• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A process for the modification, solubilisation and/or hydrolysis of a glycosidically linked carbohydrate having reducing groups using a mixture comprising water, an inorganic acid and a halide of lithium, magnesium or calcium. The process is particularly useful for converting cellulose (derived for example from wate-paper, wood or sawdust) or starch to glucose. When cellulose is the starting material the preferred halide is a lithium halide. When starch is the starting material a magnesium halide is preferred.
    公开号:SU1318171A3
    申请号:SU813312255
    申请日:1981-07-10
    公开日:1987-06-15
    发明作者:Алан Баркер Сидней；Джон Самерз Питер
    申请人:Империал Кемикал Индастриз Лимитед (Фирма)；
    IPC主号:
    专利说明:

    113
    The invention relates to chemistry, namely, to a process for the preparation of aqueous solutions of glucose or its mixture with oligaride.
    The purpose of the invention is to accelerate the process of dissolution and hydrolysis of cellulose, starch and materials containing cellulose,
    This goal is achieved by using inorganic acids and lithium, magnesium or calcium halides in certain concentrations and at certain temperatures,
    - Example 1. The composition of the feedstock,
    Duplicate samples (25 mg each) are carefully weighed in test vials with stoppers and sulfuric acid (98%, 1 cm, h, da is added). These suspensions were kept at a temperature below 0 ° C with nOMODtbW) baths with a mixture of ice and salt (10 ° C). After 48 h at 4 ° C, distilled water (8.0 cm) was added and the vials were heated for 2.5 h. in a boiling water bath. After cooling to room temperature, the content of D-glucose and the total carbohydrate content are determined.
    The results are shown in table 1.
    The composition of the materials used is expressed in weight percent with respect to glucose in terms of dry weight.
    Table 1

    .96.5 97.5
    97.8 88.0
    41.0 41.0
    41.0
    41.0
    Continuation of table 1
    5 Newspaper Paper
    Content of easily hydrolyzable neutral carbohydrates derived from
    non-cellulose polysaccharides (for example, hemicellulose),
    Samples of dry material (50–60 mg) are carefully weighed into test vials and trifluoroacetic acid (2.0 M, 2.0 cm) is added, the ampoules are sealed and heated in a bath with water for 6 hours. After cooling and opening ampoules of trifluoroacetic acid are evaporated. The residue is placed in an internal buffer (O, 13 M, pH 7.5, 1.0 cm) and analyzed using borate anion exchange chromatography (IEOL analytical system). The data obtained are given in
    Table 2,
      Table 2
    The content of neutral sugars in trifluoroacetic c-acid hydrolyzates obtained from non-cellulose polysaccharides, expressed in weight,%, calculated on the dry weight
    0
    five
    30 min 35 min Ramiosis 92 min 144 min
    0.03 0.05
    0.9
    0.1.3 0.12
    0.45
    0.10 0.15
    0.24 0.17
    Mannose
    Tracks 7.27
    3.90
    3131
    Continuation of table 2



    0.92 0.54
    Traces 1.60 0.86 0.14 2.73 1.89
    0.22 13.91 8.06 3.32 3.49 2.26
    0.03 0.11 0.10
    Example 2. Treatment of cellulose with solutions of lithium chloride and a mixture of lithium chloride and hydrochloric acid at elevated temperatures.
    Prepare two test solutions by placing portions of cellulose fiber (50 mg each) in two test ampoules and adding a saturated solution of lithium chloride (5.0 cm) to one of them, and a saturated solution of lithium chloride - reed. The vials are sealed, placed on. night in the fridge, and then in the bath with boiling water. After 5 minutes, the vial containing HCl / LiCl is removed from the bath, since the pulp is almost dissolved and cooled in an ice bath. The vial with the LiCl solution is held in a bath of boiling water for 12 hours. The solution and the supernatant are analyzed for the total carbohydrate content using standard solutions of D-glucose in the grade lithium chloride solution.
    The results are shown in table 3. These results indicate that the pretreatment with hydrochloric acid (0.5 M), with acetyl lithium chloride, provides a high degree of dissolution (approximately 54%). Dissolved carbohydrates are according to gel permeation chromatography in Os8171.
    new glucose (5.0 MG CM from
    6.0 mg-cm), and the rest - mainly
    way disaccharides.
