bromide, 0.5g of zirconium acetate and 100g of acetic acid were reacted and O was introduced2Reacting for 4 hours at 125 ℃ under 2MPa, filtering, washing and drying after the reaction is finished to obtain an FDCA powder product, and simultaneously, recovering acetic acid;
s5: and (S2) bleaching the filter residue, taking 10g of filter residue, 100g of water and 0.5g of hydrogen peroxide into a bleaching reactor for bleaching, bleaching at 80 ℃ for 6 hours, washing, filtering and drying after the reaction is finished, and sieving with a 800-mesh sieve to obtain the superfine biomass filler.
Example 2
S1: drying corn straws, and then crushing the corn straws into 300 meshes to obtain wheat straw powder;
s2: placing 0.1g of corn straw powder, 100g of isopropanol and 5g of sulfuric acid in a reaction kettle, introducing nitrogen at 0.5MPa, reacting at 160 ℃ for 4 hours, cooling in an ice-water bath after the reaction is finished, and filtering to obtain filter residue and filtrate;
s3: the same as example 1;
s4: 0.1g of HMF, 2g of cobalt acetate tetrahydrate, 0.1g of manganese acetate tetrahydrate, 5g of sodium bromide, 0.1g of copper acetate and 100g of water are reacted and O is introduced2Reacting at 150 ℃ for 0.5h under 4MPa, filtering, washing and drying after the reaction is finished to obtain an FDCA powder product, and simultaneously recovering water;
s5: and (4) bleaching the filter residue obtained in the step (S2), bleaching 5g of filter residue, 100g of water and 1g of hydrogen peroxide in a bleaching reactor at 120 ℃ for 1h, washing, filtering and drying after the reaction is finished, and sieving with a 850-mesh sieve to obtain the superfine biomass filler.
Example 3
S1: drying coniferous wood, and then crushing the coniferous wood into 400 meshes to obtain coniferous wood powder;
s2: placing 20g of needle wood powder, 100g of ethanol and 0.01g of acetic acid in a reaction kettle, introducing nitrogen at 0.5MPa, reacting at 190 ℃ for 0.5h, cooling in an ice-water bath after the reaction is finished, and filtering to obtain filter residue and filtrate;
s3: the same as example 1;
s4: reacting 20g of HMF, 0.1g of cobalt acetate tetrahydrate, 10g of manganese acetate tetrahydrate, 0.1g of sodium bromide, 2.5g of calcium acetate, 2.5g of lead acetate and 100g of acetic acid, introducing air to the reaction solution under 2MPa, reacting the reaction solution at 100 ℃ for 3 hours, filtering, washing and drying the reaction solution after the reaction is finished to obtain an FDCA powder product, and simultaneously recovering the acetic acid;
s5: and (4) bleaching the filter residue obtained in the step (S2), bleaching the filter residue 30g, water 100g and hydrogen peroxide 5g in a bleaching reactor at 100 ℃ for 4h, washing, filtering and drying after the reaction is finished, and sieving with a 800-mesh sieve to obtain the superfine biomass filler.
Example 4
S1: drying broadleaf wood, and then crushing to 400 meshes to obtain broadleaf wood powder;
s2: placing 5g of hardwood powder, 50g of ethanol, 50g of isopropanol and 0.01g of FDCA in a reaction kettle, introducing nitrogen at 0.5MPa, reacting at 160 ℃ for 6 hours, cooling in an ice-water bath after the reaction is finished, and filtering to obtain filter residue and filtrate;
s3: the same as example 1;
s4: reacting 10g of HMF, 10g of cobalt acetate tetrahydrate, 5g of manganese acetate tetrahydrate, 10g of sodium bromide, 5g of cerium chloride, 5g of chromium chloride and 100g of acetic acid, introducing air to the mixture under 0.5MPa, reacting the mixture at 80 ℃ for 8 hours, filtering, washing and drying the mixture after the reaction is finished to obtain an FDCA powder product, and simultaneously recovering the acetic acid;
s5: and (4) bleaching the filter residue obtained in the step (S2), bleaching 15g of filter residue, 100g of water and 2.5g of hydrogen peroxide in a bleaching reactor at 40 ℃ for 9 hours, washing, filtering and drying after the reaction is finished, and sieving with a 900-mesh sieve to obtain the superfine biomass filler.
