CN117164735B - Method for preparing galactoglucomannan-containing material from coffee grounds and application thereof - Google Patents
Method for preparing galactoglucomannan-containing material from coffee grounds and application thereof Download PDFInfo
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- CN117164735B CN117164735B CN202311202322.XA CN202311202322A CN117164735B CN 117164735 B CN117164735 B CN 117164735B CN 202311202322 A CN202311202322 A CN 202311202322A CN 117164735 B CN117164735 B CN 117164735B
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- 239000000463 material Substances 0.000 title claims abstract description 69
- 229920002324 Galactoglucomannan Polymers 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 49
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000007787 solid Substances 0.000 claims abstract description 45
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 230000002378 acidificating effect Effects 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000011592 zinc chloride Substances 0.000 claims description 8
- 235000005074 zinc chloride Nutrition 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 5
- 108010059892 Cellulase Proteins 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 5
- 239000001110 calcium chloride Substances 0.000 claims description 5
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 5
- 229940106157 cellulase Drugs 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- 238000011033 desalting Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229920001282 polysaccharide Polymers 0.000 abstract description 23
- 239000005017 polysaccharide Substances 0.000 abstract description 23
- 239000002131 composite material Substances 0.000 abstract description 22
- 150000004676 glycans Chemical class 0.000 abstract description 21
- 235000013305 food Nutrition 0.000 abstract description 6
- 238000004806 packaging method and process Methods 0.000 abstract description 3
- 229920002581 Glucomannan Polymers 0.000 abstract 2
- 229940046240 glucomannan Drugs 0.000 abstract 2
- 239000012153 distilled water Substances 0.000 description 13
- 238000011084 recovery Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 125000003147 glycosyl group Chemical group 0.000 description 11
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 10
- 239000001913 cellulose Substances 0.000 description 10
- 229920002678 cellulose Polymers 0.000 description 10
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 10
- 125000000311 mannosyl group Chemical group C1([C@@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 229920000926 Galactomannan Polymers 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- OMDQUFIYNPYJFM-XKDAHURESA-N (2r,3r,4s,5r,6s)-2-(hydroxymethyl)-6-[[(2r,3s,4r,5s,6r)-4,5,6-trihydroxy-3-[(2s,3s,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxan-2-yl]methoxy]oxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)[C@H](O)[C@H](O)[C@H](O)O1 OMDQUFIYNPYJFM-XKDAHURESA-N 0.000 description 5
- 108090000790 Enzymes Proteins 0.000 description 5
- 102000004190 Enzymes Human genes 0.000 description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 5
- 229940088598 enzyme Drugs 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229920002488 Hemicellulose Polymers 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229920000057 Mannan Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- LUEWUZLMQUOBSB-GFVSVBBRSA-N mannan Chemical class O[C@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@@H](O[C@@H]2[C@H](O[C@@H](O[C@H]3[C@H](O[C@@H](O)[C@@H](O)[C@H]3O)CO)[C@@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O LUEWUZLMQUOBSB-GFVSVBBRSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- LIDBEQRROMKHRT-UHFFFAOYSA-M sodium;acetic acid;chlorite Chemical compound [Na+].[O-]Cl=O.CC(O)=O LIDBEQRROMKHRT-UHFFFAOYSA-M 0.000 description 3
- -1 zinc ion polysaccharide Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- RYYVLZVUVIJVGH-UHFFFAOYSA-N caffeine Chemical compound CN1C(=O)N(C)C(=O)C2=C1N=CN2C RYYVLZVUVIJVGH-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002519 galactosyl group Chemical group C1([C@H](O)[C@@H](O)[C@@H](O)[C@H](O1)CO)* 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 2
- 229960002218 sodium chlorite Drugs 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- QQPXLQKIPGPFIK-UHFFFAOYSA-N C(C)(=O)OO.S(=O)(=O)(O)O Chemical compound C(C)(=O)OO.S(=O)(=O)(O)O QQPXLQKIPGPFIK-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- LPHGQDQBBGAPDZ-UHFFFAOYSA-N Isocaffeine Natural products CN1C(=O)N(C)C(=O)C2=C1N(C)C=N2 LPHGQDQBBGAPDZ-UHFFFAOYSA-N 0.000 description 1
