WO2024051158A1 - 一种酒糟基莱赛尔纤维浆粕的制备方法 - Google Patents
一种酒糟基莱赛尔纤维浆粕的制备方法 Download PDFInfo
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- distiller
- grains
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- powder
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- 229920000433 Lyocell Polymers 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 134
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 88
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000000843 powder Substances 0.000 claims abstract description 67
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 59
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 44
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 44
- 239000007864 aqueous solution Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 239000000725 suspension Substances 0.000 claims description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 68
- 238000003756 stirring Methods 0.000 claims description 42
- 230000007935 neutral effect Effects 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 28
- 239000000706 filtrate Substances 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 21
- 238000010306 acid treatment Methods 0.000 claims description 9
- 239000012429 reaction media Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 abstract description 38
- 239000001913 cellulose Substances 0.000 abstract description 38
- 238000001035 drying Methods 0.000 abstract description 7
- 238000010298 pulverizing process Methods 0.000 abstract 1
- 238000007873 sieving Methods 0.000 abstract 1
- 235000013339 cereals Nutrition 0.000 description 161
- 239000012153 distilled water Substances 0.000 description 50
- 238000010907 mechanical stirring Methods 0.000 description 46
- 230000000052 comparative effect Effects 0.000 description 33
- 239000000835 fiber Substances 0.000 description 19
- 229920005610 lignin Polymers 0.000 description 17
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 16
- 229940092714 benzenesulfonic acid Drugs 0.000 description 16
- 229920002488 Hemicellulose Polymers 0.000 description 14
- 229920002472 Starch Polymers 0.000 description 12
- 235000019991 rice wine Nutrition 0.000 description 12
- 235000019698 starch Nutrition 0.000 description 12
- 239000008107 starch Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000002699 waste material Substances 0.000 description 8
- 235000019750 Crude protein Nutrition 0.000 description 7
- 235000019784 crude fat Nutrition 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 235000005911 diet Nutrition 0.000 description 6
- 230000000378 dietary effect Effects 0.000 description 6
- 235000013305 food Nutrition 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 102000004169 proteins and genes Human genes 0.000 description 6
- 108090000623 proteins and genes Proteins 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000009987 spinning Methods 0.000 description 6
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 235000013405 beer Nutrition 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 235000013325 dietary fiber Nutrition 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000001814 pectin Substances 0.000 description 3
- 235000010987 pectin Nutrition 0.000 description 3
- 229920001277 pectin Polymers 0.000 description 3
- 235000018102 proteins Nutrition 0.000 description 3
- 238000013094 purity test Methods 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000002166 wet spinning Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 240000005979 Hordeum vulgare Species 0.000 description 1
- 235000007340 Hordeum vulgare Nutrition 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- 241000209094 Oryza Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000010169 landfilling Methods 0.000 description 1
- 235000018977 lysine Nutrition 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 235000006109 methionine Nutrition 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- -1 sulfite-p-toluenesulfonic acid Chemical compound 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000011514 vinification Methods 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000019156 vitamin B Nutrition 0.000 description 1
- 239000011720 vitamin B Substances 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 235000014101 wine Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
Definitions
- the invention relates to the technical field of textile raw material preparation, and in particular to a preparation method of distiller's grains-based lyocell fiber pulp.
- Lyocell fiber is a regenerated cellulose fiber produced by wet spinning using N-methylmorpholine-N-oxide (NMMO) as the solvent.
- NMMO N-methylmorpholine-N-oxide
- the German Akzo-Nobel Company first obtained the production process and product invention patents for lyocell fiber.
- the production cycle of Lyocell fiber is short, the production process is pollution-free (the solvent NMMO recycling rate can reach 99.7%), the textile products have high strength, good wearability, and the waste is biodegradable, and it has the reputation of "green fiber of the 21st century".
- China's winemaking industry has a long history. Taking rice wine that originated in China and is unique to China as an example, according to data from the National Bureau of Statistics cited by the China Liquor Industry Association, in 2020, although the wine market was greatly affected by the "new crown" epidemic , my country's rice wine production is still as high as 1.8571 million liters. Based on the approximate ratio of producing 6 kilograms of distiller's grains for every kilogram of rice wine brewed, my country's rice wine industry alone produces more than 10 million tons of distiller's grains every year. Due to the huge output of distiller's grains, most wineries currently use traditional methods such as landfilling or incineration to dispose of them.
- Landfill treatment occupies a large area, and if the landfill is too deep, it will cause harm to the soil.
- incineration treatment can effectively reduce the accumulation of distiller's grain waste, due to the complex composition of distiller's grains, the gas released by combustion contains a large amount of sulfides and nitrogen oxides, which seriously pollutes the atmospheric environment.
- distillers grains for animal feed, anaerobic digestion, and fermentation to produce ethanol fuel, etc.
- the amount of distillers grains consumed by these applications only accounts for a very small part of the distillers grains waste produced every year, and there is still a large amount of distillers grains waste.
- the lees are in urgent need of treatment.
- the volume reduction, harmlessness and resource treatment of distiller's grain waste has become an important issue related to ecological civilization, environmental protection and the development of new materials.
- distiller's grains are rich in cellulose, a polymer that can be used for wet spinning, as well as skin-beneficial amino acids and vitamins such as lysine, methionine, vitamins B and E, these substances together account for about 20% of the dry weight of the distillers' grains. %, the traditional way of treating distiller's grains as solid waste in the industry has obviously caused a huge waste of resources. At present, there are no reports at home or abroad about the use of distiller's grains to produce high-purity, high-value cellulose pulp for the preparation of lyocell fiber.
- the invention patent application with application publication number CN102356882A discloses a method of using brewer's grains to produce biological dietary cellulose. This method adds water to grind the brewer's grains, Adjust the pH value to 5-6, let it stand for 20-40 minutes, filter to remove the solid matter, then add 5-10 weight percent protease to the filtrate, keep it at 50-70°C, perform enzymatic hydrolysis for 1-3 hours, and adjust the pH value to medium.
- this patent uses the nutrients in beer grains as a culture medium for biological dietary cellulose, and then uses a fermentation method to produce biological dietary cellulose membranes. It does not separate high-purity cellulose from beer grains.
- the invention patent application with publication number CN105476031A discloses a method for producing distiller's grain dietary fiber.
- the method involves the following steps: 1) Stir the distiller's grain waste and calcium chloride and let it stand for flocculation, and filter and collect the flocs; 2) Add acid for decalcification; 3) Use sodium carbonate for alkali treatment; 4) Use hydrogen peroxide for bleaching Treatment; 5) washing to remove hydrogen peroxide; 6) drying and crushing.
- the distiller's grain fiber produced by this process is a mixture of cellulose, hemicellulose and lignin, and its core lies in the use of high-concentration soda ash solution to treat the distiller's grain. Since the mixed product is not separated after the soda ash solution treatment, the obtained dietary fiber product is only a mixture of cellulose, hemicellulose and lignin.
- the invention patent application with publication number CN108149506A discloses a method for producing high-purity cellulose, hemicellulose and lignin from distiller's grains.
- the main steps of this method include: 1) drying and grinding; 2) using biological enzymes to remove proteins in the distiller's grains; 3) high-temperature and high-pressure treatment (120-250 °C, 450-4000 kPa) of food-grade organic solvent aqueous solution to remove half of the protein.
- Cellulose and lignin are then solid-liquid separated to obtain solid cellulose and liquid components; 4) Use cooling water to mix with the filtrate, and let it stand to precipitate to obtain lignin; 5) The remaining liquid is sent to a vacuum distillation device for organic Solvent recovery and water evaporation yield high-purity hemicellulose.
- This method can effectively separate high-purity cellulose, hemicellulose and lignin from distiller's grains.
- this method requires a large amount of food-grade organic solvents and high-temperature and high-pressure equipment for production. The production cost is high and it is not suitable for Equipment requirements are also high.
- Distillers grain waste contains starch, protein, pectin, fat, ash, lignin, hemicellulose and other impurities, which makes it difficult to separate high-purity cellulose from it.
- the isolated cellulose products are mainly used in the food field, and their application in textiles is not mentioned.
- the invention provides a method for preparing distiller's grain-based lyocell fiber pulp.
- the cellulose purity of the distiller's grain pulp prepared by this method is as high as 90% or more, and can be used to prepare lyocell fiber.
- a method for preparing distiller's grains-based lyocell fiber pulp including the following steps:
- Dilute sulfuric acid treatment The distiller's grain raw materials are dried, ground into powder, and sieved in order to obtain distiller's grain powder; use water as the reaction medium to prepare the distiller's grain powder into suspension I; under stirring conditions, add the distiller's grain powder to the suspension Add dilute sulfuric acid dropwise into I, raise the temperature to 40 ⁇ 50°C, stir and filter, fully wash with water until neutral, and dry to obtain distiller's grains powder treated with dilute sulfuric acid;
- This invention first uses dilute sulfuric acid to pretreat the distiller's grain raw materials at 40-50°C, hydrolyze and remove the starch in the distiller's grains, and wash it with distilled water until neutral; then, use a caustic soda/sodium sulfite mixed aqueous solution to perform a high temperature treatment of 95-100°C on the acid-treated distiller's grains. Remove protein, pectin, fatty acids (esters), part of lignin, ash, etc.
- the cellulose in the distiller's grain pulp produced by the method of the present invention has high purity ( ⁇ 90%), good solubility in N-methylmorpholine-N-oxide solvent, and can be prepared by conventional wet spinning methods. Lyocell fiber.
- the particle size and mass fraction of the distiller's grain powder help to improve the reaction efficiency of sulfuric acid treatment. Further, in step (1), the particle size of the distiller's grain powder is between 50 and 300 mesh; in terms of mass percentage, the suspension In I, the mass percentage of distiller's grain powder is 10 ⁇ 20%.
- step (1) the mass concentration of the dilute sulfuric acid is 20 ⁇ 30%; the volume ratio of dilute sulfuric acid to water is 1:40 ⁇ 1:50, and the dripping operation is completed within 10 ⁇ 15 minutes; the stirring time It is 30 ⁇ 60 minutes.
- the selection of the above parameters will help improve the reaction efficiency and reaction uniformity of sulfuric acid treatment.
- step (2) in terms of mass percentage, the mass percentage of the distiller's grains powder treated with dilute sulfuric acid in the suspension II is 2.5% to 5.0%.
- step (2) the mass ratio of the distiller's grains powder treated with caustic soda and dilute sulfuric acid is 1:1 ⁇ 1:1.5; the mass ratio of sodium sulfite and the distiller's grains powder treated with dilute sulfuric acid is 1:9 ⁇ 1:12 ; Stirring time is 4 ⁇ 6h.
- step (3) in the suspension III, the mass percentage of the distiller's grains powder after caustic soda/sodium sulfite treatment is 5% to 10% in terms of mass percentage.
- the present invention tests the types of organic solvents and finds that p-toluenesulfonic acid can significantly improve the purity of cellulose in distiller's grains, while its analog benzenesulfonic acid has a relatively poor effect.
- step (3) the mass concentration of the p-toluenesulfonic acid aqueous solution is 20 ⁇ 30%; the volume ratio of the p-toluenesulfonic acid aqueous solution and water is 1:6-1:10, and the dripping is completed within 10 ⁇ 15 minutes. Add operation; stirring time is 6 ⁇ 8h.
- the present invention also provides distiller's grains-based lyocell fiber pulp prepared by the above preparation method.
- the present invention has the following beneficial effects:
- the present invention adopts the treatment process of dilute sulfuric acid-caustic soda/sodium sulfite-p-toluenesulfonic acid to process the distiller's grains, and the purity of the obtained distiller's grain pulp fiber is as high as more than 90%.
- the present invention can complete the separation of cellulose, hemicellulose and lignin in the distiller's grains without consuming any organic solvent or using high-temperature and high-pressure equipment, thereby reducing production costs and simplifying production equipment.
- the present invention found that the p-toluenesulfonic acid treatment method avoids the damage to the cellulose structure caused by the high temperature and high pressure environment (120-250 °C, 450-4000 kPa) in the existing methods of removing hemicellulose and lignin from distiller's grains. It is beneficial to improve the product properties of distiller's grain-based lyocell fiber (such as mechanical properties, thermal stability).
- Figure 1 is a schematic flow chart of the preparation method of distiller's grains-based lyocell fiber pulp of the present invention.
- Detection method for crude starch content in raw materials GB/T 5009.9-2008 Determination of starch in food
- Detection method for crude protein content in raw materials GB/T 5009.5-2010 Determination of starch in food Determination of protein
- detection method for crude fiber content in raw materials GB/T 5009.88-2003 Determination of insoluble dietary fiber in food
- detection method for crude fat content in raw materials GB/T 5009.6-2010 Determination of fat in food
- ash content in raw materials Testing method GB/T 5009.4-2010 Determination of ash in food
- Testing method for lignin, hemicellulose, and cellulose content in crude fiber NY/T 3494-2019 Agricultural biomass raw materials cellulose, hemicellulose, and lignin Determination.
- the distiller's grains come from a rice wine manufacturer in Zhejiang that uses glutinous rice as the main raw material; the specific preparation method of the distiller's grains-based lyocell fiber pulp is as follows:
- the mass proportions of crude starch, crude protein, crude fiber, crude fat and ash as the main components of the dilute sulfuric acid-treated distiller's grains powder are 1.97%, 54.50%, 26.62%, 12.73% and 2.81% respectively.
- the main component of the caustic soda/sodium sulfite treated distiller's grain powder is only crude fiber, which accounts for 96.02% by mass.
- Example 1 changes the heating temperature in step (3) from 80°C to 90°C, and the other contents are exactly the same as Example 1.
- the specific step (3) is: Disperse the above-mentioned 25g dry weight of caustic soda/sodium sulfite treated distiller's grains powder in 375 mL of distilled water to prepare a distiller's grain suspension with a mass concentration of 6.25%, and then move it into a distiller's grain suspension equipped with mechanical stirring, a thermometer and a dropper.
- Example 1 changes the volume of p-toluenesulfonic acid aqueous solution dropped into the suspension in step (3) from the original 37.5 mL to 62.5 mL, and the other contents are exactly the same as Example 1.
- the specific step (3) is: Disperse the above-mentioned 25g dry weight of caustic soda/sodium sulfite treated distiller's grains powder in 375 mL of distilled water to prepare a distiller's grain suspension with a mass concentration of 6.25%, and then move it into a distiller's grain suspension equipped with mechanical stirring, a thermometer and a dropper.
- This comparative example is based on Example 1, except that the type of organic acid is changed from p-toluenesulfonic acid to benzenesulfonic acid, and the other contents are exactly the same as Example 1.
- the specific step (3) is: Disperse the above-mentioned 25g dry weight of caustic soda/sodium sulfite treated distiller's grains powder in 375 mL of distilled water to prepare a distiller's grain suspension with a mass concentration of 6.25%, and then move it into a distiller's grain suspension equipped with mechanical stirring, a thermometer and a dropper.
- This comparative example is based on Comparative Example 1, except that the heating temperature in step (3) is changed from 80°C to 90°C. The rest of the contents are exactly the same as Comparative Example 1.
- the specific step (3) is: Disperse the above-mentioned 25g dry weight of caustic soda/sodium sulfite treated distiller's grains powder in 375 mL of distilled water to prepare a distiller's grain suspension with a mass concentration of 6.25%, and then move it into a distiller's grain suspension equipped with mechanical stirring, a thermometer and a dropper.
- This comparative example is based on Comparative Example 1.
- the volume of the benzenesulfonic acid aqueous solution added dropwise to the suspension in step (3) is changed from the original 37.5 mL to 62.5 mL.
- the other contents are exactly the same as Comparative Example 1.
- the specific step (3) is: Disperse the above-mentioned 25g dry weight of caustic soda/sodium sulfite treated distiller's grains powder in 375 mL of distilled water to prepare a distiller's grain suspension with a mass concentration of 6.25%, and then move it into a distiller's grain suspension equipped with mechanical stirring, a thermometer and a dropper.
- the distiller's grains come from a liquor manufacturer in Hebei that uses corn as the main raw material;
- the specific preparation method of the distiller's grains-based lyocell fiber pulp is as follows:
- the mass proportions of crude starch, crude protein, crude fiber, crude fat and ash as the main components of the dried distiller's grain raw material are 14.02%, 27.49%, 14.74%, 5.20% and 2.57% respectively.
- the mass proportions of crude starch, crude protein, crude fiber, crude fat and ash as the main components of the dilute sulfuric acid-treated distiller's grains powder are 2.71%, 48.75%, 28.58%, 8.99% and 3.07% respectively.
- the main component of the caustic soda/sodium sulfite treated distiller's grain powder is only crude fiber, which accounts for 97.58% by mass.
- Example 4 changes the heating temperature in step (3) from 80°C to 90°C, and the other contents are exactly the same as Example 4.
- the specific step (3) is: Disperse the above-mentioned 25g dry weight of caustic soda/sodium sulfite treated distiller's grain powder in 400 mL of distilled water to prepare a distiller's grain suspension with a mass concentration of 5.88%, and then move it into a funnel equipped with mechanical stirring, a thermometer and a dropping funnel.
- a 1000 mL three-neck flask under mechanical stirring conditions, drop 40 mL of 25wt% p-toluenesulfonic acid aqueous solution into the suspension within 15 minutes, raise the temperature to 90°C, stir at this temperature for 8 hours, and separate the filtrate and filter residue. , wash the filter residue with distilled water until the washing liquid is neutral, and dry the filter residue to obtain distiller's grains-based lyocell fiber pulp.
- Example 4 changes the volume of p-toluenesulfonic acid aqueous solution dropped into the suspension in step (3) from the original 40 mL to 66.7 mL, and the other contents are exactly the same as Example 4.
- the specific step (3) is: Disperse the above-mentioned 25g dry weight of caustic soda/sodium sulfite treated distiller's grain powder in 400 mL of distilled water to prepare a distiller's grain suspension with a mass concentration of 5.88%, and then move it into a funnel equipped with mechanical stirring, a thermometer and a dropping funnel.
- a 1000mL three-neck flask under mechanical stirring conditions, drop 66.7mL of 25wt% p-toluenesulfonic acid aqueous solution into the suspension within 15min, raise the temperature to 80°C, stir at this temperature for 8h, and separate the filtrate and filter residue. , wash the filter residue with distilled water until the washing liquid is neutral, and dry the filter residue to obtain distiller's grains-based lyocell fiber pulp.
- This comparative example is based on Example 4, except that the type of organic acid is changed from p-toluenesulfonic acid to benzenesulfonic acid, and the other contents are exactly the same as Example 1.
- the specific step (3) is: Disperse the above-mentioned 25g dry weight of caustic soda/sodium sulfite treated distiller's grain powder in 400 mL of distilled water to prepare a distiller's grain suspension with a mass concentration of 5.88%, and then move it into a funnel equipped with mechanical stirring, a thermometer and a dropping funnel.
- This comparative example is based on Comparative Example 4, except that the heating temperature in step (3) is changed from 80°C to 90°C, and the remaining contents are exactly the same as Comparative Example 4.
- the specific step (3) is: Disperse the above-mentioned 25g dry weight of caustic soda/sodium sulfite treated distiller's grain powder in 400 mL of distilled water to prepare a distiller's grain suspension with a mass concentration of 5.88%, and then move it into a funnel equipped with mechanical stirring, a thermometer and a dropping funnel.
- This comparative example is based on Comparative Example 4.
- the volume of the benzenesulfonic acid aqueous solution added dropwise to the suspension in step (3) is changed from the original 40 mL to 66.7 mL.
- the other contents are exactly the same as Comparative Example 1.
- the specific step (3) is: Disperse the above-mentioned 25g dry weight of caustic soda/sodium sulfite treated distiller's grain powder in 400 mL of distilled water to prepare a distiller's grain suspension with a mass concentration of 6.25%, and then move it into a container equipped with mechanical stirring, a thermometer and a In a 1000mL three-necked flask of the dropping funnel, under mechanical stirring conditions, add 66.7mL of 25wt% benzenesulfonic acid aqueous solution dropwise into the suspension within 10 minutes, raise the temperature to 80°C, stir at this temperature for 6h, and separate the filtrate and filter residue, wash the filter residue with distilled water until the washing liquid becomes neutral, and dry the filter residue to prepare liquor distiller's grain pulp.
- the purity of cellulose in the rice wine lees pulp of Examples 4 to 6 and Comparative Examples 4 to 6 was detected, and the results are shown in Table 2.
- the distiller's grains come from a beer manufacturer in Zhejiang that uses barley as the main raw material; the specific preparation method of the distiller's grains-based lyocell fiber pulp is as follows:
- Dilute sulfuric acid treatment of distiller's grain powder Under mechanical stirring conditions, add 13 mL of 25wt% dilute sulfuric acid dropwise into the suspension within 10 minutes, raise the temperature to 50°C, stir at this temperature for 60 minutes, filter, fully wash with distilled water until neutral, and dry to obtain Dilute sulfuric acid treatment of distiller's grain powder.
- the mass proportions of crude starch, crude protein, crude fiber, crude fat and ash as the main components of the dilute sulfuric acid-treated distiller's grains powder are 0.98%, 50.21%, 27.68%, 9.90% and 3.62% respectively.
- Example 7 changes the heating temperature in step (3) from 80°C to 90°C, and the other contents are exactly the same as Example 7.
- the specific step (3) is: Disperse the above-mentioned 25g dry weight of caustic soda/sodium sulfite treated distiller's grain powder in 300 mL of distilled water to prepare a distiller's grain suspension with a mass concentration of 7.69%, and then move it into a funnel equipped with mechanical stirring, a thermometer and a dropping funnel.
- a 1000mL three-neck flask under mechanical stirring conditions, drop 30 mL of 25wt% p-toluenesulfonic acid aqueous solution into the suspension within 10 minutes, raise the temperature to 90°C, stir at this temperature for 7h, and separate the filtrate and filter residue. , wash the filter residue with distilled water until the washing liquid is neutral, and dry the filter residue to obtain distiller's grains-based lyocell fiber pulp.
- Example 8 changes the volume of p-toluenesulfonic acid aqueous solution dropped into the suspension in step (3) from the original 30 mL to 50 mL, and the other contents are exactly the same as Example 8.
- the specific step (3) is: Disperse the above-mentioned 25g dry weight of caustic soda/sodium sulfite treated distiller's grain powder in 300 mL of distilled water to prepare a distiller's grain suspension with a mass concentration of 7.69%, and then move it into a funnel equipped with mechanical stirring, a thermometer and a dropping funnel.
- a 1000mL three-neck flask under mechanical stirring conditions, drop 50mL of 25wt% p-toluenesulfonic acid aqueous solution into the suspension within 10min, raise the temperature to 80°C, stir at this temperature for 7h, and separate the filtrate and filter residue.
- the filter residue is washed with distilled water until the washing liquid becomes neutral, and the distiller's grains-based lyocell fiber pulp is obtained after drying the filter residue.
- This comparative example is based on Example 7, except that the type of organic acid is changed from p-toluenesulfonic acid to benzenesulfonic acid, and the other contents are exactly the same as Example 7.
- the specific step (3) is: Disperse the above-mentioned 25g dry weight of caustic soda/sodium sulfite treated distiller's grain powder in 300 mL of distilled water to prepare a distiller's grain suspension with a mass concentration of 7.69%, and then move it into a funnel equipped with mechanical stirring, a thermometer and a dropping funnel.
- This comparative example is based on Comparative Example 7, except that the heating temperature in step (3) is changed from 80°C to 90°C, and the remaining contents are exactly the same as Comparative Example 7.
- the specific step (3) is: Disperse the above-mentioned 25g dry weight of caustic soda/sodium sulfite treated distiller's grain powder in 300 mL of distilled water to prepare a distiller's grain suspension with a mass concentration of 7.69%, and then move it into a funnel equipped with mechanical stirring, a thermometer and a dropping funnel.
- a 1000mL three-neck flask under mechanical stirring conditions, drop 30mL of 25wt% benzenesulfonic acid aqueous solution into the suspension within 10min, raise the temperature to 90°C, stir at this temperature for 7 hours, and separate the filtrate and filter residue.
- the filter residue is washed with distilled water until the washing liquid becomes neutral, and the distiller's grains-based lyocell fiber pulp is obtained after drying the filter residue.
- This comparative example is based on Comparative Example 7, in which the volume of the benzenesulfonic acid aqueous solution added dropwise to the suspension in step (3) is changed from the original 30 mL to 50 mL, and the rest of the content is exactly the same as Comparative Example 1.
- the specific step (3) is: Disperse the above-mentioned 25g dry weight of caustic soda/sodium sulfite treated distiller's grain powder in 300 mL of distilled water to prepare a distiller's grain suspension with a mass concentration of 7.69%, and then move it into a funnel equipped with mechanical stirring, a thermometer and a dropping funnel.
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Abstract
本发明公开了一种酒糟基莱赛尔纤维浆粕的制备方法，该方法包括：酒糟原料依次经烘干、研磨成粉、过筛处理后，得到酒糟粉；酒糟粉依次经稀硫酸处理、烧碱/亚硫酸钠处理和对甲苯磺酸水溶液处理，得到酒糟基莱赛尔纤维浆粕。本发明采用稀硫酸-烧碱/亚硫酸钠-对甲苯磺酸的处理工艺，对酒糟进行处理，得到的酒糟浆粕纤维素纯度高达90%以上，可用于制备莱赛尔纤维。
Description
本发明涉及纺织原料制备技术领域，尤其涉及一种酒糟基莱赛尔纤维浆粕的制备方法。
莱赛尔纤维是以N-甲基吗啉-N-氧化物（NMMO）为溶剂，用湿法纺丝制取的再生纤维素纤维。1980年德国Akzo-Nobel公司首先取得莱赛尔纤维的生产工艺和产品发明专利，1989年由国际人造纤维和合成纤维委员会正式命名。莱赛尔纤维的生产周期短，生产过程无污染（溶剂NMMO回收利用率可达99.7%），纺织制品强度高、服用性能佳，废弃物可生物降解，具有“21世纪绿色纤维”的美誉。
在我国的莱赛尔纤维工业生产中，为满足纺丝浆粕高溶解性和纺丝液高品质要求，绝大部分莱赛尔纤维的纺丝原料只能由国外进口，这成为制约我国莱赛尔纤维产业发展的主要瓶颈。因此，从可再生的工农业副产品中提取来源广泛，生物可降解的高分子材料并以此为原料开发性能优良，价格低廉的新型莱赛尔纤维已成为化纤领域研究者的当务之急。
中国酿酒产业具有悠久的历史，以源于中国且唯中国有之的黄酒为例，根据中国酒业协会引用的国家统计局数据，2020年，酒业市场虽然受到“新冠”疫情的较大冲击，我国黄酒产量仍然高达185.71万千升。按照每酿造1千克黄酒产生6千克酒糟的大致比例计算，我国仅黄酒工业每年就产生酒糟一千多万吨。由于酒糟的产量巨大，目前多数酒厂还是采用填埋或焚烧等传统方式对其进行处理。填埋处理占地面积大，若填埋过深还会对土壤造成危害。焚烧处理虽然可以有效减少酒糟废料的堆积，但是由于酒糟中成分复杂，燃烧释放的气体中含有大量的硫化物与氮氧化物，严重污染了大气环境。近年来，虽有研究者将酒糟用于动物饲料、厌氧消化、发酵制取乙醇燃料等，然而，这些应用所消耗的酒糟量只占每年所产酒糟废弃物的极少部分，仍有大量的酒糟急待处理。酒糟废弃物的减容化、无害化和资源化处理已是一项关乎生态文明、环境保护及新材料开发的重要课题。
由于酒糟中含有丰富的纤维素这一可用于湿法纺丝的聚合物以及赖氨酸、蛋氨酸、维生素B、E等益肤性氨基酸及维生素，几类物质相加约占酒糟干重的20%，工业界将酒糟作为固废垃圾的传统处理方式显然已造成了极大的资源浪费。目前，国内外尚未见到利用酒糟生产高纯度、高价值纤维素浆粕用于制备莱赛尔纤维的报道。
目前，也有一些关于从酒糟中提取纤维素的公开文献；例如：申请公布号为CN102356882A的发明专利申请公开了一种利用啤酒糟生产生物膳食纤维素的方法，该方法将啤酒糟加水磨浆，调pH值至5-6，静置20-40 min，过滤除去固体物质后再往滤液中加入5-10重量百分比的蛋白酶，保温50-70 ℃，酶解1-3h，调pH值至中性，再次过滤去除固体物质后灭菌作为生物膳食纤维素产生菌培养基使用，再接种生物膳食纤维素产生菌，发酵生产生物膳食纤维素膜。可见，此专利是利用啤酒酒糟中的营养物质作为生物膳食纤维素的培养基，继而采用发酵法生产生物膳食纤维素膜，并非从啤酒糟中分离出高纯度纤维素。
申请公布号为CN105476031A的发明专利申请公开了一种酒糟膳食纤维生产方法。该方法涉及以下步骤：1）将酒糟废弃物和氯化钙进行搅拌后静置絮凝，过滤收集絮凝物；2）加酸脱钙；3）使用碳酸钠进行碱处理；4）使用双氧水进行漂白处理；5）洗涤除去双氧水；6）烘干粉碎处理。可见，此工艺所生产的酒糟纤维是纤维素、半纤维素和木质素的混合体，其核心在于使用高浓度的纯碱溶液对酒糟进行处理。由于在纯碱溶液处理后并未对混合产物进行分离，所以得到的膳食纤维产物仅为纤维素、半纤维素以及木质素的混合物。
申请公布号为CN108149506A的发明专利申请公开了一种用酒糟生产高纯度纤维素、半纤维素及木质素的方法。此方法的主要步骤包括：1）烘干碾磨；2）使用生物酶去除酒糟中的蛋白质；3）食品级有机溶剂水溶液进行高温高压处理（120-250 ℃，450-4000 kPa）溶除半纤维素、木质素，再进行固液分离，获得固体纤维素和液体组分；4）使用冷却水与滤液进行混合，静置沉淀得到木质素；5）剩余液体被送至真空蒸馏装置进行有机溶剂回收和水分蒸发，从而得到高纯度半纤维素。
该方法可从酒糟中有效分离出高纯度的纤维素、半纤维素和木质素，然而，此法需要消耗大量食品级有机溶剂，并需借助高温高压设备才能进行生产，生产成本较高，对设备的要求亦高。酒糟废弃物中包含了淀粉、蛋白质、果胶、脂肪、灰分、木质素、半纤维素等杂质，这就导致从中分离出高纯度的纤维素具有较大的难度。现有关于酒糟资源化利用的报道中，分离出的纤维素产物主要用于食品领域，均未涉及其在纺织品中的应用。
因此，有必要开发一种工艺简便、成本低廉的方法去除酒糟中的多种杂质，从而获得具有高纯度、高质量纤维素的浆粕，使之能够较好地形成纺丝液用于莱赛尔纤维的制备。
本发明提供了一种酒糟基莱赛尔纤维浆粕的制备方法，该方法制备获得的酒糟浆粕纤维素纯度高达90%以上，可用于制备莱赛尔纤维。
具体技术方案如下：
一种酒糟基莱赛尔纤维浆粕的制备方法，包括以下步骤：
（1）稀硫酸处理：酒糟原料依次经烘干、研磨成粉、过筛处理后，得到酒糟粉；以水为反应介质，将酒糟粉配成悬浮液I；在搅拌条件下，向悬浮液I中滴加稀硫酸，升温至40~50℃，搅拌后过滤，水充分洗涤至中性，干燥后，制得稀硫酸处理后的酒糟粉；
（2）烧碱/亚硫酸钠处理：以水为反应介质，将步骤（1）稀硫酸处理后的酒糟粉配成悬浮液II，在搅拌条件下，依次向悬浮液II中加入一定质量的烧碱、亚硫酸钠，升温至95~100℃，搅拌后过滤，水充分洗涤至中性，干燥后，制得烧碱/亚硫酸钠处理后的酒糟粉；
（3）对甲苯磺酸处理：以水为反应介质，将步骤（2）烧碱/亚硫酸钠处理后的酒糟粉配成悬浮液III，在搅拌条件下，向悬浮液III中滴加对甲苯磺酸水溶液，升温至70~80 ℃，搅拌后过滤，分离滤液和滤渣，水洗涤滤渣至洗涤液为中性，滤渣干燥后，制得酒糟基莱赛尔纤维浆粕。
本发明首先利用稀硫酸对酒糟原料进行40-50℃预处理，水解去除酒糟中的淀粉，蒸馏水洗涤至中性；随后，选用烧碱/亚硫酸钠混合水溶液对酸处理酒糟进行95~100 ℃高温处理，去除酒糟中的蛋白质、果胶、脂肪酸（酯）、部分木质素、灰分等，蒸馏水洗涤至中性；然后，采用易回收的有机酸对甲苯磺酸水溶液对烧碱/亚硫酸钠处理后的酒糟进行70~80 ℃处理，溶解去除酒糟中的木质素、半纤维素，滤出、洗涤并烘干获得酒糟浆粕。本发明方法制得的酒糟浆粕中纤维素纯度高（≥90%），在N-甲基吗啉-N-氧化物溶剂中具有良好的溶解性，通过常规湿法纺丝方法即可制备莱赛尔纤维。
酒糟中仅有粗纤维（即纤维素、半纤维素、木质素的合称）中的纤维素是纺制莱赛尔纤维的有效成分，步骤1）稀硫酸处理去除淀粉和步骤2）烧碱/亚硫酸钠处理去除蛋白质、果胶、脂肪酸（酯）、部分木质素、灰分等均是为了去除杂质，获取粗纤维，如果步骤1）和2）条件改变，会使得杂质去除不净，增加对甲苯磺酸对木质素、半纤维素的去除负担，也不利于浆粕在NMMO中的溶解和纺丝；步骤2）也与之类似，若其目标杂质去除不净，也会增加对甲苯磺酸对木质素、半纤维素的去除负担。
酒糟粉粒径及质量分数有助于提高硫酸处理的反应效率，进一步地，步骤（1）中，所述酒糟粉的粒径在50~300目之间；以质量百分数计，所述悬浮液I中，酒糟粉的质量百分数为10~20%。
进一步地，步骤（1）中，所述稀硫酸的质量浓度为20~30%；稀硫酸与水的体积比为1:40~1:50，10~15 min内完成滴加操作；搅拌时间为30~60 min。上述几个参数的选择有助于提高硫酸处理的反应效率和反应均匀性。
进一步地，步骤（2）中，以质量百分数计，所述悬浮液II中，稀硫酸处理后的酒糟粉的质量百分数为2.5%~5.0%。
进一步地，步骤（2）中，烧碱与稀硫酸处理后的酒糟粉的质量比为1:1~1:1.5；亚硫酸钠与稀硫酸处理后的酒糟粉的质量比为1:9~1:12；搅拌时间为4~6h。
进一步地，步骤（3）中，以质量百分数计，所述悬浮液III中，烧碱/亚硫酸钠处理后的酒糟粉的质量百分数为5%~10%。
本发明对有机溶剂的种类进行试验，发现对甲苯磺酸能够显著提高酒糟中的纤维素纯度，而其类似物苯磺酸则效果相对较差。
进一步地，步骤（3）中，所述对甲苯磺酸水溶液的质量浓度为20~30%；对甲苯磺酸水溶液与水的体积比为1:6-1:10，10~15min内完成滴加操作；搅拌时间为6~8h。
本发明还提供了如上所述制备方法制得的酒糟基莱赛尔纤维浆粕。
与现有技术相比，本发明具有以下有益效果：
（1）本发明采用稀硫酸-烧碱/亚硫酸钠-对甲苯磺酸的处理工艺，对酒糟进行处理，得到的酒糟浆粕纤维纯度高达90%以上。
（2）本发明在无需消耗任何有机溶剂、无需借助高温高压设备的条件下就可完成酒糟中纤维素与半纤维素、木质素的分离，降低了生产成本，简化了生产设备。
（3）本发明发现对甲苯磺酸处理法避免了已有从酒糟中去除半纤维素、木质素的方法中高温高压环境（120-250 ℃，450-4000 kPa）对纤维素结构的破坏，有利于提升酒糟基莱赛尔纤维的产品性能（如力学性能、热稳定性）。
图1为本发明酒糟基莱赛尔纤维浆粕的制备方法的流程示意图。
下面结合具体实施例对本发明作进一步描述，以下列举的仅是本发明的具体实施例，但本发明的保护范围不仅限于此。
下列实施例中所涉及的检测方法及具体内容如下：原料中粗淀粉含量检测方法：GB/T 5009.9-2008 食品中淀粉的测定；原料中粗蛋白含量检测方法：GB/T 5009.5-2010 食品中蛋白质的测定；原料中粗纤维含量检测方法：GB/T 5009.88-2003 食品中不溶性膳食纤维的测定；原料中粗脂肪含量检测方法：GB/T 5009.6-2010 食品中脂肪的测定；原料中灰分含量检测方法：GB/T 5009.4-2010 食品中灰分的测定；粗纤维中木质素、半纤维素、纤维素含量检测方法：NY/T 3494-2019 农业生物质原料纤维素、半纤维素、木质素测定。
实施例1
本实施例中，酒糟来自于浙江一家以糯米为主要原料的黄酒生产厂家；具体酒糟基莱赛尔纤维浆粕的制备方法，如下：
1）将酒糟原料在研钵中精细研磨，过70目筛，在真空干燥箱中烘至绝干。根据成分分析，该烘干后酒糟原料的主要成分：粗淀粉、粗蛋白、粗纤维、粗脂肪及灰分的质量占比分别为28.20%，35.52%，18.81%，9.25%及3.11%。
将研磨后干重为100 g的酒糟粉分散于700g蒸馏水中，配制成质量浓度为12.5%的酒糟悬浮液，然后移入装有机械搅拌、温度计和滴液漏斗的2000mL的三颈烧瓶中，在机械搅拌条件下，在15 min内向悬浮液中滴加17.5 mL的25wt%的稀硫酸，升温至50 ℃，在此温度下搅拌45 min，过滤、蒸馏水充分洗涤至中性，干燥后制得稀硫酸处理酒糟粉。
根据成分分析，该稀硫酸处理酒糟粉的主要成分粗淀粉、粗蛋白、粗纤维、粗脂肪及灰分的质量占比分别为1.97%，54.50%，26.62%，12.73%及2.81%。
2）将上述干重为50g的稀硫酸处理酒糟粉分散于950 g蒸馏水中，配制成质量浓度为5%的酒糟悬浮液，然后移入装有机械搅拌、温度计和滴液漏斗的2000mL的三颈烧瓶中，在机械搅拌条件下，依次向悬浮液中加入37.5g烧碱、4.5g亚硫酸钠，升温至100 ℃，在此温度下搅拌4h，过滤、蒸馏水充分洗涤至中性，干燥后制得烧碱/亚硫酸钠处理酒糟粉。
根据成分分析，该烧碱/亚硫酸钠处理酒糟粉的主要成分仅剩粗纤维，其质量占比为96.02%。
3）将上述干重为25g的烧碱/亚硫酸钠处理后的酒糟粉分散于375mL蒸馏水中，配制成质量浓度为6.25%的酒糟悬浮液，然后移入装有机械搅拌、温度计和滴液漏斗的1000mL的三颈烧瓶中，在机械搅拌条件下，在10min内向悬浮液中滴加37.5mL的25wt%的对甲苯磺酸水溶液，升温至80 ℃，在此温度下搅拌6h，分离滤液和滤渣，用蒸馏水洗涤滤渣至洗涤液为中性，滤渣干燥后制得酒糟基莱赛尔纤维浆粕。
实施例2
在实施例1的基础上，本实施例将步骤（3）中升温温度由80℃变为90℃，其余内容与实施例1完全相同。
具体步骤（3）为：将上述干重为25g的烧碱/亚硫酸钠处理后的酒糟粉分散于375mL蒸馏水中，配制成质量浓度为6.25%的酒糟悬浮液，然后移入装有机械搅拌、温度计和滴液漏斗的1000 mL的三颈烧瓶中，在机械搅拌条件下，在10min内向悬浮液中滴加37.5 mL的25wt%的对甲苯磺酸水溶液，升温至90 ℃，在此温度下搅拌6h，分离滤液和滤渣，用蒸馏水洗涤滤渣至洗涤液为中性，滤渣干燥后制得酒糟基莱赛尔纤维浆粕。
实施例3
在实施例1的基础上，本实施例将步骤（3）的向悬浮液中滴加对甲苯磺酸水溶液的体积由原来的37.5mL变为62.5mL，其余内容与实施例1完全相同。
具体步骤（3）为：将上述干重为25g的烧碱/亚硫酸钠处理后的酒糟粉分散于375mL蒸馏水中，配制成质量浓度为6.25%的酒糟悬浮液，然后移入装有机械搅拌、温度计和滴液漏斗的1000 mL的三颈烧瓶中，在机械搅拌条件下，在10min内向悬浮液中滴加37.5mL的25wt%的对甲苯磺酸水溶液，升温至80 ℃，在此温度下搅拌6h，分离滤液和滤渣，用蒸馏水洗涤滤渣至洗涤液为中性，滤渣干燥后制得酒糟基莱赛尔纤维浆粕。
对比例1
本对比例是在实施例1的基础上，将有机酸种类由对甲苯磺酸改为苯磺酸，其余内容与实施例1完全相同。
具体步骤（3）为：将上述干重为25g的烧碱/亚硫酸钠处理后的酒糟粉分散于375mL蒸馏水中，配制成质量浓度为6.25%的酒糟悬浮液，然后移入装有机械搅拌、温度计和滴液漏斗的1000mL的三颈烧瓶中，在机械搅拌条件下，在10min内向悬浮液中滴加37.5mL的25wt%的苯磺酸水溶液，升温至80 ℃，在此温度下搅拌6h，分离滤液和滤渣，用蒸馏水洗涤滤渣至洗涤液为中性，滤渣干燥后制得黄酒酒糟浆粕。
对比例2
本对比例是在对比例1的基础上，将步骤（3）中升温温度由80℃变为90℃，其余内容与对比例1完全相同。
具体步骤（3）为：将上述干重为25g的烧碱/亚硫酸钠处理后的酒糟粉分散于375mL蒸馏水中，配制成质量浓度为6.25%的酒糟悬浮液，然后移入装有机械搅拌、温度计和滴液漏斗的1000mL的三颈烧瓶中，在机械搅拌条件下，在10min内向悬浮液中滴加37.5mL的25wt%的苯磺酸水溶液，升温至90 ℃，在此温度下搅拌6h，分离滤液和滤渣，用蒸馏水洗涤滤渣至洗涤液为中性，滤渣干燥后制得黄酒酒糟浆粕。
对比例3
本对比例是在对比例1的基础上，将步骤（3）的向悬浮液中滴加苯磺酸水溶液的体积由原来的37.5mL变为62.5mL，其余内容与对比例1完全相同。
具体步骤（3）为：将上述干重为25g的烧碱/亚硫酸钠处理后的酒糟粉分散于375mL蒸馏水中，配制成质量浓度为6.25%的酒糟悬浮液，然后移入装有机械搅拌、温度计和滴液漏斗的1000mL的三颈烧瓶中，在机械搅拌条件下，在10min内向悬浮液中滴加62.5mL的25wt%的苯磺酸水溶液，升温至80 ℃，在此温度下搅拌6h，分离滤液和滤渣，用蒸馏水洗涤滤渣至洗涤液为中性，滤渣干燥后制得黄酒酒糟浆粕。检测实施例1~3和对比例1~3的黄酒酒糟浆粕中纤维素的纯度，结果如表1所示。