Example 5
S1: drying wheat straw and broad-leaved wood, and pulverizing to 200 meshes to obtain wheat straw-broad-leaved wood powder;
s2: placing 10g of wheat straw-hardwood powder, 50g of ethanol, 50g of isopropanol and 2.5g of carbon-based solid acid into a reaction kettle, introducing nitrogen at 0.5MPa, reacting at 170 ℃ for 5 hours, cooling in an ice-water bath after the reaction is finished, and filtering to obtain filter residue and filtrate;
s3: the same as example 1;
s4: 2g of HMF, 5g of cobalt acetate tetrahydrate, 2.5g of manganese acetate tetrahydrate, 5g of sodium bromide, 2g of magnesium acetate, 3g of copper acetate and 100g of water were reacted, and O was introduced2Reacting at 120 ℃ for 4h under 2.5MPa, filtering, washing and drying after the reaction is finished to obtain an FDCA powder product, and simultaneously recovering water;
s5: and (5) bleaching the filter residue obtained in the step (S2), bleaching 20g of filter residue, 100g of water and 4g of hydrogen peroxide in a bleaching reactor at 80 ℃ for 9h, washing, filtering and drying after the reaction is finished, and sieving with a 850-mesh sieve to obtain the superfine biomass filler.
Example 6
S1: drying wheat straws and corn straws, and then crushing the dried wheat straws and corn straws into 400 meshes to obtain wheat straw-corn straw powder;
s2: placing 5g of wheat straw-corn straw powder, 50g of ethanol and 1g of carbon-based solid acid in a reaction kettle, introducing nitrogen gas at 0.5MPa, reacting at 170 ℃ for 2 hours, cooling in an ice-water bath after the reaction is finished, and filtering to obtain filter residue and filtrate;
s3: the same as example 1;
s4: 8g of HMF, 3g of cobalt acetate tetrahydrate, 5g of manganese acetate tetrahydrate, 7g of sodium bromide, 6g of titanium tetrachloride and 100g of water were reacted, and O was introduced2Reacting at 100 ℃ for 4h under 3MPa, filtering, washing and drying after the reaction is finished to obtain an FDCA powder product, and simultaneously recovering water;
s5: and (5) bleaching the filter residue obtained in the step (S2), bleaching 15g of filter residue, 100g of water and 2g of hydrogen peroxide in a bleaching reactor at 80 ℃ for 6h, washing, filtering and drying after the reaction is finished, and sieving with a 800-mesh sieve to obtain the superfine biomass filler.
Test example 1 measurement of yield of HMF and FDCA
And (3) test groups: example 1-example 6;
the test method comprises the following steps:
(1) HMF yieldThe determination of (1): reaction product HMF reaction solution was filtered through a 0.22 μm organic pin filter. The filtrate was diluted with deionized water. HMF was quantitatively analyzed by High Performance Liquid Chromatography (HPLC) using VYDAC 214TP54(C18,
5 μm, 250 × 4.6mm), uv detector. The mobile phase is water/methanol (80:20, v/v), the flow rate is 0.6ml/min, the maximum absorption wavelength of HMF is 280nm, and the column temperature is 30 ℃. The average was taken in triplicate. Pure 5-hydroxymethylfurfural is used as a standard substance, and a standard curve of the hydroxymethylfurfural is prepared. The yield of HMF is defined as follows:
(2) determination of FDCA yield: the FDCA reaction solution was dissolved with an excess of base and filtered through a 0.22 μm organic needle filter. The filtrate was diluted with deionized water. HMF was quantitatively analyzed by High Performance Liquid Chromatography (HPLC) using VYDAC 214TP54(C18,
5 μm, 250 × 4.6mm), uv detector. The mobile phase is 0.05mol/L ammonium acetate water/methanol (50:50, v/v), the flow rate is 0.6ml/min, the maximum absorption wavelength of HMF is 265nm, and the column temperature is 30 ℃. The average was taken in triplicate. A standard curve of 2, 5-furandicarboxylic acid (FDCA) was prepared using pure 2, 5-furandicarboxylic acid as a standard. The yield of HMF is defined as follows:
and (3) test results: see table 1 for details.
