CN103013165B - Method for preparing monascus red pigment by utilizing immobilized enzymes - Google Patents
Method for preparing monascus red pigment by utilizing immobilized enzymes Download PDFInfo
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- CN103013165B CN103013165B CN201210549801.4A CN201210549801A CN103013165B CN 103013165 B CN103013165 B CN 103013165B CN 201210549801 A CN201210549801 A CN 201210549801A CN 103013165 B CN103013165 B CN 103013165B
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- immobilized enzyme
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- 108010093096 Immobilized Enzymes Proteins 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 40
- 241000228347 Monascus <ascomycete fungus> Species 0.000 title abstract description 16
- 239000001054 red pigment Substances 0.000 title abstract 9
- 239000007788 liquid Substances 0.000 claims abstract description 49
- 102000004190 Enzymes Human genes 0.000 claims abstract description 26
- 108090000790 Enzymes Proteins 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 238000000855 fermentation Methods 0.000 claims abstract description 14
- 230000004151 fermentation Effects 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 230000007071 enzymatic hydrolysis Effects 0.000 claims abstract description 4
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 84
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 35
- 229940088598 enzyme Drugs 0.000 claims description 25
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 239000006187 pill Substances 0.000 claims description 16
- 238000001556 precipitation Methods 0.000 claims description 16
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 15
- 235000010413 sodium alginate Nutrition 0.000 claims description 13
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 13
- 241000031003 Monascus ruber Species 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 238000003916 acid precipitation Methods 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 11
- 239000000661 sodium alginate Substances 0.000 claims description 11
- 229940005550 sodium alginate Drugs 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 229920002521 macromolecule Polymers 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 235000017550 sodium carbonate Nutrition 0.000 claims description 9
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- FYGDTMLNYKFZSV-URKRLVJHSA-N (2s,3r,4s,5s,6r)-2-[(2r,4r,5r,6s)-4,5-dihydroxy-2-(hydroxymethyl)-6-[(2r,4r,5r,6s)-4,5,6-trihydroxy-2-(hydroxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1[C@@H](CO)O[C@@H](OC2[C@H](O[C@H](O)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O FYGDTMLNYKFZSV-URKRLVJHSA-N 0.000 claims description 5
- 239000004382 Amylase Substances 0.000 claims description 5
- 108010065511 Amylases Proteins 0.000 claims description 5
- 102000013142 Amylases Human genes 0.000 claims description 5
- 229920002498 Beta-glucan Polymers 0.000 claims description 5
- 108010059892 Cellulase Proteins 0.000 claims description 5
- 229920000858 Cyclodextrin Polymers 0.000 claims description 5
- 108010010803 Gelatin Proteins 0.000 claims description 5
- 239000004368 Modified starch Substances 0.000 claims description 5
- 229920000881 Modified starch Polymers 0.000 claims description 5
- 102000035195 Peptidases Human genes 0.000 claims description 5
- 108091005804 Peptidases Proteins 0.000 claims description 5
- 108010059820 Polygalacturonase Proteins 0.000 claims description 5
- 235000019418 amylase Nutrition 0.000 claims description 5
- 229940106157 cellulase Drugs 0.000 claims description 5
- 229920000159 gelatin Polymers 0.000 claims description 5
- 239000008273 gelatin Substances 0.000 claims description 5
- 235000019322 gelatine Nutrition 0.000 claims description 5
- 235000011852 gelatine desserts Nutrition 0.000 claims description 5
- 235000019426 modified starch Nutrition 0.000 claims description 5
- 235000010987 pectin Nutrition 0.000 claims description 5
- 239000001814 pectin Substances 0.000 claims description 5
- 229920001277 pectin Polymers 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 5
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000000049 pigment Substances 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 239000000084 colloidal system Substances 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000003472 neutralizing effect Effects 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 abstract 2
- 230000008021 deposition Effects 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 239000012530 fluid Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- FRXSZNDVFUDTIR-UHFFFAOYSA-N 6-methoxy-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=CC(OC)=CC=C21 FRXSZNDVFUDTIR-UHFFFAOYSA-N 0.000 description 4
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- -1 carboxylate salt Chemical class 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 0 CC(C)C=*[C@@](C(C)C1)OCC(C(C(C)(C(*)=C2[C@@](C3*)C3=O)OC2=O)=O)C1=* Chemical compound CC(C)C=*[C@@](C(C)C1)OCC(C(C(C)(C(*)=C2[C@@](C3*)C3=O)OC2=O)=O)C1=* 0.000 description 1
- 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 1
- 244000113306 Monascus purpureus Species 0.000 description 1
- 235000002322 Monascus purpureus Nutrition 0.000 description 1
- 108010091086 Recombinases Proteins 0.000 description 1
- 102000018120 Recombinases Human genes 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 235000013334 alcoholic beverage Nutrition 0.000 description 1
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- 235000012970 cakes Nutrition 0.000 description 1
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- 239000003638 chemical reducing agent Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000008121 dextrose Substances 0.000 description 1
- 235000013681 dietary sucrose Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000576 food coloring agent Substances 0.000 description 1
- 235000002864 food coloring agent Nutrition 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
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- 235000015094 jam Nutrition 0.000 description 1
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Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention relates to a method for preparing a monascus pigment, in particular to a method for preparing a monascus red pigment by utilizing immobilized enzymes. The method comprises the steps as follows: taking a monascus liquid fermentation solution as a raw material, homogenizing, enzymatically hydrolyzing the immobilized enzymes, alkalifying and filtering to obtain a monascus red pigment solution; and carrying out acid deposition on the monascus red pigment solution, washing and neutralizing the deposits, dehydrating and drying to obtain the monascus red pigment. The method has the advantages as follows: on one hand, the fermentation solution is effectively dispersed, broken, emulsified and mixed by utilizing a colloid mill, so that the subsequent enzymatic hydrolysis efficiency is improved and the monascus red pigment in monascus is fully released; and on the other hand, an enzyme preparation can be recycled, the reaction conditions are moderate, the monascus red pigment is concentrated through the acid deposition method, the process is simple, the energy consumption is low, and the product is easy to separate. The production cost can be remarkably reduced through the monascus red pigment prepared with the method. The monascus red pigment has the maximum absorption wavelength of 499 nm, is good in water solubility and light, heat, acid, alkali and metal stabilities, and is favorable for the monascus pigment industry development.
Description
Technical field
The present invention relates to a kind of preparation method of monascorubin, particularly a kind of method of utilizing immobilized enzyme to prepare monascorubin.
Background technology
Along with the development of foodstuffs industry and the raising day by day of people's living standard, food color is more and more subject to people's attention as integral part important in foodstuff additive, particularly in recent years, along with the attention of its people to food-safety problem, adopting natural pigment to replace synthetic colour has been trend of the times.Monascorubin is as the deep processed product of agricultural-food, safe, and good stability has good development prospect.
Chinese invention patent ZL200510044948.8 discloses a kind of method of utilizing enzymolysis process to extract water-soluble monascus pigment, a kind of method of utilizing enzymolysis process to extract water-soluble monascus pigment of the present invention, comprises the steps: Red kojic rice → immersion alkaline hydrolysis → heating gelatinization → enzymolysis → filtering separation → Acid precipitation → washing → neutralization → dry → pulverize → packing.This invention, take Red kojic rice as raw material, through soaking alkaline hydrolysis, is heated gelatinization, and the techniques such as enzymolysis, Acid precipitation, extract water-soluble monascus pigment.This patent adopts free enzyme liquid to carry out enzymolysis, because resolvase is dissolved in reaction system, make enzyme cannot be from reaction system Separation and Recovery, cause the production cost of monascorubin high, be unfavorable for continuous suitability for industrialized production.
Summary of the invention
The object of this invention is to provide one take monascus ruber liquid fermentation liquid as raw material, by homogenizing, immobilized enzyme enzymolysis, Acid precipitation enrichment, prepare the method for monascorubin.Dispersion, fragmentation, emulsification, mixed fermentation liquid, improve follow-up enzymolysis efficiency effectively, allows the monascorubin in thalline fully discharge simultaneously, improves pigment lixiviate yield; And solve certainly enzyme liquid in traditional technology and be difficult for Separation and Recovery, purification enrichment process complexity, cost is high, the problem that product look valency is low, and can improve resource utilization.
The present invention is take monascus ruber liquid fermentation liquid as raw material, by homogenizing, immobilized enzyme enzymolysis, alkalization, filter to obtain monascorubin solution; Monascorubin solution is by Acid precipitation, and washing of precipitate neutralization, dehydration, dry, obtain monascorubin.
First, utilize milling treatment of colloid Monascus anka Nakazawa et sato fermented liquid, utilize fluid foods to be subject to the effect of centrifugal force, force by shearing between the stator in high speed relative movement and rotor, friction, high-frequency vibration, effectively pulverize, emulsification, homogeneous, dispersion, mixing etc., thereby the material that obtains retrofit, impels the colour component in thalline to discharge fully, is conducive to improve the efficiency of later stage enzymolysis simultaneously.
Utilize immobilization prozyme to carry out enzymolysis processing to fermented liquid, one side proteolytic enzyme wherein can make the protein in fermented liq system be hydrolyzed into rapidly the protein fragments of solubility, obviously improves the water-soluble of monascorubin, effectively improves the quality of product; On the other hand, amylase and/or polygalacturonase and/or cellulase and/or zytase and/or beta-glucan enzyme can impel the degraded of somatic cells wall, increase the saturating property of thalline, are conducive to the release of monascorubin component, and then have improved the utilization ratio of resource.Process, by reclaiming immobilized enzyme, realizes the recycle of enzyme, reduces material consumption.
Enzymolysis solution, through alkalization, opens the lactone bond in monascorubin molecule wherein, generates carboxylate salt, impels colour component to be dissolved in solution system, improves the yield of monascorubin.
After alkalization finishes, remove by filter insolubles wherein, obtain monascorubin solution.Then utilize Acid precipitation that monascorubin is precipitated out from reaction solution, realize the object of enrichment; In alkali and the method for dissolving, make monascorubin acid deposit generate carboxylate salt soluble in water again, improve the water-soluble and homogeneity of pigment, obtain monascorubin.
Its conversion process is as follows:
A kind of method of utilizing immobilized enzyme to prepare monascorubin of the present invention, concrete steps are as follows:
(1) preparation of immobilized enzyme
Macromolecular compound carrier adds water and is mixed with the solution of 15 g/L～100g/L concentration, is under 20 ℃～60 ℃ conditions in temperature, stirs, and makes its dissolving; Then the enzyme that to add with macromolecular compound carrier mass ratio be 1:1～1:50, stirs, and is placed on the constant-temperature table of 20 ℃～60 ℃ vibration 0.5h～6h; Above-mentioned mixed solution is dropwise splashed in the calcium chloride solution of 0.1mol/L～2.5 mol/L, under 3 ℃～5 ℃ conditions, leave standstill 30min～150min, its cohesion is solidified, collect gelled pill, and with the sodium chloride solution washing of 0.08 mol/L～0.3 mol/L, suction filtration is removed free water content, collects the gelled pill obtaining and is immobilized enzyme;
(2) preparation of monascorubin
1. raw material: take monascus ruber liquid fermentation liquid as raw material;
2. homogenizing: fermented liquid is entered to colloidal mill and grind, broken fineness is at 0.1 μ m～10 μ m, colloidal mill action time is 5 min ~ 120min, obtains liquid after homogenizing;
3. enzymolysis: regulating step 2. the liquid after homogenizing to pH 4.0～pH 6.0, then the immobilized enzyme that adds wherein step (1) to prepare carries out enzymolysis, the mass ratio of immobilized enzyme and homogenized liquid is 1:1～1:100, and enzymatic hydrolysis condition is 20 ℃～70 ℃, and enzymolysis time is 1h～48h;
4. immobilized enzyme reclaims: by the 3. reaction solution coarse filtration after enzymolysis processing of step, reclaim immobilized enzyme, obtain filtrate simultaneously and be enzymolysis solution;
5. alkalization: add alkali lye in the enzymolysis solution 4. obtaining to step, regulate enzymolysis solution to pH 8.0～pH13.0, concentration of lye is 0.5mol/L～10.0 mol/L.
6. filter: by 5. reacting liquid filtering of step, remove insolubles, obtain monascorubin solution;
7. Acid precipitation: 6. add acid solution in the monascorubin solution of gained to step, regulator solution, to pH 1～pH3, makes its precipitation, leaves standstill after 0.5h～24h collecting precipitation thing;
8. wash, neutralize: the throw out that 7. step is obtained is washed with water to pH5～pH6, with the alkaline solution dissolution precipitation thing of 0.01 mol/L～5.0 mol/L, and be adjusted to pH 7～pH12, obtain the monascorubin aqueous solution;
9. dry, pulverizing: the monascorubin aqueous solution that 8. step is obtained dewaters, drying treatment, and the dried powder obtaining is prepared monascorubin.
Wherein the described macromolecular compound carrier of step (1) is sodium alginate, and one or more mixture in sodium alginate and gelatin, modified starch, pectin and cyclodextrin;
Alkaline solution in the described alkaline hydrolysis of step (2) is one or more the mixture in sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution and sodium hydrogen carbonate solution;
Acid solution in the described Acid precipitation of step (2) is one or more the mixture in hydrochloric acid, sulfuric acid, acetic acid, citric acid, phosphoric acid and lactic acid;
The described washing of step (2), to neutralize alkaline solution used be one or more the mixture in sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution, solution of potassium carbonate, sodium hydrogen carbonate solution, potassium bicarbonate solution and ammonium bicarbonate soln.
The above-mentioned enzyme for enzymolysis is immobilized enzyme, and the enzyme being fixed is the prozyme that contains proteolytic enzyme and amylase and/or polygalacturonase and/or cellulase and/or zytase and/or beta-glucan enzyme.Immobilized enzyme enzymolysis process is the stirring enzymolysis carrying out in reactor, or immobilized enzyme is packed in packed column, then acidizing fluid is pumped into the circulation enzymolysis that packed column carries out.
Monascorubin prepared by the inventive method, soluble in water; Possess good thermostability, under 0 ℃～120 ℃ environment on pigment without impact; Pigment has satisfactory stability within the scope of pH>3, Oxidizing and Reducing Agents does not have detrimentally affect to pigment, dextrose plus saccharose solution does not affect pigment, and the use of various common foodstuff additive does not affect the quality of pigment substantially, stable to metal ion.
Monascorubin prepared by the inventive method can be for textile industry, plastic cement industry and press painted; Can be used as painted for the processing of the industry such as grain, meat product, fishery products of food colorant, can be used for assembled alcoholic drinks, soda pop, fruit juice (taste) type beverage, jam, candy, cake etc.; Can be painted for the processing of the industry such as pharmaceuticals and makeup.
The present invention assists homogenizing technology and enzyme immobilization technology for the preparation of monascorubin colloidal mill, can reduce production costs, and improves pigment lixiviate yield, and reduces the contaminating impurity that enzyme liquid causes pigment product, is conducive to improve the quality of products.
The present invention compares with traditional method, has the following advantages:
1, utilize colloidal mill to carry out homogenizing processing to monascus ruber fermented liquid, effectively pulverize, emulsification, homogeneous, dispersion, mixing etc., improve the rate of releasing of the colour component in thalline, be conducive to improve the efficiency of later stage enzymolysis simultaneously.
2, utilize immobilized enzyme to carry out enzymolysis, the stability of enzyme is increased, easily Separation and Recovery from reactive system, can saving resource, reduces costs.
3, the preparation method of monascorubin of the present invention, dissolves to realize the purification enrichment to monascorubin by Acid precipitation and basic solution, capable of reducing energy consumption.
The monascorubin that adopts the inventive method to prepare, its maximum absorption wavelength is 499nm, and look valency is higher than 200, and monascorubin extraction rate reached is more than 95%.
Gordian technique explanation:
1, colloidal mill homogenizing technology
Colloidal mill is to utilize fluid or semi-fluid material to be subject to the effect of centrifugal force, force by shearing between the stator in high speed relative movement and rotor, friction, high-frequency vibration, effectively pulverize, emulsification, homogeneous, dispersion, mixing etc., wherein broken fineness and colloidal mill action time, treatment effect impact on material is larger, a kind of method of utilizing immobilized enzyme to prepare monascorubin of the present invention, fermented liquid is entered to colloidal mill to be ground, broken fineness is at 0.1 μ m～10 μ m, colloidal mill action time is 5 min ~ 120min, obtains liquid after homogenizing.
2, immobilized enzyme zymolysis technique
Macromolecular compound carrier adds water and is mixed with the solution of 15 g/L～100g/L concentration, is under 20 ℃～60 ℃ conditions in temperature, stirs, and makes its dissolving; Then the enzyme that to add with macromolecular compound carrier mass ratio be 1:1～1:50, stirs, and is placed on the constant-temperature table of 20 ℃～60 ℃ vibration 0.5h～6h; Above-mentioned mixed solution is dropwise splashed in the calcium chloride solution of 0.1mol/L～2.5 mol/L, under 3 ℃～5 ℃ conditions, leave standstill 30min～150min, its cohesion is solidified, collect gelled pill, and with the sodium chloride solution washing of 0.08 mol/L～0.3 mol/L, suction filtration is removed free water content, collects the gelled pill obtaining and is immobilized enzyme; Macromolecular compound carrier used comprises sodium alginate, and one or more mixture in sodium alginate and gelatin, modified starch, pectin and cyclodextrin.Described enzyme is immobilized enzyme, and the enzyme being fixed is the prozyme that contains proteolytic enzyme and amylase and/or polygalacturonase and/or cellulase and/or zytase and/or beta-glucan enzyme.
Immobilized enzyme enzymatic hydrolysis condition is 20 ℃～70 ℃, pH 4.0～pH 6.0, and enzymolysis time is 1h～48h; The mass ratio of immobilized enzyme and homogenized liquid is 1:1～1:100, and enzymolysis process is the stirring enzymolysis carrying out in reactor, or immobilized enzyme is packed in packed column, then acidizing fluid is pumped into the circulation enzymolysis that packed column carries out.Immobilized enzyme recycling still keeps more than 90% enzymolysis yield for 20 times.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described, so that those skilled in the art more understands the present invention, but does not therefore limit the present invention.
Embodiment 1
(1) preparation of immobilized enzyme
The sodium alginate of 35 g is mixed with 25 g gelatin, be added in 1L water, under 45 ℃ of conditions, stirring and dissolving, adds the prozyme of 35g, stirring and evenly mixing, on 45 ℃ of constant-temperature tables, the 100r/min 0.5h that vibrates, then dropwise injects this mixed solution the calcium chloride solution of 1.5mol/L, under 4 ℃ of conditions, leave standstill 50min, its cohesion is solidified, collect gelled pill, with the sodium chloride solution washing of 0.2 mol/L, suction filtration is removed free water content, collects being fixed of gelled pill enzyme.
(2) preparation of monascorubin
The liquid fermentation liquid of monascus ruber is entered to colloidal mill and carry out homogenizing processing, broken fineness is 5 μ m, and the treatment time is 30min; After homogenizing finishes, regulator solution is to pH4.5, and the amount that is 1:50 according to the mass ratio of weight in wet base and homogenized liquid adds immobilization prozyme, filters after 8 hours in 50 ℃ of shaking table enzymolysis, reclaims immobilized enzyme; Then the sodium hydroxide solution that is 0.5mol/L by concentration regulates enzymolysis solution to pH8.0, filters, and removes insolubles, obtain monascorubin solution, to pH 2.7, leave standstill 2 hours with the phosphoric acid solution adjusting reaction solution of 5 mol/L, filter, collecting precipitation, water washing and precipitating, to pH5, with the sodium carbonate solution dissolution precipitation thing of 0.1 mol/L, and is adjusted to pH8.0, spray-dried, obtain monascorubin powder.
Embodiment 2
(1) preparation of immobilized enzyme
The sodium alginate soln of 4g is mixed with the modified starch of 2g, be added in 100ml water, under 45 ℃ of conditions, stirring and dissolving, adds the prozyme of 2g, stirring and evenly mixing, on 37 ℃ of constant-temperature tables, the 60r/min 1.5h that vibrates, then dropwise injects this mixed solution the calcium chloride solution of 1.5mol/L, under 4 ℃ of conditions, leave standstill 110min, its cohesion is solidified, collect gelled pill, with the sodium chloride solution washing of 0.2 mol/L, suction filtration is removed free water content, collects being fixed of gelled pill enzyme.
(2) preparation of monascorubin
The liquid fermentation liquid of monascus ruber is entered to colloidal mill and carry out homogenizing processing, broken fineness is 1 μ m, and the treatment time is 20min; After homogenizing finishes, regulator solution is to pH5.0, and the amount that is 1:30 according to the mass ratio of weight in wet base and homogenized liquid adds immobilization prozyme, filters after 6 hours in 55 ℃ of shaking table enzymolysis, reclaims immobilized enzyme; Then the sodium hydroxide solution that is 0.8mol/L by concentration regulates enzymolysis solution to pH8.5, filters, and removes insolubles, obtain monascorubin solution,, place 4 hours to pH 2.5 with the citric acid solution adjusting reaction solution of 5.5 mol/L, centrifugal, collecting precipitation, water washing and precipitating, to pH5, with the sodium hydroxide solution dissolution precipitation thing of 0.1 mol/L, and is adjusted to pH8, spray-dried, obtain monascorubin powder.
Embodiment 3
(1) preparation of immobilized enzyme
100g sodium alginate is added in 8L water, and stirring and dissolving at 40 ℃, adds the prozyme of 50g, stirring and evenly mixing, on 37 ℃ of constant-temperature tables, the 90r/min 0.6h that vibrates, dropwise injects this mixed solution the calcium chloride solution of 2.0mol/L, under 3 ℃ of conditions, leave standstill 120min, its cohesion is solidified, collect gelled pill, with the sodium chloride solution washing of 0.15mol/L, suction filtration is removed free water content, collects being fixed of gelled pill enzyme.
(2) preparation of monascorubin
The liquid fermentation liquid of monascus ruber is entered to colloidal mill and carry out homogenizing processing, broken fineness is 4 μ m, and the treatment time is 60min; After homogenizing finishes, regulator solution is to pH4.5, and the amount that is 1:40 according to the mass ratio of weight in wet base and homogenized liquid adds immobilization prozyme, filters after 5 hours in 65 ℃ of shaking table enzymolysis, reclaims immobilized enzyme; Then the potassium hydroxide solution that is 2mol/L by concentration regulates enzymolysis solution to pH10.0, filters, and removes insolubles, obtain monascorubin solution,, place 3 hours to pH 2.0 with the hydrochloric acid soln adjusting reaction solution of 5 mol/L, filter, collecting precipitation, water washing and precipitating, to pH5, with the sodium carbonate solution dissolution precipitation thing of 0.3 mol/L, and is adjusted to pH8.5, spray-dried, obtain monascorubin powder.
Embodiment 4
(1) preparation of immobilized enzyme
30 g sodium alginates and 20g cyclodextrin are added in 1L water, stirring and dissolving at 37 ℃, add 30g prozyme, stirring and evenly mixing, on 37 ℃ of constant-temperature tables, the 120r/min 2.5h that vibrates, this mixed solution is dropwise injected to the calcium chloride solution of 1.0mol/L, under 5 ℃ of conditions, leave standstill 30min, its cohesion is solidified, collect gelled pill, with the sodium chloride solution washing of 0.2 mol/L, suction filtration is removed free water content, collects being fixed of gelled pill enzyme, immobilized enzyme is packed in glass column, make immobilized enzyme column;
(2) preparation of monascorubin
The liquid fermentation liquid of monascus ruber is entered to colloidal mill and carry out homogenizing processing, broken fineness is 8 μ m, and the treatment time is 50min; After homogenizing finishes, regulator solution, to pH4.5, pumps into immobilized enzyme column by homogenized liquid and carries out enzymolysis, and enzymolysis effluent liquid is got back in stainless steel reactor, so circulating reaction, and 55 ℃ of hydrolysis temperatures, enzymolysis time 10 hours, after enzymolysis finishes, reclaims immobilized enzyme; Then the sodium carbonate solution that is 4mol/L by concentration regulates enzymolysis solution to pH9.0, filters, and removes insolubles, obtain monascorubin solution,, place 6 hours to pH 2.0 with the hydrochloric acid soln adjusting reaction solution of 6mol/L, centrifugal, collecting precipitation, water washing and precipitating, to pH5, with the sodium hydrogen carbonate solution dissolution precipitation thing of 0.3 mol/L, and is adjusted to pH7.5, spray-dried, obtain monascorubin powder.
Embodiment 5
(1) preparation of immobilized enzyme
30 g sodium alginates and 20g pectin are added in 1L water, and stirring and dissolving at 45 ℃, adds the prozyme of 10g, stirring and evenly mixing, on 45 ℃ of constant-temperature tables, the 150r/min 1.5h that vibrates, dropwise injects this mixed solution the calcium chloride solution of 2mol/L, under 4 ℃ of conditions, leave standstill 120min, its cohesion is solidified, collect gelled pill, with the sodium chloride solution washing of 0.1 mol/L, suction filtration is removed free water content, collects being fixed of gelled pill enzyme;
(2) preparation of monascorubin
The liquid fermentation liquid of monascus ruber is entered to colloidal mill and carry out homogenizing processing, broken fineness is 0.5 μ m, and the treatment time is 15min; After homogenizing finishes, regulator solution is to pH5.0, and the amount that is 1:80 according to the mass ratio of weight in wet base and homogenized liquid adds immobilization prozyme, filters after 2 hours in 60 ℃ of shaking table enzymolysis, reclaims immobilized enzyme; Then regulate enzymolysis solution to pH9.0 with the potassium hydroxide solution that concentration is 1 mol/L, filter, remove insolubles, obtain monascorubin solution,, place 6 hours to pH 2.5 with the sulphuric acid soln adjusting reaction solution of 6mol/L, filter, collecting precipitation, water washing and precipitating, to pH5, with the sodium hydrogen carbonate solution dissolution precipitation thing of 0.1 mol/L, and is adjusted to pH8.5, spray-dried, obtain monascorubin powder.
In above-described embodiment 1～6, macromolecular compound carrier comprises sodium alginate, and one or more mixture in sodium alginate and gelatin, modified starch, pectin and cyclodextrin; The enzyme being fixed is the prozyme that contains proteolytic enzyme and amylase and/or polygalacturonase and/or cellulase and/or zytase and/or beta-glucan enzyme; Comprise one or more mixture of sodium hydroxide, potassium hydroxide, sodium carbonate and sodium bicarbonate for the alkali of alkaline hydrolysis; Enzymolysis process is the stirring enzymolysis carrying out in reactor, or immobilized enzyme is packed in packed column, then acidizing fluid is pumped into the circulation enzymolysis that packed column carries out; Comprise one or more mixture of hydrochloric acid, sulfuric acid, acetic acid, citric acid, phosphoric acid and lactic acid for the acid of Acid precipitation; For neutralizing and the sedimentary alkali of dissolving acid comprises one or more mixture of sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus and bicarbonate of ammonia; The recycling number of times and should do suitable adjustment depending on particular case of its kind and consumption and immobilized enzyme.