    Table 3 Dissolution of cellulose fiber in a saturated solution of LiCl and in hydrochloric acid (0.5 M) saturated with LiCl
    Solution
    Total concentration of carbohydrates in supernatant liquid, mg-cm
    LiCl / HCl
    LiCl
    6.0
    2.4
    Example 3. Treatment of cellulosic fiber with hydrochloric acid of various concentrations, using acetylene chloride.
    Samples of cellulose fiber (50 mg each) are placed in test ampoules, to each of which a solution (5.0 cm) of hydrochloric acid (0.1.0.5, 1.0, 2.0, 3.0 or 4 is added. , 0 M), saturated with lithium chloride. The ampoules are sealed and placed in a bath with boiling water. The vials are removed as dissolution occurs, which is observed visually, and a noticeable discoloration is observed. After being removed from the bath, the ampoules are cooled in an ice bath and stored in a refrigerator until the analysis of the total carbohydrate content in the solution.
    The results are shown in table 4. The data of Table 4 shows that hydrochloric acid (4.0 M), saturated with lithium chloride, allows to achieve almost complete dissolution.
    Table 4
    50
    55
    5131
    Continuation of table 4,

    2 min 3,4 57 s
    5 5 30
    7.3 1, A
    32
    68 13
    There is no dim
    dissolving
    Example 4 Treatment of cellulose fiber with hydrochloric acid (4.0 M) containing lithium chloride,
    The procedure of Example 3 is repeated using hydrochloric acid concentrations (4.0 M) with different contents of lithium chloride,
    The results are shown in Table 5.
    Table 5
    Example 5 Treatment of cellulose fibers with hydrochloric acid of various concentrations, saturated with lithium chloride, at room temperature, followed by heating.
    The procedure of Example 3 is repeated using hydrochloric acid solutions (0.1, 0.5 and 1.0 M) saturated with lithium chloride. These test solutions were allowed to stand for 60 hours at room temperature before heating.
    The results are shown in Table 6. The data obtained, when compared with the data in Table 4, indicates that the pretreatment increases the solubility of cellulose.
    W
    Table
    Cellulose fiber solubility when treated with hydrochloric acid saturated with lithium chloride, after pretreatment at room temperature
    40
     Example 6, Treatment of various materials containing cellulose, hydrochloric acid (1.0 M), saturated with lithium chloride.
    45 Test cellulose fiber, mechanical pulp, newsprint 1 (Daily Mirror), newsprint 2 (Observer, no paint) and yeast glucan. Samples of each of
    50 materials (50 mg each) are suspended in a solution (5 cm) of hydrochloric acid (0.1 M) saturated with lithium chloride, and treated as in Example 5. The resulting solutions are clarified
    55 by centrifugation prior to analysis for the full content of the coalheads and before the study using gel permeation chromatography for obtaining 713
    PII of data on milk-weight distribution.
    The results are shown in table 7. The data presented in Table 7 indicate that the cellulose fiber was completely solubilized (within the limits of the experiment), and the solubilized carbohydrate for mechanical pulp and newsprint is quite comparable to its true content in these materials.
    Table 7 Time to reach maximum concentration of sugar in solution, Solubilization of various cellulose-containing materials in hydrochloric acid (1.0 M) saturated with lithium chloride
    Example 7, Treatment of various cellulose-containing materials with hydrochloric acid (4.0 M) saturated with lithium chloride.
    0
    81718
    Examine cellulose fiber, mechanical pulp, newsprint 1 (Daily Mirror), newsprint 2 (Observer, no paint), and as
    5 control glucose and cellobiose. Samples (50 mg) of each material are suspended in a solution (5.0 cm) of hydrochloric acid (4.0 M) poured with lithium chloride. These suspensions are sealed in glass ampoules and placed in a bath of boiling water. Then the ampoules are processed and analyzed as in Example 2 for the total content of carbohydrate j, a p-but-weight distribution of molecules is obtained using gel permeation chromatography.
    The results are shown in table 8. The data obtained indicate complete dissolution of cellulose fiber.
    Table 8
    five
    0
    Cellulose
    Mechanical pulp
    1.33 10.5
    1.75
    5.2
    55
    Relative molecular distribution,%: G1 28.9; G2 17.0; G3 13.3; G4 11.7; G5 8.8; G6 7.1; G7 4.5; G8 3.1; G9 2.4; G10 1.3; GI1 50 1.0; G 12 0.8,
    Example 8. Treatment of cellulosic fiber with various acids in solutions saturated with inorganic salts.