Table 1 results of yield measurement of HMF and FDCA in examples 1 to 6
| Group of | HMF yield/%) | FDCA yield/% |
| Example 1 | 40.6 | 86.4 |
| Example 2 | 51.3 | 90.6 |
| Example 3 | 57.8 | 89.7 |
| Example 4 | 41.3 | 91.6 |
| Example 5 | 49.5 | 92.5 |
| Example 6 | 39.4 | 88.7 |
As can be seen from the data in the table, the preparation of the biological platform molecules HMF and FDCA from non-grain fiber materials such as straws, broad-leaved wood and needle-leaved wood has better yield, and the high yield and self-separation of FDCA can be realized by adopting a Co/Mn/Br system to catalyze HMF to prepare FDCA.
Experimental example 2 Effect of Pre-treatment pulverized particle size on HMF and FDCA yields
And (3) test groups: example 1, comparative example 1 to comparative example 5 were different from example 1 in the crushed particle size in step S1, and comparative example 1 to comparative example 5 were 100 mesh, 300 mesh, 400 mesh, 500 mesh, and 600 mesh in this order in the crushed particle size in step S1, and the rest was the same as example 1;
the test method comprises the following steps: the same as in test example 1;
and (3) test results: see table 2 for details.
TABLE 2 results of yield measurement of HMF and FDCA in example 1, comparative example 1 to comparative example 5
| Group of | Crushed particle size/mesh | HMF yield/%) | FDCA yield/% |
| Comparative example 1 | 100 | 28.9 | 60.3 |
| Example 1 | 200 | 40.6 | 86.4 |
| Comparative example 2 | 300 | 50.2 | 89.2 |
| Comparative example 3 | 400 | 58.3 | 92.6 |
| Comparative example 4 | 500 | 62.1 | 93.5 |
| Comparative example 5 | 600 | 62.9 | 92.8 |
As shown in the reference table 2, as the pre-treatment crushed particle size increases, the yield of HMF and FDCA in the later period also increases, but when the pre-treatment crushed particle size exceeds 400 meshes, the increase rate of the yield of HMF and FDCA decreases, and the pre-treatment crushed particle size of the combined application is selected to be 200-400 meshes.
Test example 3 measurement of Properties of ultrafine Filler
And (3) test groups:
(1) blank group: no filler is added to the PBAT;
(2) test groups: mixing the biomass powder prepared in the embodiment 1 with PBAT, wherein the mixture accounts for 10%, 20%, 30% and 40% of the weight of the PBAT, and the mixture is sequentially marked as a test group 1, a test group 2, a test group 3 and a test group 4;
(3) comparison group: mixing calcium carbonate and PBAT, wherein the calcium carbonate accounts for 20% of the weight of the PBAT
The test method comprises the following steps:
and (3) putting the raw materials of the blank group, the test group and the comparison group into a double-screw extruder, extruding and granulating at the granulation temperature of 180 ℃, putting the extruded and granulated product into an oven at the temperature of 80 ℃ for drying for 4 hours, preparing a standard test sample strip by using an injection molding machine, and testing.
(1) Tensile Property test
The specimens subjected to the tensile test had a dumbbell-shaped appearance, a total length of 115mm, a thickness of 4mm, a narrow portion length of 100mm, a narrow portion width of 10mm, and a tensile rate of 500mm/min, and were tested in accordance with the national standard GB-T1040.
(2) Density test
The test is carried out by a plastic densitometer, which measures the weight of the sample in air first and then in water, and the instrument automatically determines the density of the sample.
And (3) test results: see table 3 for details.