表1 不同处理工艺下黄酒酒糟浆粕中纤维素的纯度
注：每种浆粕的纤维素纯度测试实验重复3次，数据统计时使用SAS软件分析数据，置信区间设置为95%，p值若小于0.05被认为是具有统计学意义的差异。在表1中，具有相同小写字母的数据点在统计学上被认为彼此间无显著差异。
实施例4
本实施例中，酒糟来自于河北一家以玉米为主要原料的白酒生产厂家；具体酒糟基莱赛尔纤维浆粕的制备方法，如下：
1）将酒糟原料在研钵中精细研磨，过60目筛，在真空干燥箱中烘至绝干。
根据成分分析，该烘干后酒糟原料的主要成分粗淀粉、粗蛋白、粗纤维、粗脂肪及灰分的质量占比分别为14.02%，27.49%，14.74%，5.20%及2.57%。
将研磨后干重为100g的酒糟粉分散于900g蒸馏水中，配制成质量浓度为10%的酒糟悬浮液，然后移入装有机械搅拌、温度计和滴液漏斗的2000mL的三颈烧瓶中，在机械搅拌条件下，在15min内向悬浮液中滴加18mL的25wt%的稀硫酸，升温至45 ℃，在此温度下搅拌30min，过滤、蒸馏水充分洗涤至中性，干燥后制得稀硫酸处理酒糟粉。
根据成分分析，该稀硫酸处理酒糟粉的主要成分粗淀粉、粗蛋白、粗纤维、粗脂肪及灰分的质量占比分别为2.71%，48.75%，28.58%，8.99%及3.07%。
2）将上述干重为50g的稀硫酸处理酒糟粉分散于1000g蒸馏水中，配制成质量浓度为4.76%的酒糟悬浮液，然后移入装有机械搅拌、温度计和滴液漏斗的2000mL的三颈烧瓶中，在机械搅拌条件下，依次向悬浮液中加入50g烧碱、5.5g亚硫酸钠，升温至95 ℃，在此温度下搅拌2h，过滤、蒸馏水充分洗涤至中性，干燥后制得烧碱/亚硫酸钠处理酒糟粉。
根据成分分析，该烧碱/亚硫酸钠处理酒糟粉的主要成分仅剩粗纤维，其质量占比为97.58%。
3）将上述干重为25g的烧碱/亚硫酸钠处理酒糟粉分散于400mL蒸馏水中，配制成质量浓度为5.88%的酒糟悬浮液，然后移入装有机械搅拌、温度计和滴液漏斗的1000mL的三颈烧瓶中，在机械搅拌条件下，在15min内向悬浮液中滴加40mL的25wt%的对甲苯磺酸水溶液，升温至80 ℃，在此温度下搅拌8h，分离滤液和滤渣，用蒸馏水洗涤滤渣至洗涤液为中性，滤渣干燥后制得酒糟基莱赛尔纤维浆粕。
实施例5
在实施例4的基础上，本实施例将步骤（3）中升温温度由80℃变为90℃，其余内容与实施例4完全相同。
具体步骤（3）为：将上述干重为25g的烧碱/亚硫酸钠处理酒糟粉分散于400mL蒸馏水中，配制成质量浓度为5.88%的酒糟悬浮液，然后移入装有机械搅拌、温度计和滴液漏斗的1000mL的三颈烧瓶中，在机械搅拌条件下，在15min内向悬浮液中滴加40 mL的25wt%的对甲苯磺酸水溶液，升温至90℃，在此温度下搅拌8h，分离滤液和滤渣，用蒸馏水洗涤滤渣至洗涤液为中性，滤渣干燥后制得酒糟基莱赛尔纤维浆粕。
实施例6
在实施例4的基础上，本实施例将步骤（3）的向悬浮液中滴加对甲苯磺酸水溶液的体积由原来的40mL变为66.7mL，其余内容与实施例4完全相同。
具体步骤（3）为：将上述干重为25g的烧碱/亚硫酸钠处理酒糟粉分散于400mL蒸馏水中，配制成质量浓度为5.88%的酒糟悬浮液，然后移入装有机械搅拌、温度计和滴液漏斗的1000mL的三颈烧瓶中，在机械搅拌条件下，在15min内向悬浮液中滴加66.7mL的25wt%的对甲苯磺酸水溶液，升温至80 ℃，在此温度下搅拌8h，分离滤液和滤渣，用蒸馏水洗涤滤渣至洗涤液为中性，滤渣干燥后制得酒糟基莱赛尔纤维浆粕。
对比例4
本对比例是在实施例4的基础上，将有机酸种类由对甲苯磺酸改为苯磺酸，其余内容与实施例1完全相同。
具体步骤（3）为：将上述干重为25g的烧碱/亚硫酸钠处理酒糟粉分散于400mL蒸馏水中，配制成质量浓度为5.88%的酒糟悬浮液，然后移入装有机械搅拌、温度计和滴液漏斗的1000mL的三颈烧瓶中，在机械搅拌条件下，在15min内向悬浮液中滴加40mL的25wt%的苯磺酸水溶液，升温至80 ℃，在此温度下搅拌8h，分离滤液和滤渣，用蒸馏水洗涤滤渣至洗涤液为中性，滤渣干燥后制得白酒酒糟浆粕。
对比例5
本对比例是在对比例4的基础上，将步骤（3）中升温温度由80℃变为90℃，其余内容与对比例4完全相同。
具体步骤（3）为：将上述干重为25g的烧碱/亚硫酸钠处理酒糟粉分散于400mL蒸馏水中，配制成质量浓度为5.88%的酒糟悬浮液，然后移入装有机械搅拌、温度计和滴液漏斗的1000mL的三颈烧瓶中，在机械搅拌条件下，在15min内向悬浮液中滴加40mL的25wt%的苯磺酸水溶液，升温至90 ℃，在此温度下搅拌8h，分离滤液和滤渣，用蒸馏水洗涤滤渣至洗涤液为中性，滤渣干燥后制得白酒酒糟浆粕。
对比例6
本对比例是在对比例4的基础上，将步骤（3）的向悬浮液中滴加苯磺酸水溶液的体积由原来的40mL变为66.7mL，其余内容与对比例1完全相同。
具体步骤（3）为：将上述干重为25g的烧碱/亚硫酸钠处理后的酒糟粉分散于400 mL蒸馏水中，配制成质量浓度为6.25%的酒糟悬浮液，然后移入装有机械搅拌、温度计和滴液漏斗的1000mL的三颈烧瓶中，在机械搅拌条件下，在10min内向悬浮液中滴加66.7mL的25wt%的苯磺酸水溶液，升温至80 ℃，在此温度下搅拌6h，分离滤液和滤渣，用蒸馏水洗涤滤渣至洗涤液为中性，滤渣干燥后制得白酒酒糟浆粕。检测实施例4~6和对比例4~6的黄酒酒糟浆粕中纤维素的纯度，结果如表2所示。
表2 不同处理工艺下白酒酒糟浆粕中纤维素的纯度
注：每种浆粕的纤维素纯度测试实验重复3次，数据统计时使用SAS软件分析数据，置信区间设置为95%，p值若小于0.05被认为是具有统计学意义的差异。在表1中，具有相同小写字母的数据点在统计学上被认为彼此间无显著差异。
实施例7
本实施例中，酒糟来自于浙江一家以大麦为主要原料的啤酒生产厂家；具体酒糟基莱赛尔纤维浆粕的制备方法，如下：
1）将酒糟原料在研钵中精细研磨，过50目筛，在真空干燥箱中烘至绝干。根据成分分析，该烘干后酒糟原料的主要成分粗淀粉、粗蛋白、粗纤维、粗脂肪及灰分的质量占比分别为13.10%，28.26%，15.82%，6.75%及3.34%。将研磨后干重为100 g的酒糟粉分散于600 g蒸馏水中，配制成质量浓度为14.3%的酒糟悬浮液，然后移入装有机械搅拌、温度计和滴液漏斗的2000mL的三颈烧瓶中，在机械搅拌条件下，在10 min内向悬浮液中滴加13 mL的25wt%的稀硫酸，升温至50 ℃，在此温度下搅拌60 min，过滤、蒸馏水充分洗涤至中性，干燥后制得稀硫酸处理酒糟粉。根据成分分析，该稀硫酸处理酒糟粉的主要成分粗淀粉、粗蛋白、粗纤维、粗脂肪及灰分的质量占比分别为0.98%，50.21%，27.68%，9.90%及3.62%。
2）将上述干重为50 g的稀硫酸处理酒糟粉分散于1100g蒸馏水中，配制成质量浓度为4.35%的酒糟悬浮液，然后移入装有机械搅拌、温度计和滴液漏斗的2000 mL的三颈烧瓶中，在机械搅拌条件下，依次向悬浮液中加入40 g烧碱、5 g亚硫酸钠，升温至98 ℃，在此温度下搅拌1 h，过滤、蒸馏水充分洗涤至中性，干燥后制得烧碱/亚硫酸钠处理酒糟粉。根据成分分析，该烧碱/亚硫酸钠处理酒糟粉的主要成分仅剩粗纤维，其质量占比为96.06%。
3）将上述干重为25 g的烧碱/亚硫酸钠处理酒糟粉分散于300 mL蒸馏水中，配制成质量浓度为7.69%的酒糟悬浮液，然后移入装有机械搅拌、温度计和滴液漏斗的1000 mL的三颈烧瓶中，在机械搅拌条件下，在10 min内向悬浮液中滴加30 mL的25wt%的对甲苯磺酸水溶液，升温至80 ℃，在此温度下搅拌7 h，分离滤液和滤渣，用蒸馏水洗涤滤渣至洗涤液为中性，滤渣干燥后制得酒糟基莱赛尔纤维浆粕。
实施例8
在实施例7的基础上，本实施例将步骤（3）中升温温度由80℃变为90℃，其余内容与实施例7完全相同。
具体步骤（3）为：将上述干重为25g的烧碱/亚硫酸钠处理酒糟粉分散于300mL蒸馏水中，配制成质量浓度为7.69%的酒糟悬浮液，然后移入装有机械搅拌、温度计和滴液漏斗的1000mL的三颈烧瓶中，在机械搅拌条件下，在10min内向悬浮液中滴加30 mL的25wt%的对甲苯磺酸水溶液，升温至90 ℃，在此温度下搅拌7h，分离滤液和滤渣，用蒸馏水洗涤滤渣至洗涤液为中性，滤渣干燥后制得酒糟基莱赛尔纤维浆粕。
实施例9
在实施例8的基础上，本实施例将步骤（3）的向悬浮液中滴加对甲苯磺酸水溶液的体积由原来的30mL变为50mL，其余内容与实施例8完全相同。
具体步骤（3）为：将上述干重为25g的烧碱/亚硫酸钠处理酒糟粉分散于300mL蒸馏水中，配制成质量浓度为7.69%的酒糟悬浮液，然后移入装有机械搅拌、温度计和滴液漏斗的1000mL的三颈烧瓶中，在机械搅拌条件下，在10min内向悬浮液中滴加50mL的25wt%的对甲苯磺酸水溶液，升温至80 ℃，在此温度下搅拌7h，分离滤液和滤渣，用蒸馏水洗涤滤渣至洗涤液为中性，滤渣干燥后制得酒糟基莱赛尔纤维浆粕。
对比例7
本对比例是在实施例7的基础上，将有机酸种类由对甲苯磺酸改为苯磺酸，其余内容与实施例7完全相同。
具体步骤（3）为：将上述干重为25g的烧碱/亚硫酸钠处理酒糟粉分散于300mL蒸馏水中，配制成质量浓度为7.69%的酒糟悬浮液，然后移入装有机械搅拌、温度计和滴液漏斗的1000mL的三颈烧瓶中，在机械搅拌条件下，在10min内向悬浮液中滴加30mL的25wt%的苯磺酸水溶液，升温至80 ℃，在此温度下搅拌7h，分离滤液和滤渣，用蒸馏水洗涤滤渣至洗涤液为中性，滤渣干燥后制得酒糟基莱赛尔纤维浆粕。
对比例8
本对比例是在对比例7的基础上，将步骤（3）中升温温度由80℃变为90℃，其余内容与对比例7完全相同。
具体步骤（3）为：将上述干重为25g的烧碱/亚硫酸钠处理酒糟粉分散于300mL蒸馏水中，配制成质量浓度为7.69%的酒糟悬浮液，然后移入装有机械搅拌、温度计和滴液漏斗的1000mL的三颈烧瓶中，在机械搅拌条件下，在10min内向悬浮液中滴加30mL的25wt%的苯磺酸水溶液，升温至90 ℃，在此温度下搅拌7 h，分离滤液和滤渣，用蒸馏水洗涤滤渣至洗涤液为中性，滤渣干燥后制得酒糟基莱赛尔纤维浆粕。
对比例9
本对比例是在对比例7的基础上，将步骤（3）的向悬浮液中滴加苯磺酸水溶液的体积由原来的30mL变为50mL，其余内容与对比例1完全相同。
具体步骤（3）为：将上述干重为25g的烧碱/亚硫酸钠处理酒糟粉分散于300mL蒸馏水中，配制成质量浓度为7.69%的酒糟悬浮液，然后移入装有机械搅拌、温度计和滴液漏斗的1000mL的三颈烧瓶中，在机械搅拌条件下，在10 min内向悬浮液中滴加50 mL的25wt%的苯磺酸水溶液，升温至80 ℃，在此温度下搅拌7 h，分离滤液和滤渣，用蒸馏水洗涤滤渣至洗涤液为中性，滤渣干燥后制得酒糟基莱赛尔纤维浆粕。检测实施例7~9和对比例7~9的黄酒酒糟浆粕中纤维素的纯度，结果如表3所示。
表3 不同有机酸处理工艺下啤酒酒糟中纤维素的纯度
注：每种浆粕的纤维素纯度测试实验重复3次，数据统计时使用SAS软件分析数据，置信区间设置为95%，p值若小于0.05被认为是具有统计学意义的差异。在表1中，具有相同小写字母的数据点在统计学上被认为彼此间无显著差异。
Claims (8)
- 一种酒糟基莱赛尔纤维浆粕的制备方法，其特征在于，包括以下步骤：（1）稀硫酸处理：酒糟原料依次经烘干、研磨成粉、过筛处理后，得到酒糟粉；以水为反应介质，将酒糟粉配成悬浮液I；在搅拌条件下，向悬浮液I中滴加稀硫酸，升温至40~50℃，搅拌后过滤，水充分洗涤至中性，干燥后，制得稀硫酸处理后的酒糟粉；（2）烧碱/亚硫酸钠处理：以水为反应介质，将步骤（1）稀硫酸处理后的酒糟粉配成悬浮液II，在搅拌条件下，依次向悬浮液II中加入一定质量的烧碱、亚硫酸钠，升温至95~100℃，搅拌后过滤，水充分洗涤至中性，干燥后，制得烧碱/亚硫酸钠处理后的酒糟粉；（3）对甲苯磺酸处理：以水为反应介质，将步骤（2）烧碱/亚硫酸钠处理后的酒糟粉配成悬浮液III，在搅拌条件下，向悬浮液III中滴加对甲苯磺酸水溶液，升温至70~80 ℃，搅拌后过滤，分离滤液和滤渣，水洗涤滤渣至洗涤液为中性，滤渣干燥后，制得酒糟基莱赛尔纤维浆粕。
- 如权利要求1所述的酒糟基莱赛尔纤维浆粕的制备方法，其特征在于，步骤（1）中，所述酒糟粉的粒径在50~300目之间；以质量百分数计，所述悬浮液I中，酒糟粉的质量百分数为10~20%。
- 如权利要求1所述的酒糟基莱赛尔纤维浆粕的制备方法，其特征在于，步骤（1）中，所述稀硫酸的质量浓度为20~30%；稀硫酸与水的体积比为1:40~1:50，10~15 min内完成滴加操作；搅拌时间为30~60 min。
- 如权利要求1所述的酒糟基莱赛尔纤维浆粕的制备方法，其特征在于，步骤（2）中，以质量百分数计，所述悬浮液II中，稀硫酸处理后的酒糟粉的质量百分数为2.5%~5.0%。
- 如权利要求1所述的酒糟基莱赛尔纤维浆粕的制备方法，其特征在于，步骤（2）中，烧碱与稀硫酸处理后的酒糟粉的质量比为1:1~1:1.5；亚硫酸钠与稀硫酸处理后的酒糟粉的质量比为1:9~1:12；搅拌时间为4~6h。
- 如权利要求1所述的酒糟基莱赛尔纤维浆粕的制备方法，其特征在于，步骤（3）中，以质量百分数计，所述悬浮液III中，烧碱/亚硫酸钠处理后的酒糟粉的质量百分数为5%~10%。
- 如权利要求1所述的酒糟基莱赛尔纤维浆粕的制备方法，其特征在于，步骤（3）中，所述对甲苯磺酸水溶液的质量浓度为20~30%；对甲苯磺酸水溶液与水的体积比为1:6~1:10，10~15 min内完成滴加操作；搅拌时间为6~8h。
- 如权利要求1~7任一项所述的制备方法制得的酒糟基莱赛尔纤维浆粕。
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