    Cellulose samples (50 mg each) are suspended in various solutions (5.0 cm), as indicated in Table 9. All these solutions are kept at 4 ° C in
    9131817110
    For 20 hours, before being mixed with ice, before performing them in a bath of boiling water, an ERA is an analysis of the total carbohydrate. The charger is followed by the procedure described in Example 2. All ampu-
    ly after heating up
     Table 9 Dissolution of cellulose fiber in various acid / salt combinations


    Obtained from a solution of HBr (45% w / v) in glacial acetic acid.
    Received from.
    Forms two phases, and analyzed the upper phase.
    in tables 9 and 10,
    eleven
    Table
    Dissolving Cellulose Fiber in Hydrochloric Acid, Used with Lithium Chloride, and Hydrochloric Acid Saturated with Magnesium Chloride
    ,
    Not
    thirty
    24
    Example 9. Treatment of cellulose fiber with hydrochloric acid only.
    Samples of cellulose fiber (50 mg each) are placed in test ampoules, hydrochloric acid (3.5 M, 5.0 cm) is added to each of them. The ampoules are sealed and placed in a boiling water bath, the Apmules are removed after 2.4, 8 and 12 hours. The solutions after B and 12 hours were yellow, and the residual cellulose turned black, while the solutions after 2 and 4 hours were colorless and the residual cellulose was white; The analysis of the supernatant for the total carbohydrate content,
    , The results are shown in Table 11, Comparison of the data in Table 11 with Table 4 shows the effectiveness of hydrochloric acid in combination with lithium chloride. Thus, 17% of solubility is reached with HC1 (3.5 M) in 720 minutes compared to the full solubility in 55 s using HC1 (4.0 M), saturated with lithium chloride or 83% solubility in 55 s using HC1 (3.0 M), using lithium chloride.
    1318171
    ten
    12
    Table 11
     heating, min
    The total carbohydrate content in solution in%
    0
    five
    0
    five
    0
    five
    0
    five
    Example 10, the Dissolution and hydrolysis of cellulose fiber in hydrochloric acid and lithium chloride at 50 ° C.
    Cellulose fiber samples are placed in flasks with a screw cap and appropriate test solutions (10 cm) are added to them, as indicated in Table 12. Sklki nki placed in a bath of water at 50 ° C and mix the contents with magnetic stirrers. Samples (0.1 cm) are removed at the indicated time intervals, diluted with water (up to 10 cm) and stored at 4 ° C until analysis. The analysis for total carbohydrate and H-glucose is performed by diluting samples with a high concentration of cellulose. The results are shown in Table 12, the data presented in it demonstrate the effectiveness of hydrochloric acid (4.0 M) saturated with lithium chloride as a solvent for cellulose fiber at a ratio of 1.5 or 10 vol / weight, and complete dissolution is reached at 50 ° C within an hour within the experimental error.
    Example 11. Solubilization and hydrolysis of cellulose fiber with hydrochloric acid (4.0 M) saturated with lithium chloride when treated at 50 ° C, followed by an increase in temperature.
    Samples of cellulose fiber (0.5 or 1.0 g) are placed in flasks with screw caps, to each of which hydrochloric acid (4, O.M), saturated with lithium chloride (10.0 cm) is added. These flasks are placed in a bath with water at 50 ° C for 1 or 2 hours, and their contents are stirred on a magnetic stirrer.
    1313181
    At the end of the first CTaflHtj, the aliquots are selected (1.0 cm) and placed in smaller bottles. Then these flasks are placed in a bath with a temperature of 80 ° C or with boiling water, the Skl n – s ki are removed at certain intervals, cooled and maintained at C until analysis. These samples are diluted 1000-fold prior to analysis for the total carbohydrate content, D-gluco-fOs, and molecular weight distribution is determined by gel chromatography. The results are shown in table, 13 and 14, hydrochloric acid solutions (4.0 M), saturated with lithium chloride,
    71
    14
    characterized by measuring the refractive index at 20 ° C using a sodium line. The refractive indices of solutions of various concentrations of lithium chloride are also measured. The results are given in Table 15. On the basis of these d, as well as density measurements, the estimated composition of the hydrochloric acid solution (4.0 M) saturated with lithium chloride, g / l:
    HC1 146.0
    15
    LiCl479.0
    HjO640,7
    Table 12 Solubilization of cellulose fiber at various treatments at 50 ° C
    1.0
    HC1 (4.0 M),
    saturated LiCl
    1.0
    HC1 (4.0 M)
    HC1 (1.0 M),
    saturated
    LiCl,
    with pre 3.0
    by treatment
    4 seconds
    20 h
    71
    14
    characterized by measuring the refractive index at 20 ° C using a sodium line. The refractive indices of solutions of various concentrations of lithium chloride are also measured. The results are shown in Table 15. On the basis of these d, ana, and also density measurements, the estimated composition of the hydrochloric acid solution (4.0 M) saturated with lithium chloride, g / l:
    HC1 146.0
    97
    1680
    15
    HC1 (4.0 M),
    saturated LiCl
    1.0
    2.0 H., 0 5.5
    HC1 (4.0 M), 1.0 107.6 42.4
    Nacional LiCl
    2.0 106.0 61.9
    10.0
    3.0 104.7 65.3 5.5 100.3 68.5
    An analysis of the molecular distribution of this sample indicates the following composition,%: G1 57.1; G2 23.5; G3 7.7; 04 2.5; G5 1.2; G6 0.4; 07 0.2; 08 0.1; unidentified 7.4.
    P
    12, Dissolution and hydrolysis of starch (Amylum maydis) with hydrochloric acid (2.0 M), saturated with magnesium chloride, when heated.
    Samples of starch (Amylum maydis), 2.0 g each, are placed in flasks with screw-in plugs and a solution (20.0 cm) of hydrochloric acid (2.0 M) saturated with magnesium chloride 6Hj, 0 is added to each. The containers are immersed in a bath with a constant temperature of 50 ° C for 30 and J80 minutes, and the contents are stirred with magnesium furniture with a temperature of 90 ° C for up to 20 minutes. After cooling, the total carbohydrate and D-glucose content in the solution is determined. The results obtained are shown in Table 16. A control solution of hydrochloric acid (1.0 M and 4.0 M) is also used as a medium for dissolution and hydrolysis. The results of the control experiment are shown in Table 17. It can be seen that under these conditions the glucose hydrolysis is insignificant in the absence of magnesium chloride, and in its presence dissolution is achieved easily at higher levels.
    . After a certain period of time, the content of the hydrochloric pussy of time is transferred to the containers in lots.
    .Table13
    Full coning. carbohydrates and D-glucose after treating cellulose fiber with a solution of HC1 (4.0 M), saturated with lithium chloride, under various conditions
    131817
    16 Continuation of table 12
    104
    100
    bath with a temperature of 90 ° C for up to 20 minutes. After cooling, the total carbohydrate and D-glucose content in the solution is determined. The results are shown in table. A control solution of hydrochloric acid (1.0 M and 4.0 M) is also used as a medium for dissolution and hydrolysis. The results of the control experiment are given in table 17. It can be seen that under these conditions the glucose hydrolysis is insignificant in the absence of magnesium chloride, and in its presence dissolution is achieved easily at higher levels.
    10.0
    1.0
    80
    10.0
    2.0
    100
    5.0
    1.0
    100
    Continuation of table 13
    54
    40
    radio
    tsesh
    ei,
    Immersed in a bath of boiling water, nominal.
    Table -14
    Distribution of lithium chloride and carbohydrates by molecular weights
    10.0
    10.0
    10.0
    50, 60 100, 3 50, 60 100, 7 50, 120 100, 3
    65.9 19.8 3.9 0.8 0.2 9.4
    60.3 21.6 4.4 0.9 0.2 12.6
    65.3 23.0 4.3 0.8 0.8 6.3
    5.0 5.0, 60 81.8 10.6 1.3 100, 2
     100 ° С nominal, immersed in a boiling water bath.
    Table 15 Refractive indices for lithium chloride solutions
    HC1 (4.0 M) LiCl (9.0 M) 1.4180 HC1 (4.0 M) LiCl (10.0 M) 1.4251 HC1 (4.0 M) LiCl (II, OM) 1.4300
    Table 16
    Dissolution and hydrolysis of starch in hydrochloric acid and in hydrochloric acid saturated with magnesium chloride
    20
    40
    60
    90
    120
    150
    180
    thirty
    0.2
    6.1
    Continuation tabl, 15
    Table 17
    Example 13. The dissolution and hydrolysis of starch hydrochloric acid (2.0 M), saturated. with the addition of water during the hydrolysis phase and without the addition of water
    The procedure of Example 12 is repeated using starch (1.5 g) and hydrochloric acid, (2.0 M), saturated with MgCli (10 cm). After 3 hours, at 50 ° C, water (0.15 cm) was added to one set of solutions, and the hydrolysis was continued at 50 ° C. D-glucose was kept in solution at various time intervals given in Table 18.