Table 3 extrusion Property test results for each group
| Group of | Addition amount/%) | Density/kg/m3 | Tensile Strength/N/(mm)2 | Elongation at break% |
| Blank group | 0 | 1.2 | 21.25 | 756 |
| Test group 1 | 10 | 1.15 | 19.4 | 590 |
| Test group 2 | 20 | 1.04 | 17.2 | 504 |
| Test group 3 | 30 | 0.99 | 10.3 | 420 |
| Test group 4 | 40 | 0.93 | 8.1 | 293 |
| Comparison group | 20 | 1.31 | 13.15 | 433 |
Referring to table 3, the FDCA is used for preparing the filter residue to prepare the ultrafine biomass fine powder, and the non-grain fiber is pulverized to 200-400 meshes, so that the preparation of the biological platform molecule is facilitated, the non-grain fiber can be further refined in the reaction, the particle size (more than 800 meshes) which cannot be achieved by adopting a conventional pulverization method is achieved, and two purposes are achieved at one stroke. And the PBAT filler obtained by filling the superfine biomass fine powder has lower density compared with the calcium carbonate filler, and the biomass fine powder filler has higher tensile strength and elongation at break when being filled by 20 percent.
While there have been shown and described what are at present considered the fundamental principles and essential features of the invention and its advantages, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing exemplary embodiments, but is capable of other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A method for preparing FDCA and full bio-based filler by using non-grain biomass raw materials is characterized by comprising the following steps:
s1: drying the non-grain fiber and then crushing to obtain non-grain fiber powder;
s2: reacting non-grain fiber powder, a solvent A and a catalyst, and filtering to obtain filter residue and filtrate;
s3: distilling the filtrate obtained in the step S2 to recover the solvent, so as to obtain 5-hydroxymethylfurfural;
s4: reacting 5-hydroxymethylfurfural, cobalt acetate tetrahydrate, manganese acetate tetrahydrate, sodium bromide, a fourth component metal salt and a solvent B, filtering, washing and drying to obtain FDCA powder;
s5: and bleaching the filter residue obtained in the step S2, washing, drying and crushing to obtain the superfine biomass filler.
2. The method for preparing FDCA and total bio-based filler using non-grain biomass feedstock as claimed in claim 1, wherein the non-grain fiber powder particle size in step S1 is 200-400 mesh.
3. The method of claim 1, wherein the non-grain fiber powder in step S2 is 0.1 to 20 parts by weight, the solvent a is 100 parts by weight, and the catalyst is 0.01 to 5 parts by weight.
4. The method for preparing FDCA and total bio-based filler using non-grain biomass feedstock as claimed in claim 1 or 3, wherein the non-grain fiber powder, solvent A and catalyst reaction conditions in step S2 are: introducing nitrogen into the reaction kettle at 0.5MPa and 190 ℃ for reaction for 0.5-8h, and cooling in an ice-water bath after the reaction is finished.
5. The method for preparing FDCA and total bio-based filler using non-food biomass feedstock as claimed in claim 4, wherein solvent A in step S2 is a low boiling point solvent, specifically one or more of tetrahydrofuran, ethanol, isopropanol; the catalyst is one or more of inorganic acid, organic acid and solid acid, the inorganic acid is hydrochloric acid or sulfuric acid, the organic acid is acetic acid or FDCA, and the solid acid is carbon-based solid acid.
6. The method of claim 5, wherein the non-grain cellulose is one or more of grass fiber and wood fiber; the grass fiber is one or more of wheat straw and corn straw; the wood fiber is one or more of coniferous wood and broadleaf wood.
7. The method of claim 1, wherein in step S4, the amount of 5-hydroxymethylfurfural is 0.1 to 20 parts by weight, the amount of cobalt acetate tetrahydrate is 0.1 to 10 parts by weight, the amount of manganese acetate tetrahydrate is 0.1 to 10 parts by weight, the amount of sodium bromide is 0.1 to 10 parts by weight, the amount of the fourth component metal salt is 0.1 to 10 parts by weight, and the amount of the solvent B is 100 parts by weight.