- 241000186660 Lactobacillus Species 0.000 description 1
- 241000533293 Sesbania emerus Species 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229960001948 caffeine Drugs 0.000 description 1
- VJEONQKOZGKCAK-UHFFFAOYSA-N caffeine Natural products CN1C(=O)N(C)C(=O)C2=C1C=CN2C VJEONQKOZGKCAK-UHFFFAOYSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007979 citrate buffer Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- 229940039696 lactobacillus Drugs 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011846 petroleum-based material Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 235000013406 prebiotics Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 231100000027 toxicology Toxicity 0.000 description 1
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Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses a method for preparing galacto-glucomannan-containing material from coffee grounds and application thereof, wherein the method comprises the steps of combining the coffee grounds with acidic hydrogen peroxide, reacting at 20-150 ℃, and carrying out solid-liquid separation, wherein the obtained solid is the galacto-glucomannan-containing material. The method for preparing the galactoglucomannan-enriched material from the coffee grounds can extract the galactoglucomannan in the coffee grounds with high yield, effectively solves the problem of low yield of polysaccharide extracted from the coffee grounds, and the polysaccharide product obtained by the method has higher purity. The polysaccharide composite film provided by the invention has certain toughness, and is suitable for the fields of food packaging, materials and the like. The galactoglucomannan material prepared from the coffee grounds and the application method thereof have reference significance for the application of coffee grounds in the fields of food, materials and the like.
Description
Technical Field
The invention belongs to the technical field of comprehensive utilization of agricultural and forestry biomass, and particularly relates to a method for preparing a galactoglucomannan-containing material from coffee grounds and application thereof.
Background
Coffee Grounds (SCG) are a by-product of coffee production, which produces about 600 ten thousand tons of SCG per year. SCG is currently used as fertilizer, feed and fuel in many countries and regions, but direct treatment of SCG containing abundant organic components creates ecological toxicological problems and environmental pollution problems, and decomposition of coffee grounds-containing soil causes release of caffeine, tannin and polyphenol in the atmosphere; incineration leads to the generation of carbon monoxide and nitrogen oxides, which accelerates global warming.
The coffee contains 13.2-18.4% cellulose and 20-30% mannans, wherein the SCG retains the main polysaccharide substances, about 50% of the dry weight of the coffee beans, and the mannans component has potential application value as polysaccharide. The current research shows that the mannans can play a prebiotic role in promoting the growth of beneficial bacteria in human intestinal tracts, and can promote the formation of biological films of lactobacillus strains. Apart from polysaccharides, some other substances, such as lignin, oils and proteins, are retained in SCG. Is a necessary factor to be considered in the production and purification of the coffee grounds polysaccharide.
Chinese invention CN114286829a discloses a process for preparing hemicellulose and holocellulose products from carbohydrate rich materials including coffee grounds, which combines an aqueous slurry of coffee grounds with an alkaline hydrogen peroxide solution, separates the solid fraction from the liquid fraction of the alkaline hydrogen peroxide treated slurry, adjusts the pH of the remaining concentrated liquid to a pH of 4.0-6.0 by means of a pH adjuster stage, and finally precipitates the hemicellulose product by adding ethanol to obtain the hemicellulose product. The final yield of glycans obtained using this method is low, and the hemicellulose and cellulose products obtained only account for about 16% -30% (w/w) and about 25% -35% (w/w) of SCG dry weight. The core of this method is to dissolve the coffee grounds polysaccharides first by alkaline conditions and then regenerate the polysaccharides by precipitation. The obtained glycan has low yield, the natural structure is destroyed in the dissolving process, the molecular weight is small, and the glycan material performance is weak.
The zinc ion polysaccharide film is a novel biological material and is mainly characterized by good biocompatibility and degradability, and excellent mechanical strength and bioactivity. The zinc ion membrane-making principle is based on O 3H···O5 hydrogen bond, which is the reason for the tight and insoluble cellulose network structure. Zn 2+ ions facilitate cellulose dissolution by breaking or breaking the O 3H···O5 hydrogen bond of cellulose, while Ca 2+ ions exist to easily crosslink zinc-cellulose chains, form nanofibrils and produce strong transparent films. The zinc ion polysaccharide composite membrane prepared by the galactomannan material obtained by the method belongs to a degradable biological film material, wherein the added galactomannan oligosaccharide can enhance the mechanical property and air permeability of the film, supplement the antioxidant and antibacterial properties of the film, and can be applied to food packaging.
Disclosure of Invention
The invention aims to: the invention aims to solve the technical problem of providing a method for preparing a galactoglucomannan-containing material from coffee grounds.
The invention also solves the technical problem of providing the application of the galactoglucomannan-containing material.
The invention also solves the technical problem of providing a film prepared from a galactoglucomannan-containing material.
In order to solve the technical problems, the invention discloses the following technical scheme:
In a first aspect, the present invention discloses a method for preparing a galactoglucomannan-containing material from coffee grounds.
The method comprises the following steps: combining coffee grounds with acidic hydrogen peroxide, reacting at 20-150 ℃, and carrying out solid-liquid separation to obtain a solid which is a galactoglucomannan-containing material or adopting other oxidation pretreatment methods.
Wherein the coffee grounds are deoiled coffee grounds; the deoiling coffee grounds are obtained by extracting deoiling with an organic solvent, wherein the organic solvent comprises any one or a combination of at least two of n-hexane, petroleum ether, n-pentane, acetone, ethanol and isopropanol, and is preferably n-hexane.
Wherein the acidic hydrogen peroxide is a combination of hydrogen peroxide and acetic acid; wherein the volume ratio of the hydrogen peroxide to the acetic acid is 3:7-7:3, and is preferably 1:0.5-1.5.
Wherein the mass volume ratio of the coffee grounds to the acidic hydrogen peroxide is 1:5-25 g/ml, preferably 1:10-20 g/ml, and preferably 1:14-16 g/ml.
Wherein, inorganic acid is used as a catalyst in the reaction process; preferably, the inorganic acid comprises any one or a combination of sulfuric acid, hydrochloric acid and phosphoric acid; preferably, the final concentration of the inorganic acid in the reaction system is 80 to 300mM, preferably 130 to 260mM, and preferably 180 to 220mM.
Wherein the temperature of the reaction is 35-120 ℃, preferably 50-90 ℃.
Wherein the reaction time is 0.2 to 7 hours, preferably 0.6 to 5 hours, preferably 1 to 3 hours.
Other oxidative pretreatment methods are any one or a combination of at least two of sodium chlorite pretreatment, alkaline hydrogen peroxide pretreatment, sodium chlorite acetic acid pretreatment.
Further, the method further comprises any one of the following methods:
the method comprises the following steps: the obtained solid is combined with strong alkali, reacted and separated from solid and liquid, and the obtained solid is a galactoglucomannan-containing material.
Wherein the strong base comprises sodium hydroxide and/or potassium hydroxide; preferably, the strong base is added in the form of a strong base solution having a concentration of strong base of 2-5M, preferably 4M.
Wherein the temperature of the reaction is 15-30 ℃, preferably 20-30 ℃, and preferably 25 ℃.
Wherein the reaction is carried out with stirring, preferably at a rate of 100 to 1400rpm, preferably 500 to 900rpm, preferably 600 to 700rpm.
Wherein the reaction time is 1 to 6 hours, preferably 3 to 5 hours, preferably 2 to 4 hours.
The second method is as follows: the obtained solid is subjected to enzymolysis by cellulase, and solid-liquid separation, and the obtained solid is a galactoglucomannan-containing material.
Wherein the dosage of the cellulase is 15-25 FPU/g solid, preferably 17-22 FPU/g solid;
wherein the enzymolysis temperature is 50-70 ℃, preferably 55-65 ℃;
wherein the enzymolysis time is 43-53 h.
In a second aspect, the invention discloses the use of a galactoglucomannan-containing material for preparing a film.
Wherein the galactoglucomannan-containing material is prepared by the method of the first aspect described above, preferably by method one.
In a third aspect, a film is disclosed.
Wherein the film is prepared from a galactoglucomannan-containing material prepared by the method of the first aspect described above, preferably prepared by method one.
In the above second aspect and the above third aspect,
The tensile strength of the film is 1 to 15N/mm 2, preferably 8 to 12N/mm 2, preferably 9.5 to 10.5N/mm 2.
The preparation method of the film comprises the following steps: mixing the galactoglucomannan-containing material with zinc chloride and water, heating and stirring to obtain a mixed solution containing the galactoglucomannan-containing material and the zinc chloride; adding calcium chloride into the obtained mixed solution, and stirring to realize crosslinking to obtain a gel solution; after the obtained gel solution is solidified, a film is obtained.
The film is prepared by the following method: mixing the galactoglucomannan-containing material with zinc chloride and water, heating and stirring to obtain a mixed solution containing the galactoglucomannan-containing material and the zinc chloride; adding calcium chloride into the obtained mixed solution, and stirring to realize crosslinking to obtain a gel solution; after the obtained gel solution is solidified, a film is obtained.
Wherein the dosage ratio of the galactoglucomannan-containing material to zinc chloride to water is 0.08-0.3 g: 5-10 g:1 to 5ml, preferably 0.05 to 0.2g: 6-8.5 g:2 to 4ml, preferably 0.1g:7g:3ml.
Wherein the temperature of the heating and stirring is 60-80 ℃, preferably 60-70 ℃, preferably 65 ℃.
Wherein the heating and stirring time is 60-120 min, preferably 80-100 min, preferably 90min;
wherein the mass ratio of the calcium chloride to the galactoglucomannan-containing material is 0.1:0.1 to 0.2, preferably 0.1:0.15.
Wherein, after the obtained gel solution is solidified, the obtained film specifically comprises: cooling the gel solution on a plate to room temperature, immersing the gel solution in absolute ethyl alcohol to solidify the film completely, desalting the film by a hot bath, and plasticizing the film by a glycerol bath to obtain the film; in some embodiments, to pour the film solution into a dish, the gel-loaded dish is immersed in absolute ethanol at 4-8deg.C for 40-90min, after the mixture has cooled to below 50deg.C. Taking out the composite membrane after solidification, immersing the composite membrane in hot water at 65-85 ℃ for 5-15 min for desalting, immersing the composite membrane in glycerol for 15-30 min for plasticizing, and drying the obtained composite membrane sample for 48h under the conditions of 18-28 ℃ and relative humidity of 40-80%.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
(1) The method for preparing the galactoglucomannan-enriched material from the coffee grounds can extract the galactoglucomannan in the coffee grounds with high yield, effectively solves the problem of low yield of polysaccharide extracted from the coffee grounds, and the polysaccharide product obtained by the method has higher purity. The recovery rate of the solid after the raw material treatment is 40.26 to 79.1 percent, the retention rate of the total glycosyl is 66.55 to 96.8 percent, the percentage of the medium glycosyl is 10.2 to 24.5 percent, the percentage of the galactosyl is 0.5 to 1.48 percent, and the percentage of the mannosyl is 46.78 to 84.1 percent
(2) The polysaccharide composite film provided by the invention has certain toughness, and is suitable for the fields of food packaging, materials and the like.
(3) The galactoglucomannan material prepared from the coffee grounds and the application method thereof have reference significance for the application of coffee grounds in the fields of food, materials and the like.
Drawings
The foregoing and/or other advantages of the invention will become more apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings and detailed description.
FIG. 1 is a composite film appearance prepared from the galactoglucomannan material of the present invention.
FIG. 2 is a graph showing a tensile analysis of a coffee galactoglucomannan composite membrane prepared according to the present invention.
Detailed Description
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are commercially available.
In the following examples, the hydrogen peroxide was 30% hydrogen peroxide unless otherwise specified.
In the following examples, the acetic acid was 99.5% acetic acid unless otherwise specified.
In the following examples, the sulfuric acid was 98% sulfuric acid and the hydrochloric acid was 37.5% hydrochloric acid unless otherwise specified.
In the following examples, the galactomannan material is a galactomannan-containing material unless otherwise specified.
In the following examples, the polysaccharide glycosyl component is galactomannan, unless otherwise specified.
EXAMPLE 1 peroxyacetic acid sulfuric acid Process
Taking 2g of deoiled coffee grounds, mixing hydrogen peroxide and acetic acid at a ratio of 1:1 (v/v) to prepare 30ml hydrogen peroxide solution, 1:15 The solid-to-liquid ratio of (w/v) was added while 98% concentrated sulfuric acid was added as a catalyst at a final concentration of 200mM, and the mixture was pretreated in an oil bath at 60℃for 2 hours. Centrifuging to separate solid residues, washing with distilled water to neutrality, and vacuum drying to obtain galactoglucomannan material. The total solid recovery rate was 79.1% and the total polysaccharide glycosyl component content was 69.55%. Wherein the galactose group accounts for 1.48%, the glucose group accounts for 20.03%, and the mannose group accounts for 48.04%.
EXAMPLE 2 peroxyacetate acid treatment
Taking 2g of deoiled coffee grounds, mixing hydrogen peroxide and acetic acid at a ratio of 1:1 (v/v) to prepare 30ml hydrogen peroxide solution, 1:15 (w/v) solid to liquid ratio while hydrochloric acid (200 mM) was added as a catalyst, and the mixture was pretreated in an oil bath at 60℃for 2 hours. Centrifuging to separate solid residues, washing with distilled water to neutrality, and vacuum drying to obtain galactoglucomannan material. The total solid recovery rate is 77.6%, and the total content of glycosyl components is 68.07%. Wherein the galactose group accounts for 1.42%, the glucose group accounts for 19.87%, and the mannose group accounts for 46.78%.
Example 3 acid peroxyacetic acid combined alkaline treatment
Taking 2g of deoiled coffee grounds, hydrogen peroxide and acetic acid at a ratio of 1:1 (v/v) to prepare hydrogen peroxide solution by mixing according to the proportion of 1:15 The solid-to-liquid ratio of (w/v) was added to 30ml of hydrogen peroxide solution, and sulfuric acid (200 mM) was added as a catalyst, followed by pretreatment in an oil bath at 60℃for 2 hours. The solid residue was centrifuged and washed with distilled water to neutrality. The residue was mixed at a solid-to-liquid ratio of 1:25g/ml are added to 4M sodium hydroxide solution and reacted at 700rpm for 4 hours at room temperature. After the reaction, the solid residue was centrifuged, washed with distilled water to neutrality and dried under vacuum to obtain a galactoglucomannan-enriched material having a total content of glycosyl components of 96.8%. The total solids recovery was 40.26% with a galactosyl ratio of 0.5%, a glucosyl ratio of 24.5% and a mannosyl ratio of 71.8%.
Example 4 acid peroxyacetic acid Combined enzymatic treatment
Taking 2g of deoiled coffee grounds, hydrogen peroxide and acetic acid at a ratio of 1:1 (v/v) to prepare hydrogen peroxide solution by mixing according to the proportion of 1:15 The solid-to-liquid ratio of (w/v) was added to 30ml of hydrogen peroxide solution, and sulfuric acid (200 mM) was added as a catalyst, followed by pretreatment in an oil bath at 60℃for 2 hours. The solid residue was centrifuged and washed with distilled water to neutrality. The residue was enzymatically hydrolyzed in a constant temperature shaker at 50℃and 150rpm at an enzyme loading of 20FPU/g of absolute substrate for 48 hours using Xia Cheng cellulase (filter paper enzyme activity 51.8FPIU/g, enzyme activity defined as the amount of enzyme required to produce 1. Mu. Mol of glucose at 50℃and pH4.8, expressed as FPIU/mL) in 50mM citrate buffer at pH 4.8. And (5) drying the residues after enzymolysis under vacuum to obtain the galactoglucomannan material. The total solid recovery rate was 66.7% and the total glycosyl component content was 84.9%. Wherein the galactose group content is 0.6%, the glucose group content is 6.3%, and the mannose group content is 78.0%.
Comparative example 1 sodium hydroxide alkaline peroxide process
2G of deoiled coffee grounds are taken and 5% hydrogen peroxide is brought to pH 11.5 using 15% sodium hydroxide to give 30ml of an alkaline hydrogen peroxide solution at 1:15 (w/v) solid-to-liquid ratio and adding the coffee grounds. The mixture was stirred magnetically continuously in an Erlenmeyer flask at 90℃and 350rpm for 3h. Centrifuging to separate solid residues, washing the solid with distilled water to be neutral, and vacuum drying to obtain the galactoglucomannan material. The total solid recovery rate is 38.7%, and the total content of glycosyl components is 85.19%. Wherein the galactose radical accounts for 2.17 percent, the glucose radical accounts for 30.43 percent, and the mannose radical accounts for 52.59 percent.
Comparative example 2 treatment with alkaline Hydrogen peroxide by Potassium hydroxide
2G of deoiled coffee grounds were taken and 5% hydrogen peroxide was brought to pH 11.5 using 15% potassium hydroxide to give 30ml of an alkaline hydrogen peroxide solution at 1:15 (w/v) solid-to-liquid ratio and adding the coffee grounds. The mixture was stirred magnetically continuously in an Erlenmeyer flask at 90℃and 350rpm for 3h. Centrifuging to separate solid residues, washing the solid with distilled water to be neutral, and vacuum drying to obtain the galactoglucomannan material. The total solid recovery rate was 32.5% and the total glycosyl component content was 84.36%. Wherein the galactose group content is 2.26%, the glucose group content is 28.91%, and the mannose group content is 53.19%.
Comparative example 3 sodium carbonate alkaline peroxide process treatment
2G of deoiled coffee grounds were taken and 5% hydrogen peroxide was brought to pH 11.5 using 15% sodium carbonate to give 30ml of an alkaline hydrogen peroxide solution at 1:15 (w/v) solid-to-liquid ratio and adding the coffee grounds. The mixture was stirred magnetically continuously in an Erlenmeyer flask at 90℃and 350rpm for 3h. Centrifuging to separate solid residues, washing the solid with distilled water to be neutral, and vacuum drying to obtain the galactoglucomannan material. The total solid recovery rate is 35.4%, and the total content of glycosyl components is 83.25%. Wherein the galactose group content is 2.07%, the glucose group content is 28.30%, and the mannose group content is 52.88%.
Comparative example 4 sodium chlorite treatment
20G of deoiled coffee grounds and 20g of NaClO 2 were taken at a ratio of 1:15 (w/v) solid-to-liquid ratio to distilled water 300ml, continuously magnetically stirring at 90℃and 350rpm in an Erlenmeyer flask for 3 hours, centrifuging to separate a solid residue, washing the solid with distilled water to neutrality, and vacuum drying to obtain a galactoglucomannan material. The total solid recovery rate is 65.7%, and the total content of glycosyl components is 69.84%. Wherein the galactose group accounts for 1.38%, the glucose group accounts for 21.54%, and the mannose group accounts for 46.92%.
Comparative example 5 sodium chlorite acetic acid treatment
20G of deoiled coffee grounds and 20g of NaClO 2 were taken at a ratio of 1:15 (w/v) solid-to-liquid ratio, adding distilled water 300ml, adjusting pH to 4.0 with acetic acid, stirring with continuous magnetic force at 90deg.C and 350rpm in an erlenmeyer flask for 3h, centrifuging to separate solid residue, washing the solid with distilled water to neutrality, and vacuum drying to obtain galactoglucomannan material. The total solid recovery rate is 49.0%, and the total content of glycosyl components is 88.06%. Wherein the galactose group content is 1.67%, the glucose group content is 27.21%, and the mannose group content is 59.18%.
The solid recovery and the compositional characteristics of the galactoglucomannan material obtained above are shown in table 1.
Table 1: solid recovery of galactoglucomannan material and glycosyl duty cycle
The following comparative examples and examples describe a specific method for preparing the galactoglucomannan material obtained in the above steps into a composite film comprising the steps of: and respectively taking 0.1g of the materials obtained in the partial steps, dissolving in 3ml of distilled water, adding 7g of ZnCl 2, heating to 65 ℃ in a water bath, stirring for 90min, adding 0.15g of CaCl 2 into the mixture, and stirring for 20min to realize crosslinking of the polymer. The film solution was poured into a plate and cooled to T <50 ℃ to form a gel. The gel was coagulated by an ethanol bath at 8℃for 60min, and then was subjected to desalting by a hot water bath at 75℃and plasticization by a glycerin bath (mixture of glycerin and water) (glycerin 10% v/v) to give a composite film. The resulting composite film sample was dried at 25℃and 50% relative humidity for 48 hours.
Comparative example 6: the galactomannan material obtained by pretreatment of the sodium chlorite acetic acid process of comparative example 5 was used to prepare a composite film. The obtained zinc ion composite film has a tensile strength of 3.36+/-0.12N/mm 2 and an elongation at break of 0.24+/-0.02 mm/mm.
Example 5: a composite film was prepared using the acidic peroxyacetic acid of example 3 in combination with the alkali treatment of the resulting galactoglucomannan material. The obtained zinc ion composite film has a tensile strength of 10.11+/-0.16N/mm < 2 >, and an elongation at break of 0.26+/-0.02 mm/mm.
Comparative example 7: a composite film was prepared using the acid peroxyacetic acid co-enzymatic treatment of the resulting galactoglucomannan material of example 4. The obtained zinc ion composite film has a tensile strength of 1.71+ -0.07N/mm 2 and an elongation at break of 0.09+ -0.01 mm/mm.
The mechanical properties of the composite film prepared from the galactoglucomannan material are shown in table 2 and fig. 2. The tensile strength of the film of example 5 was 10.11.+ -. 0.16N/mm 2 and the elongation at break was 0.26.+ -. 0.02mm/mm as determined by mechanical tensile analysis of the zinc ion film using a tensile tester. The elongation at break of the film of comparative example 6 is 0.24+/-0.02 mm/mm, which is close to that of the film of example 5, but the tensile strength is obviously reduced to 3.36+/-0.12N/mm 2, which proves that the mechanical strength of the material is seriously affected by different extraction methods; the enzyme treatment method used in comparative example 7 removed most of the glucosyl groups, so that the mechanical properties of the corresponding film were the lowest, the tensile strength was 1.71.+ -. 0.07N/mm 2, and the elongation at break was 0.09.+ -. 0.01mm/mm, which indicated that the content of the glucosyl group component had an important influence on the rigidity of the composite film structure.
Table 2: the characteristics of the polysaccharide material and the mechanical properties of the corresponding composite film
The appearance of the composite film prepared from the galactoglucomannan material is shown in figure 1. From the figure, the method can prepare a uniform, semitransparent and thinner film. The film has good mechanical properties, and Zn 2+ ions in the film can break or fracture O 3 H … O5 hydrogen bonds in cellulose, break a compact network structure of the cellulose and enable the cellulose to be dissolved. The presence of Ca 2+ ions readily crosslinks the zinc-cellulose chains to form nanofibrils and produce a strong transparent film.
The method provided by the invention can extract polysaccharide from SCG, and can obtain high-purity and high-yield polysaccharide, and particularly, the method creatively adopts a peracetic acid combined alkali treatment method to realize the efficient preparation of polysaccharide by solid phase stripping of impurities, so that the high-purity galactoglucomannan is separated and prepared from SCG to the maximum extent.
The method provided by the invention can effectively solve the problem of utilization of coffee grounds, the method for extracting the galactoglucomannan material from the coffee grounds is not extracted from polysaccharide liquid, but removes impurities in the coffee grounds by subtracting, so that the polysaccharide is obtained, the polysaccharide obtained by the method has high purity and yield which are far higher than those of the traditional method, and the method is simple to operate and can be suitable for industrialization. In addition, the method provided by the invention can be applied to the fields of biomedicine, pharmacy, food and the like in the future. The coffee grounds are environmental friendly and are a viable alternative to petroleum-based materials. Thus, its successful application may help design and develop new packaging materials, water purification systems, sensors, etc.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. A method of preparing a galactoglucomannan-containing material from coffee grounds, comprising:
Combining coffee grounds with acidic hydrogen peroxide, reacting at 20-150 ℃, and carrying out solid-liquid separation to obtain a solid which is a galactoglucomannan-containing material; the acidic hydrogen peroxide is a combination of hydrogen peroxide and acetic acid; inorganic acid is used as a catalyst in the reaction process.
2. The method of claim 1, wherein the volume ratio of hydrogen peroxide to acetic acid is from 3:7 to 7:3;
The mass volume ratio of the coffee grounds to the acidic hydrogen peroxide is 1:10-20 g/ml; the inorganic acid comprises any one or a combination of more than one of sulfuric acid, hydrochloric acid and phosphoric acid; the final concentration of the inorganic acid in the reaction system is 180-220 mM;
the temperature of the reaction is 50-120 ℃.
3. The method as recited in claim 1, further comprising
Combining the obtained solid with strong alkali, reacting, and separating solid from liquid, wherein the obtained solid is a galactoglucomannan-containing material;
the strong base comprises sodium hydroxide and/or potassium hydroxide;
The temperature of the reaction is 15-30 ℃.
4. The method as recited in claim 1, further comprising
The obtained solid is subjected to enzymolysis by cellulase, and is subjected to solid-liquid separation, and the obtained solid is a galactoglucomannan-containing material;
The dosage of the cellulase is 17-22 FPU/g solid;
The enzymolysis temperature is 50-65 ℃.
5. Use of a galactoglucomannan-containing material for the preparation of a film, characterized in that the galactoglucomannan-containing material is prepared by the method according to any one of claims 1 to 4.
6. A film prepared from a galactoglucomannan-containing material prepared by the method of any one of claims 1-4.
7. The use according to claim 5 or the film according to claim 6, wherein the tensile strength of the film is 8-12N/mm 2.
8. The use according to claim 5 or the film according to claim 6, comprising
Mixing the galactoglucomannan-containing material with zinc chloride and water, heating and stirring to obtain a mixed solution containing the galactoglucomannan-containing material and the zinc chloride;
adding calcium chloride into the obtained mixed solution, and stirring to realize crosslinking to obtain a gel solution;
after the obtained gel solution is solidified, a film is obtained.
9. The use or film according to claim 8, wherein the ratio of the galactoglucomannan-containing material to zinc chloride to water is between 0.05 and 0.2g: 6-8.5 g: 2-5 ml; the temperature of the heating and stirring is 60-70 ℃;
the mass ratio of the calcium chloride to the galactoglucomannan-containing material is 0.1:0.1 to 0.2.
10. The use or film according to claim 8, wherein after curing the obtained gel solution, the film obtained comprises in particular:
Cooling the gel solution to room temperature on a plate, immersing the plate in absolute ethyl alcohol to solidify the film completely, desalting by a hot bath, and plasticizing by a glycerol bath to obtain the film.
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