Claims (7)
1. utilize immobilized enzyme to prepare a method for monascorubin, comprise following step: take monascus ruber liquid fermentation liquid as raw material, by homogenizing, immobilized enzyme enzymolysis, alkalization, filter to obtain monascorubin solution; Monascorubin solution is by Acid precipitation, and washing of precipitate neutralization, dehydration, dry, obtain monascorubin;
The described immobilized enzyme that utilizes is prepared the method for monascorubin, specifically comprises following step:
(1) preparation of immobilized enzyme
Macromolecular compound carrier adds water and is mixed with the solution of 15～100g/L concentration, is under 20 ℃～60 ℃ conditions in temperature, is stirred to its dissolving; Then the enzyme that to add with macromolecular compound carrier mass ratio be 1:1～1:50, stirs, and is placed on the constant-temperature table of 20 ℃～60 ℃ vibration 0.5h～6h; Above-mentioned mixed solution is dropwise splashed in the calcium chloride solution of 0.1mol/L～2.5 mol/L, under 3 ℃～5 ℃ conditions, leave standstill 30～150min, its cohesion is solidified, collect gelled pill, and with the sodium chloride solution washing of 0.08 mol/L～0.3 mol/L, suction filtration is removed free water content, collects the gelled pill obtaining and is immobilized enzyme;
The described enzyme of step (1) is the prozyme that contains proteolytic enzyme and amylase and/or polygalacturonase and/or cellulase and/or zytase and/or beta-glucan enzyme;
(2) preparation of monascorubin
1. raw material: take monascus ruber liquid fermentation liquid as raw material;
2. homogenizing: fermented liquid is entered to colloidal mill and grind, broken fineness is at 0.1～10 μ m, colloidal mill action time is 5 min～120min, obtains liquid after homogenizing;
3. enzymolysis: regulating step 2. the liquid after homogenizing to pH 4.0～6.0, then the immobilized enzyme that adds wherein step (1) to prepare carries out enzymolysis, the mass ratio of immobilized enzyme and homogenized liquid is 1:1～1:100, and enzymatic hydrolysis condition is 20 ℃～70 ℃, and enzymolysis time is 1～48h;
4. immobilized enzyme reclaims: by the 3. reaction solution coarse filtration after enzymolysis processing of step, reclaim immobilized enzyme, obtain filtrate simultaneously and be enzymolysis solution;
5. alkalization: add alkali lye in the enzymolysis solution 4. obtaining to step, regulate enzymolysis solution to pH 8.0～13.0, concentration of lye is 0.5～10.0 mol/L;
6. filter: by 5. reacting liquid filtering of step, remove insolubles, obtain monascorubin solution;
7. Acid precipitation: 6. add acid solution in the monascorubin solution of gained to step, regulator solution, to pH 1～3, makes its precipitation, leaves standstill after 0.5h～24h collecting precipitation thing;
8. wash, neutralize: the throw out that 7. step is obtained is washed with water to pH5～pH6, with the alkaline solution dissolution precipitation thing of 0.01～5.0 mol/L, and be adjusted to pH 7～12, obtain the monascorubin aqueous solution;
9. dry, pulverizing: the monascorubin aqueous solution that 8. step is obtained dewaters, drying treatment, and the dried powder obtaining is prepared monascorubin.
2. the method for utilizing immobilized enzyme to prepare monascorubin according to claim 1, it is characterized in that: the described macromolecular compound carrier of step (1) is sodium alginate, and at least one in sodium alginate and gelatin, modified starch, pectin and cyclodextrin.
3. the method for utilizing immobilized enzyme to prepare monascorubin according to claim 1, is characterized in that: the alkaline solution in the alkalization described in step (2) is at least one in sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution and sodium hydrogen carbonate solution.
4. the method for utilizing immobilized enzyme to prepare monascorubin according to claim 1, is characterized in that: the acid solution in the Acid precipitation described in step (2) is at least one in hydrochloric acid, sulfuric acid, acetic acid, citric acid, phosphoric acid and lactic acid.
5. the method for utilizing immobilized enzyme to prepare monascorubin according to claim 1, is characterized in that: the described washing of step (2), to neutralize alkaline solution used be at least one in sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution, solution of potassium carbonate, sodium hydrogen carbonate solution, potassium bicarbonate solution and ammonium bicarbonate soln.
6. a kind of method of utilizing immobilized enzyme to prepare monascorubin according to claim 1, is characterized in that: the described enzymolysis process of step (2) is the stirring enzymolysis carrying out in reactor.
7. a kind of method of utilizing immobilized enzyme to prepare monascorubin according to claim 1, it is characterized in that: the described enzymolysis process of step (2) is: immobilized enzyme is packed in packed column, then monascus ruber liquid fermentation liquid is pumped into the circulation enzymolysis that packed column carries out.
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| WO2022008503A1 (en) * | 2020-07-06 | 2022-01-13 | Chromologics Aps | Atrorosins as food colors |
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| CN104448919B (en) * | 2014-12-26 | 2016-06-01 | 天津商业大学 | The purification process of the pigment of hydroxyl |
| CN110205342B (en) * | 2019-06-28 | 2020-11-27 | 福州大学 | Method for increasing pigment yield in fermentation process of immobilized monascus |
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