8. The method for preparing FDCA and total bio-based filler using non-food biomass feedstock as claimed in claim 1 or 7, wherein the reaction conditions of 5-hydroxymethylfurfural, cobalt acetate tetrahydrate, manganese acetate tetrahydrate, sodium bromide, fourth component metal salt and solvent B in step S4 are as follows: introduction of O2Or air 0.5-4MPa, and reacting at 80-150 deg.C for 0.5-8 h.
9. The method of claim 8, wherein the solvent B is acetic acid or water; the fourth component metal salt is one or more of zirconium acetate, copper acetate, magnesium acetate, calcium acetate, lead acetate, titanium tetrachloride, cerium chloride and chromium chloride.
10. The method for preparing FDCA and total bio-based filler using non-grain biomass feedstock as claimed in claim 1, wherein the bleaching treatment in step S5 is specifically: 5-30 parts of filter residue, 100 parts of water and 0.5-5 parts of hydrogen peroxide by weight are taken, bleached for 1-9 hours at 40-120 ℃, and washed, filtered, dried and crushed after the reaction is finished to obtain the superfine biomass filler, wherein the particle size of the superfine biomass filler is not less than 800 meshes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210223966.6A CN114605359A (en) | 2022-03-09 | 2022-03-09 | Method for preparing FDCA (fully drawn yarn) and total bio-based filler by using non-grain biomass raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210223966.6A CN114605359A (en) | 2022-03-09 | 2022-03-09 | Method for preparing FDCA (fully drawn yarn) and total bio-based filler by using non-grain biomass raw material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114605359A true CN114605359A (en) | 2022-06-10 |
Family
ID=81861192
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210223966.6A Pending CN114605359A (en) | 2022-03-09 | 2022-03-09 | Method for preparing FDCA (fully drawn yarn) and total bio-based filler by using non-grain biomass raw material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114605359A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040571A (en) * | 2009-10-19 | 2011-05-04 | 佳能株式会社 | Method of producing 2,5-furandicarboxylic acid |
| CN102617523A (en) * | 2012-03-09 | 2012-08-01 | 中南大学 | Method for preparing 5-hydroxymethylfurfural by hydrothermally decomposing wood fibers |
| CN106336386A (en) * | 2016-07-20 | 2017-01-18 | 南京林业大学 | Method for synthesizing furan diacid from biomass raw material |
| CN106565647A (en) * | 2016-10-29 | 2017-04-19 | 华东理工大学 | Method for preparing 2, 5-furandicarboxylic acid by conducting catalytic oxidation on 5-hydroxymethylfurfural |
| CN106832424A (en) * | 2017-03-15 | 2017-06-13 | 苏州普利金新材料有限公司 | A kind of method that cellulose powder and Biodegradable resin blending modified material prepare inflation film |
| CN108997278A (en) * | 2018-07-17 | 2018-12-14 | 中国科学院长春应用化学研究所 | A kind of 2,5- furandicarboxylic acid and 2,5- furyl preparation process of polyester |
| CN110218424A (en) * | 2019-06-05 | 2019-09-10 | 辽宁东盛塑业有限公司 | Straw powder/PLA/PBAT biomass full degradable plastics and preparation method |
| CN111377890A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Method for producing 2,5-furandicarboxylic acid from 5-hydroxymethylfurfural |
| CN112830915A (en) * | 2019-11-19 | 2021-05-25 | 中国科学院宁波材料技术与工程研究所 | Low-temperature preparation method of 2, 5-furandicarboxylic acid |
-
2022
- 2022-03-09 CN CN202210223966.6A patent/CN114605359A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040571A (en) * | 2009-10-19 | 2011-05-04 | 佳能株式会社 | Method of producing 2,5-furandicarboxylic acid |
| CN102617523A (en) * | 2012-03-09 | 2012-08-01 | 中南大学 | Method for preparing 5-hydroxymethylfurfural by hydrothermally decomposing wood fibers |