    Table 18
    Example 14. A sample of filter paper is treated with an aqueous solution containing 11 wt.% Calcium chloride and 31 wt.% (8.5 mol / kg) hydrogen chloride and 5% solids at 70 ° C for 10 minutes. Analysis of the resulting solution showed that the solubility of the feedstock was 79.2%.
    Example 15. A sample of filter paper is treated with hydrochloric acid (10 mol / kg) containing calcium chloride. The resulting reaction mixture has the following composition,%: hydrochloric acid 36.4, chloride
    2513
    calcium 5.1; filter paper 5.0; water 53.5.
    Filter paper processing. carried out with stirring, for 10 minutes at 70 ° C. At the end of treatment, 89.3% of the filter paper dissolved. Conversion of filter paper to glucose 73.3%,
    The reaction mixture is diluted with water: 1.1 water is added to 30 kg of the mixture and the treatment is continued for 30 minutes at 130 ° C. At the end of the treatment, it was found that the conversion of filter paper to glucose increased to 82.6%,
    Example 16, Dissolving and hydrolysis of cellulose using low concentrations of calcium chloride and high concentrations of acid,
    J 50 g of hydrochloric acid (35.4%) is kept overnight in a freezer at -20 ° C. Then 50 g of anhydrous calcium chloride (molten granular, 8-16 mesh,) are added to it. The mixture is agitated and returned in the freezer, where it is stored for 24 hours, shaking occasionally. During this period of time, the liquid is decanted into a cold vessel and analyzed for calcium chloride and HC1. The analysis result is as follows:
    Weight,%
    4.7
    43.4
    mol / kg
    0.42
    11.89
    27 g of the liquid thus prepared is added to 3 g of dry filter paper (Whatman No. 1) in a 30 mm glass tube, which is then sealed. Thereafter, the reaction is carried out by keeping this tube in a water bath at 70 ° C and slightly shaking. This is done for 10 minutes, after which the filter paper appears almost dissolved. The resulting liquid solution is diluted with deionized water, topping up to a volume of 1 l. This solution is analyzed for glucose monomer and filtered to determine the amount of undissolved filter paper remaining.
    The experiment is repeated for 12 minutes.
    The results are shown in Table 19.
    Thus, the invention makes it possible to eliminate the preliminary stage of lignin separation, to increase the rate of cellulose hydrolysis both in homogeneous and heterogeneous systems, to increase the working concentration of cellulose in solution. In addition, pre-processing of the raw material by the proposed method facilitates its subsequent enzymatic processing. Methods of analysis.
    Determination of total carbohydrate content
    The cysteine – sulfuric acid reagent mixture (700 mg of L-cysteine hydrochloride, read monohydrate in 1 liter of 86% sulfuric acid) is added to a portion of the mixture sample – standard so that the ratio of reagent to sample (standard) is 5: 1 cm
    1 cm).
    0
    five
    0
    five
    The reagent is added to the sample in ampoules immersed in an ice bath. Then the ampoules are placed in a boiling water bath for 3 minutes, after which they are removed and left to sit at room temperature. The absorbance of each solution is measured at 420 nm and the concentration of carbohydrates is determined compared to the absorbance of the corresponding standard, resulting in the results given in the examples.
    Determination of reducing sugars,
    Buffer: Sodium acetate - acetic acid: 0.05 M, pH 4.8,
    Reagent: Potassium ferricyanide (0.117 g) and sodium carbonate (1.95 g) are dissolved in distilled water and brought to 100 cm. This solution is re-prepared every morning.
    Standard solutions (0-600 µg / cm D-glucose; 0.4 cm) samples
    2713
    (0.4 cm) is added to test vials cooled in an ice bath, containing the reagent - (2.0 cm) and buffer (1.5 cm). After mixing, the test ampoules are immersed in a boiling water bath for 5 minutes, then cooled to room temperature. The reaction mixture is then diluted by adding water (4, -O cm), and the absorbance of each sample is measured at 420 nm. The difference in the absorption of the standard or sample and the cuvette (in which the sample is replaced by water) makes it possible to calculate the content of reducing sugar relative to D-glucose. I
    Determination of D-glucose.
    Buffer: 2-amino-2- (hydroxymethyl) propane (l, 2-diol) (TRIS), 0.5 M, pH 7.0.
    Reagent A: Glucose oxidase (19,500 units per g 50 mg) dissolved in buffer (50 cm).
    Reagent B: Peroxidase (seaside spoon, 90 units per mg, 10 mg) and 2,2-aniso-di- (Z-ztilbenzthiazoline) - sulfuric acid (ABTS), 50 mg, dissolved in buffer (100 cm).
    Standard solutions of D-glucose or unknown solutions containing D-glucose (D d about 0.1 mg per cm, 0.2 cm) are smeared with reagent A (0.5 cm) and reagent B (1.0 cm). After 30 minutes at 37 ° C., the absorbance of each sample at A20 nm is measured and the concentration of D-glucose of unknown solutions is determined by comparison with calibrated standard solutions of D-glucose.
    | d (Gel Permeation Chromatography.
    Chromatographic data were obtained on a Biogel P-2 instrument (Bielad Laboratories Linuted). Depending on the method of analysis, columns of two sizes were used to determine the material in the column of eluate.
    Method A: Chromatography was performed on a BiogelP-2 in a glass column (A25 cm, 50 cm length) with a water jacket, the temperature of which was maintained at 60 ° C. The column was pumped at a rate of 0.8. The eluate from the column was separated and analyzed by differential refractometry (Waters Associates Model R401) in a mode of 0.32 cm / min and / or by an automated method using a mixture of cysteine-sulfuric acid for complete determination of the hexose content of S.A
    ker. M.I. Hon P.V. Peplov and P.I. Sotners Anal. Biochen 26, (1968), 219) in 0.1 mode for the sample flow rate. Sample volume
    introduced into the Biogel P-2 column, was 0-0.1 cm, and contained 0 - 5 mg of carbohydrate.
    Method B: Chromatography was carried out as in Method A, only a 145 cm x X 0.6 cm internal diameter column was used and
    operated at a flow rate of 0.15 cm / min. Analysis of the column sylvate was performed using
    Cysteine-sulfuric acid mixtures for the complete determination of hexose as in Method A. The sample volume was O - 0.01 cm, and contained O - 0.5 mg of carbohydrate.
    The peak areas for the carbohydrate-containing material were integrated and compared with the area values obtained for the D-glucose standards. The results were expressed in
    The percentage of total carbohydrate content determined in zluate, in cases where the products were a series of oligomers, used the notation G-1, G-2, -C "to
    indicate the number of sugar fragments in each oligomer.
    The moisture content in the samples after stripping over,%: cellulose fiber 3.7; mechanical
    pulp 8.1, newsprint 7.2.
    权利要求:
    Claims (2)
    [1]
    Invention Formula
    1, A method for producing water glucose solutions or mixtures thereof with oligosaccharides from cellulose or starch or materials containing cellulose by treating them with an aqueous solution of inorganic acid and a metal halide at elevated temperatures, characterized in that, in order to speed up the process, as a halide lithium, magnesium or calcium halides from the metal are used
    the concentration of 0.5 mol / kg of the reaction mass to the concentration of the na-scene, the concentration of inorganic acid is 1-10 mol / kg of the reaction mass, and the reaction temperature
    support in the range of 50 - 100 ° C.
    [2]
    2. Method 1, characterized in that an additional amount of water is added during the process.
    类似技术:
    公开号 | 公开日 | 专利标题
    SU1318171A3|1987-06-15|Method for producing aqueous solutions of glucose or its mixture with oligosaccharides
    Haug et al.1971|Biosynthesis of alginate: Part II. Polymannuronic acid C-5-epimerase from Azotobacter vinelandii |
    Vasseur1948|A spectrophotometric study on the orcinol reaction with carbohydrates
    Rees1981|Polysaccharide shapes and their interactions-some recent advances
    Thom et al.1982|Characterisation of cation binding and gelation of polyuronates by circular dichroism
    CA2677862C|2015-09-01|Fractionation of a lignocellulosic material
    Pollard et al.1992|Nucleotide exchange, structure, and mechanical properties of filaments assembled from ATP-actin and ADP-actin.
    Piculell et al.1992|Effects of small amounts of kappa-carrageenan on the rheology of aqueous iota-carrageenan
    KR20050057550A|2005-06-16|Method of determining specific groups forming heparins
    CN1224717C|2005-10-26|Sugarcane sugaring process substituted sulphurous acid method
    Hoermann et al.1971|Reversible and irreversible denaturation of collagen fibers
    Braudo et al.1991|Studies on the mechanisms of gelation of kappa-carrageenan and agarose
    US6586589B1|2003-07-01|Process for treating alginic acid to produce polyguluronic acids or concentrated solutions for use in producing polyguluronic acids
    Borrego et al.1989|Properties of pectinesterase immobilized on glycophase-coated controlled-pore glass
    CA1192541A|1985-08-27|Solubilisation and hydrolysis of carbohydrates
    Elliot et al.1977|The micro-assay of the disaccharide isomers of chondroitin sulphate
    Chapin1919|ARSENIOUS OXIDE AS A STANDARD SUBSTANCE IN IODIMETRY.
    Anderson et al.1963|Studies on uronic acid materials: Part VIII1. a comparative study of some colorimetric methods of estimating the uronic acid contents of polysaccharides
    SU1407401A3|1988-06-30|Method of producing glucose and fructose containing solution
    SU777051A1|1980-11-07|Composition for dehydrating and desalinization of oil
    RU1792420C|1993-01-30|Reagent for treatment of drilling fluid on water base, and a method of its preparing
    SU1402938A1|1988-06-15|Method of determining water in lubricant greases
    Scott et al.1997|Crystallization and preliminary X-ray analysis of arabinofuranosidase C from Aspergillus niger strain 3M43
    Donceel et al.1982|The size and conformation of Artemia | ribosomal RNA free in solution
    SU1234427A1|1986-05-30|Method of vegetative raw material hydrolysis
    同族专利:
    公开号 | 公开日
    NO812358L|1982-01-12|
    ZA814472B|1982-08-25|
    EP0044622A2|1982-01-27|
    DE3171911D1|1985-09-26|
    NO156287B|1987-05-18|
    EP0044622A3|1982-06-09|
    NO156287C|1987-08-26|
    EP0044622B1|1985-08-21|
    US4787939A|1988-11-29|
    JPH0133113B2|1989-07-11|
    US4713118A|1987-12-15|
    ZW14981A1|1983-02-02|
    JPS5748997A|1982-03-20|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US1355415A|1916-11-01|1920-10-12|Ostenberg Zeno|Process of preparing solutions of cellulose|
    CH93275A|1917-05-23|1922-03-01|Alexander Dr Classen|Process for converting substances containing cellulose into fermentable sugar.|
    DD106866A1|1973-07-12|1974-07-05|
    US4018620A|1975-05-19|1977-04-19|Biocel Corporation|Method of hydrolyzing cellulose to monosaccharides|
    US3977897A|1975-09-08|1976-08-31|National Starch And Chemical Corporation|Process for preparing a non-chemically inhibited starch|
    JPS573340B2|1977-06-25|1982-01-21|US4452640A|1982-05-11|1984-06-05|Purdue Research Foundation|Quantitative hydrolysis of cellulose to glucose using zinc chloride|
    US4525218A|1982-05-11|1985-06-25|Purdue Research Foundation|Selective hydrolysis of cellulose to glucose without degradation of glucose using zinc chloride|
    JPS5941302A|1982-09-01|1984-03-07|Noda Shiyokukin Kogyo Kk|Preparation of polysaccharide|
    JPH0445146B2|1983-07-22|1992-07-23|Japan Maize Prod|
    US4699124A|1985-06-28|1987-10-13|Power Alcohol, Inc.|Process for converting cellulose to glucose and other saccharides|
    US4637835A|1985-06-28|1987-01-20|Power Alcohol, Inc.|Methods of hydrolyzing cellulose to glucose and other saccharides|
    US5324828A|1986-12-11|1994-06-28|Genzyme Corporation|1-amino-1-deoxyoligosaccharides and derivatives thereof|
    CA2036490A1|1990-02-20|1991-08-21|Ruth G. Chiou|Method of preparing reduced fat foods|
    US5395640A|1990-02-20|1995-03-07|A.E. Staley Manufacturing Company|Method of preparing reduced fat foods|
    US5374442A|1990-02-20|1994-12-20|A. E. Staley Manufacturing Company|Method of preparing reduced fat foods|
    US5409726A|1990-02-20|1995-04-25|A. E. Staley Manufacturing Co.|Method of preparing reduced fat foods|
    US5436019A|1990-02-20|1995-07-25|A. E. Staley Manufacturing Co.|Method of preparing reduced fat foods|
    US5372835A|1990-02-20|1994-12-13|A. E. Staley Manufacturing Company|Method of preparing reduced fat foods|
    US5387426A|1990-02-20|1995-02-07|A.E. Staley Manufacturing Company|Method of preparing reduced fat foods|
    US5368878A|1990-02-20|1994-11-29|A. E. Staley Manufacturing Company|Reduced fat meat products|
    US5378491A|1990-02-20|1995-01-03|A. E. Staley Manufacturing Co.|Method of preparing a starch hydrolysate, an aqueous starch hydrolysate dispersion, method of preparing a food containing a starch hydrolysate, and a food formulation containing a starch hydrolysate|
    MX9206591A|1991-11-19|1994-05-31|Nippon Shinyaku Co Ltd|PROCESS FOR THE PRODUCTION OF SACARIDES.|
    US5376399A|1992-05-15|1994-12-27|A.E. Staley Manufacturing Co.|Reduced fat cremes|
    USH1394H|1992-05-22|1995-01-03|A. E. Staley Manufacturing Company|Method of preparing reduced fat spreads|
    USH1395H|1992-05-22|1995-01-03|A. E. Staley Manufacturing Company|Composition and method of preparing reduced fat spreads|
    US5766366A|1995-10-13|1998-06-16|A. E. Staley Manufacturing Co.|Dry thinned starches, process for producing dry thinned starches, and products and compositions thereof|
    JP4279482B2|2001-08-06|2009-06-17|富士フイルム株式会社|Photothermographic material|
    WO2005123669A1|2004-06-10|2005-12-29|Board Of Trustees Of Michigan State University|Synthesis of caprolactam from lysine|
    JP5190858B2|2006-07-12|2013-04-24|独立行政法人農業・食品産業技術総合研究機構|Production method of low molecular weight carbohydrates from materials containing polysaccharides|
    US8283466B2|2007-02-20|2012-10-09|Board Of Trustees Of Michigan State University|Catalytic deamination for caprolactam production|
    KR100887563B1|2007-07-06|2009-03-09|한국과학기술연구원|Method for Hydrolyzing Cellulose Using a Solid Acid-Catalyst|
    US8846902B2|2007-10-09|2014-09-30|Bioecon International Holding N.V.|Process for the conversion of cellulose in hydrated molten salts|
    EP2318373A1|2008-07-24|2011-05-11|Draths Corporation|Methods of making cyclic amide monomers, and related derivatives and methods|
    US20100044210A1|2008-08-20|2010-02-25|The Board Of Regents Of The University Of Texas System|METHOD OF DIGESTING CELLULOSE TO GLUCOSE USING SALTS AND MICROWAVEENERGY|
    US8198057B2|2009-06-08|2012-06-12|Alternative Green Technologies, Llc|Ethanol production by fermentation of chinese tallow tree|
    EP2448951B1|2009-07-01|2016-06-01|Wisconsin Alumni Research Foundation|Biomass hydrolysis|
    FR2963009B1|2010-07-23|2013-01-04|IFP Energies Nouvelles|PROCESS FOR PRODUCING SUGARS FROM LIGNOCELLULOSIC BIOMASS PRETREATED WITH HYDRATES INORGANIC SALTS|
    FR2979913B1|2011-09-08|2015-01-16|IFP Energies Nouvelles|PROCESS FOR PRETREATMENT OF LIGNOCELLULOSIC BIOMASS AVRC HYDRATE IRON SALT|
    EP2620442A1|2012-01-27|2013-07-31|BIOeCON International Holding N.V.|Process for recovering saccharides from cellulose hydrolysis reaction mixture|
    US9187790B2|2012-03-25|2015-11-17|Wisconsin Alumni Research Foundation|Saccharification of lignocellulosic biomass|
    US9695484B2|2012-09-28|2017-07-04|Industrial Technology Research Institute|Sugar products and fabrication method thereof|
    CN103710472B|2012-09-28|2016-07-06|财团法人工业技术研究院|Sugar product and preparation method thereof|
    US9850512B2|2013-03-15|2017-12-26|The Research Foundation For The State University Of New York|Hydrolysis of cellulosic fines in primary clarified sludge of paper mills and the addition of a surfactant to increase the yield|
    TWI476203B|2013-03-18|2015-03-11|Ind Tech Res Inst|Method of separating carbohydrate|
    AU2014201106B2|2014-02-28|2015-11-19|Industrial Technology Research Institute|Sugar Products And Fabrication Method Thereof|
    US9951363B2|2014-03-14|2018-04-24|The Research Foundation for the State University of New York College of Environmental Science and Forestry|Enzymatic hydrolysis of old corrugated cardboardfines from recycled linerboard mill waste rejects|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    GB8022715|1980-07-11|
    [返回顶部]