| CN106336386A (en) * | 2016-07-20 | 2017-01-18 | 南京林业大学 | Method for synthesizing furan diacid from biomass raw material |
| CN106565647A (en) * | 2016-10-29 | 2017-04-19 | 华东理工大学 | Method for preparing 2, 5-furandicarboxylic acid by conducting catalytic oxidation on 5-hydroxymethylfurfural |
| CN106832424A (en) * | 2017-03-15 | 2017-06-13 | 苏州普利金新材料有限公司 | A kind of method that cellulose powder and Biodegradable resin blending modified material prepare inflation film |
| CN108997278A (en) * | 2018-07-17 | 2018-12-14 | 中国科学院长春应用化学研究所 | A kind of 2,5- furandicarboxylic acid and 2,5- furyl preparation process of polyester |
| CN111377890A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Method for producing 2,5-furandicarboxylic acid from 5-hydroxymethylfurfural |
| CN110218424A (en) * | 2019-06-05 | 2019-09-10 | 辽宁东盛塑业有限公司 | Straw powder/PLA/PBAT biomass full degradable plastics and preparation method |
| CN112830915A (en) * | 2019-11-19 | 2021-05-25 | 中国科学院宁波材料技术与工程研究所 | Low-temperature preparation method of 2, 5-furandicarboxylic acid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101835609B1 (en) | Catalyst for producing 2,5- furandicarboxlic acid and method for producing 2,5- furandicarboxlic acid using the same | |
| Gallezot | Conversion of biomass to selected chemical products | |
| KR101936966B1 (en) | Process for the synthesis of 2,5-furandicarboxylic acid | |
| EP2513080B1 (en) | Method for producing furfural from lignocellulosic biomass material | |
| DE102011077232B4 (en) | Process for the catalytic production of formic acid | |
| Yamaguchi et al. | One-pot conversion of cellulose to isosorbide using supported metal catalysts and ion-exchange resin | |
| Yi et al. | Formaldehyde formation during the preparation of dialdehyde carboxymethyl cellulose tanning agent | |
| KR102046210B1 (en) | Process for making 2,5-furandicarboxylic acid | |
| US8440845B2 (en) | Process for converting polysaccharides in an inorganic molten salt hydrate | |
| Wang et al. | Production of furfural with high yields from corncob under extremely low water/solid ratios | |
| WO2017076947A1 (en) | Process for preparing furan-2,5-dicarboxylic acid | |
| EP2994459B1 (en) | Process and intermediates for the production of furan-2,5-dicarboxylic acid or derivatives thereof | |
| DE112016001317T5 (en) | Carbonate-assisted carboxylation reaction for the synthesis of valuable organic compounds | |
| EP2431394A1 (en) | Simultaneous hydrolysis and hydrogenation of cellulose | |
| US20150246865A1 (en) | Process for making levulinic acid | |
| Zhang et al. | Deconstruction of biomass into lignin oil and platform chemicals over heteropoly acids with carbon-supported palladium as a hybrid catalyst under mild conditions | |
| Peng et al. | Effect of metal salts existence during the acid-catalyzed conversion of glucose in methanol medium | |
| KR20150091384A (en) | Process for the production of a biomass hydrolysate | |
| Kasmi et al. | Effective and facile solvent-free synthesis route to novel biobased monomers from vanillic acid: Structure–thermal property relationships of sustainable polyesters | |
| CN114773300A (en) | Method for preparing 2, 5-furandicarboxylic acid from furfural | |
| CN114605359A (en) | Method for preparing FDCA (fully drawn yarn) and total bio-based filler by using non-grain biomass raw material | |
| CN111187238B (en) | Synthetic method of 2, 5-furandicarboxylic acid | |
| CN110102343B (en) | Composite acid catalyst and method for preparing 5-hydroxymethylfurfural by catalyzing saccharides through composite acid catalyst | |
| Mishra et al. | Furfuryl alcohol—a promising platform chemical | |
| CN108863770A (en) | A kind of technique of levulic acid preparation and its solvent and catalyst recycling |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |