CN111153786A - Coenzyme Q10 extraction method and device - Google Patents
Coenzyme Q10 extraction method and device Download PDFInfo
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- CN111153786A CN111153786A CN201911412590.8A CN201911412590A CN111153786A CN 111153786 A CN111153786 A CN 111153786A CN 201911412590 A CN201911412590 A CN 201911412590A CN 111153786 A CN111153786 A CN 111153786A
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- ACTIUHUUMQJHFO-UHFFFAOYSA-N Coenzym Q10 Natural products COC1=C(OC)C(=O)C(CC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)C)=C(C)C1=O ACTIUHUUMQJHFO-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 235000017471 coenzyme Q10 Nutrition 0.000 title claims abstract description 71
- ACTIUHUUMQJHFO-UPTCCGCDSA-N coenzyme Q10 Chemical compound COC1=C(OC)C(=O)C(C\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CCC=C(C)C)=C(C)C1=O ACTIUHUUMQJHFO-UPTCCGCDSA-N 0.000 title claims abstract description 71
- 229940110767 coenzyme Q10 Drugs 0.000 title claims abstract description 71
- 238000000605 extraction Methods 0.000 title claims description 8
- 239000012528 membrane Substances 0.000 claims abstract description 136
- 239000000919 ceramic Substances 0.000 claims abstract description 93
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 84
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000007127 saponification reaction Methods 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000001471 micro-filtration Methods 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000000706 filtrate Substances 0.000 claims abstract description 37
- 238000001914 filtration Methods 0.000 claims abstract description 33
- 238000000855 fermentation Methods 0.000 claims abstract description 26
- 230000004151 fermentation Effects 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 239000011148 porous material Substances 0.000 claims abstract description 26
- 238000001728 nano-filtration Methods 0.000 claims abstract description 23
- 239000003513 alkali Substances 0.000 claims abstract description 19
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 19
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 19
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 18
- 239000012043 crude product Substances 0.000 claims abstract description 17
- 238000001704 evaporation Methods 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 60
- 239000012535 impurity Substances 0.000 claims description 44
- 239000012295 chemical reaction liquid Substances 0.000 claims description 30
- 239000000047 product Substances 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 25
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 12
- 239000012530 fluid Substances 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 230000002209 hydrophobic effect Effects 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 230000001580 bacterial effect Effects 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- LJQKCYFTNDAAPC-UHFFFAOYSA-N ethanol;ethyl acetate Chemical compound CCO.CCOC(C)=O LJQKCYFTNDAAPC-UHFFFAOYSA-N 0.000 claims description 4
- UREBWPXBXRYXRJ-UHFFFAOYSA-N ethyl acetate;methanol Chemical compound OC.CCOC(C)=O UREBWPXBXRYXRJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 238000001694 spray drying Methods 0.000 claims description 4
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 238000000935 solvent evaporation Methods 0.000 claims 1
- 239000012074 organic phase Substances 0.000 abstract description 10
- 239000006227 byproduct Substances 0.000 abstract description 8
- 238000010438 heat treatment Methods 0.000 abstract description 8
- 238000000746 purification Methods 0.000 abstract description 8
- 239000002699 waste material Substances 0.000 abstract description 5
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002798 polar solvent Substances 0.000 description 19
- 239000012466 permeate Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000012071 phase Substances 0.000 description 8
- 230000001476 alcoholic effect Effects 0.000 description 7
- 238000000502 dialysis Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000004945 emulsification Methods 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
- 230000006870 function Effects 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- 241001052560 Thallis Species 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000010627 oxidative phosphorylation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
- C07C46/10—Separation; Purification; Stabilisation; Use of additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/58—Multistep processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/26—Further operations combined with membrane separation processes
- B01D2311/263—Chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/26—Further operations combined with membrane separation processes
- B01D2311/2649—Filtration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/26—Further operations combined with membrane separation processes
- B01D2311/2669—Distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method and a device for efficiently purifying coenzyme Q10 from fermentation liquor. The method comprises the following steps: (1) continuously adding a nonpolar solvent with the volume of 3-4 times into a coenzyme Q10 crude product obtained by fermentation production; (2) filtering through a ceramic membrane with small pore diameter; (3) adding alkali into the obtained filtrate, and heating to carry out saponification reaction; (4) carrying out centrifugal treatment on the feed liquid after saponification, sequentially and continuously adding methanol, ethanol and water into the filtrate, carrying out micro-filtration treatment step by step, wherein the filtrate is a waste liquid phase, and the trapped liquid is an organic phase, namely purified coenzyme Q10 liquid after saponification and purification, and can be further treated; (5) and (4) performing nanofiltration treatment on the filtrate in the third section, namely the waste liquid phase in the step (4), so as to recover water and alcohol, and evaporating trapped liquid to obtain a protein byproduct.
Description
Technical Field
The invention relates to a method for efficiently purifying coenzyme Q10 from fermentation liquor, belonging to the field of fermentation.
Background
Coenzyme Q10 has attracted considerable attention because of its functions of promoting oxidative phosphorylation reactions and protecting the structural integrity of biological membranes. Fermentation is used as the main production process of coenzyme Q10, and the product purity is the main factor limiting large-scale production. The product obtained by the fermentation method contains a large amount of impurities such as fatty acid and the like besides the coenzyme Q10 purified product, and most of the products are insoluble in water and have high separation difficulty, so that the product purity is influenced. The current main method is to transfer the impurities to the aqueous phase by saponification and purify them by extraction via a layer. However, the process belongs to indirect operation, the single-batch operation time is long, the feed liquid is easy to generate emulsification phenomenon to cause product loss, and the equipment has large volume and low actual utilization rate.
Disclosure of Invention
The invention provides a method for efficiently purifying coenzyme Q10 from fermentation liquor. The process not only shortens the time for purification, but also recycles the reagent used in the saponification reaction, reduces the discharge of waste liquid, and has simple method and high purification efficiency.
The technical scheme is as follows:
a method for extracting coenzyme Q10 comprises the following steps:
step 1, adding a nonpolar solvent into a crude coenzyme Q10 product prepared by a fermentation method to dissolve coenzyme Q10;
step 2, filtering the solution obtained in the step 1 by using a small-aperture ceramic membrane to remove insoluble impurities and high-molecular-weight impurities;
step 3, adding alkali liquor into the filtrate obtained in the step 2 to perform saponification reaction;
step 4, sequentially adding methanol, ethanol and water into the saponification reaction liquid, simultaneously filtering by using a ceramic microfiltration membrane, and distilling the concentrated solution of the ceramic microfiltration membrane under reduced pressure to remove the solvent to obtain coenzyme Q10;
and 5, filtering the filtrate of the ceramic microfiltration membrane in the step 4 by using a nanofiltration membrane, wherein the filtrate is an alcohol aqueous solution, the trapped fluid is protein, and the trapped fluid is spray-dried to obtain the recovered protein.
In one embodiment, the coenzyme Q10 crude product is obtained by leaching fermented bacterial powder with a solvent and evaporating to dryness; the solvent can adopt tetrahydrofuran-methanol, ethyl acetate-methanol and ethyl acetate-ethanol mixed solvent.
In one embodiment, the non-polar solvent is selected from one of pentane, n-hexane, petroleum ether, or heptane.
In one embodiment, the small pore ceramic membrane of step 2 has an average pore size of 1 to 100nm, preferably 5 to 10 nm.
In one embodiment, in the step 3, the alkali solution is sodium hydroxide, potassium hydroxide or sodium bicarbonate solution, the concentration of the alkali solution is 5-10wt%, the addition amount of the alkali solution is 0.4-1 times of the filtrate, and the temperature is controlled to be 20-50 ℃.
In one embodiment, the average pore size of the microfiltration membrane used in step 4 is in the range of 50 to 500 nm; the surface of the microfiltration membrane is subjected to hydrophobic modification treatment, and the water drop contact angle of the surface of the microfiltration membrane ranges from 100 DEG to 160 deg.
In one embodiment, the nanofiltration membrane in step 5 has a molecular weight cut-off of 200-.
In one embodiment, the total volume of methanol and ethanol added is controlled to be 5-8 times the volume of the saponification reaction liquid, and the amount of water washing added is controlled to be 1-3 times the volume of the saponification reaction liquid.
An extraction device of coenzyme Q10, comprising:
the raw material tank is used for preliminarily dissolving a coenzyme Q10 crude product;
the nonpolar solvent adding tank is connected to the raw material tank and is used for adding a nonpolar solvent into the raw material tank;
the small-aperture ceramic membrane is connected to the raw material tank and is used for filtering and removing impurities from the coenzyme Q10 solution dissolved by the nonpolar solvent to remove insoluble impurities and high-molecular-weight impurities;
the saponification reactor is connected to the permeation side of the small-aperture ceramic membrane and is used for performing saponification reaction on the permeation liquid of the small-aperture ceramic membrane;
an alkali solution inlet connected to the saponification reactor for adding an alkali solution to the saponification reactor 7;
the reaction liquid tank is connected with the saponification reactor and is used for mixing the saponification reaction liquid with a solvent;
the methanol tank, the ethanol tank and the water tank are respectively connected to the reaction liquid tank and are respectively used for adding methanol, ethanol and water into the reaction liquid tank;
the ceramic microfiltration membrane is connected to the reaction liquid tank and is used for separating the organic solvent from water of the feed liquid in the reaction liquid tank;
and the dryer is connected to the concentration side of the ceramic microfiltration membrane and used for drying the solvent of the concentrated solution of the ceramic microfiltration membrane to dryness to obtain a finished product coenzyme Q10.
In one embodiment, further comprising:
the nanofiltration membrane is connected to the permeation side of the ceramic microfiltration membrane and is used for performing nanofiltration treatment on penetrating fluid of the ceramic microfiltration membrane so as to intercept protein;
and the spray dryer is connected to the concentration side of the nanofiltration membrane and is used for spray drying the concentrated solution of the nanofiltration membrane.
In one embodiment, the small pore ceramic film has an average pore size of 1 to 100 nm.
In one embodiment, the small pore ceramic film has an average pore size of 5 to 10 nm.
In one embodiment, the ceramic microfiltration membrane has an average pore size in the range of 50 to 500 nm.
In one embodiment, the water droplet contact angle of the surface of the ceramic microfiltration membrane ranges from 100 ° to 160 °.
In one embodiment, the molecular weight cut-off of the nanofiltration membrane is 200-.
The ceramic microfiltration membrane is applied to the separation of the saponification reaction liquid of the coenzyme Q10.
Advantageous effects
The invention solves the problem of efficiently purifying coenzyme Q10 from fermentation liquor by taking a membrane integration technology as a core. The method has the following beneficial effects:
1. by the interfacial chemistry principle, the oleophylic and hydrophobic characteristics of the ceramic membrane are utilized, the separation of an organic phase and a water phase in the material after saponification reaction is efficiently realized, impurities are remained in the water phase, the membrane is filtered out, and the product is remained in the organic phase to realize the separation.
2. By utilizing the advantage that the membrane device can continuously filter, the solvent is continuously added to permeate out the product, the reagent dosage is reduced, the operation time is shortened, and the cost is reduced.
3. In the first step, a small-aperture membrane is selected for microfiltration to remove insoluble and soluble macromolecular impurities, so that the difficulty of subsequent purification is reduced.
4. By adding alcohol and washing water, protein, fatty acid and residual alkaline alcohol remained in the organic phase are removed by utilizing the polarity or solubility of the alcohol and water to the product and impurities, and the concentration of the product is further improved.
5. Utilize the constantly endless characteristic of membrane device filtration, the intensive mixing separation edulcoration effect is better, and whole separation process is shorter in time-consuming, reduces the loss that the product emulsification caused, and the phase change has improved the product yield.
6. The filtrate, namely the waste liquid phase, can be concentrated and recycled by the treatment of a nanofiltration membrane, the concentrated phase mainly contains protein, the added value is improved, and the effluent COD is low, so that the biochemical treatment can be directly carried out. The method not only realizes the resource utilization of the waste liquid, but also can reduce the consumption of alcohol and water in the process, and further reduces the purification cost.
7. The membrane pollution degree is reduced by utilizing the advantages of multi-channel membrane treatment, and compared with the traditional extraction process, the membrane treatment method saves resources, is environment-friendly, reduces the cost and greatly improves the purification efficiency.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a diagram of the apparatus of the present invention.
Wherein, 1, a raw material tank; 2. a non-polar solvent addition tank; 3. a small pore size ceramic membrane; 4. a saponification reactor; 5. an alkaline solution inlet; 6. a reaction liquid tank; 7. a methanol tank; 8. an ethanol tank; 9. a water tank; 10. a ceramic microfiltration membrane; 11. a dryer; 12. a nanofiltration membrane; 13. a spray dryer.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments. It will be understood by those skilled in the art that the following examples are illustrative of the present invention only and should not be taken as limiting the scope of the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Approximating language, as used herein throughout the specification and claims, may be applied to modify any quantitative representation that could permissibly vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as "about," is not to be limited to the precise value specified. In at least some instances, the approximating language may correspond to the precision of an instrument for measuring the value. Unless context or language indicates otherwise, range limitations may be combined and/or interchanged, and such ranges are identified and include all the sub-ranges included herein. Other than in the operating examples, or where otherwise indicated, all numbers or expressions referring to quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as modified in all instances by the word "about".
The recitation of values by ranges is to be understood in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a concentration range of "about 0.1% to about 5%" should be interpreted to include not only the explicitly recited concentration of about 0.1% to about 5%, but also include individual concentrations (e.g., 1%, 2%, 3%, and 4%) and sub-ranges (e.g., 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%) within the indicated range.
The term "removal" in the present specification includes not only a case where a target substance is completely removed but also a case where the target substance is partially removed (the amount of the substance is reduced). "purification" in this specification includes the removal of any or specific impurities.
The words "include," "have," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The method of the invention is detailed as follows:
a method for extracting coenzyme Q10 comprises the following steps:
step 1, adding a nonpolar solvent into a crude coenzyme Q10 product prepared by a fermentation method to dissolve coenzyme Q10; in the step, the coenzyme Q10 crude product is obtained by leaching and evaporating fermented bacterial powder by using a solvent; the solvent can adopt tetrahydrofuran-methanol, ethyl acetate-methanol and ethyl acetate-ethanol mixed solvent. After leaching, coenzyme Q10 can be dissolved out of the bacterial powder, and a crude dry powder is obtained after evaporation to dryness; the purpose of adding the nonpolar solvent is to dissolve the crude product again for subsequent purification, and the nonpolar solvent is selected from one of pentane, normal hexane, petroleum ether or heptane;
step 2, filtering the solution obtained in the step 1 by using a small-aperture ceramic membrane to remove insoluble impurities and high-molecular-weight impurities; in the step, the average pore diameter of the small-pore-diameter ceramic membrane is 1-100nm, preferably 5-10nm, so that the solvent dissolved with the crude product can be primarily purified, and some suspended particles and macromolecular impurities are filtered.
Step 3, adding alkali liquor into the filtrate obtained in the step 2 to perform saponification reaction; the purpose of the step is to carry out saponification reaction on the solution, the reaction process and the used reaction raw materials can be carried out according to the prior art, the alkali liquor is sodium hydroxide, potassium hydroxide or sodium bicarbonate solution, the concentration of the alkali liquor is 5-10wt%, the addition amount of the alkali liquor is 0.4-1 time of that of the filtrate, and the temperature is controlled to be 20-50 ℃.
Step 4, sequentially adding methanol, ethanol and water into the saponification reaction liquid, simultaneously filtering by using a ceramic microfiltration membrane, and distilling the concentrated solution of the ceramic microfiltration membrane under reduced pressure to remove the solvent to obtain coenzyme Q10; in the step, when the ceramic microfiltration membrane filters the saponification reaction liquid, the organic phase can be intercepted, and the water phase can permeate, so that the purpose of separating impurities is achieved; the purpose of adding methanol, ethanol and water is to improve the product purity by dialyzing the feed liquid to make more impurities dissolved in the polar solvent permeate the ceramic membrane, the total volume of the added methanol and ethanol is controlled to be 5-8 times of the volume of the saponification reaction liquid, and the water washing amount of the added methanol and ethanol is controlled to be 1-3 times of the volume of the saponification reaction liquid. In this step, in order to achieve a better separation effect between the organic phase and the aqueous phase, it is preferable to use a hydrophobic modified microfiltration membrane, wherein the contact angle of the water drop on the surface of the microfiltration membrane is in the range of 100-160 °.
And 5, filtering the filtrate of the ceramic microfiltration membrane in the step 4 by using a nanofiltration membrane with the molecular weight cutoff of 200-1000Da, wherein the filtrate is an alcohol aqueous solution, the cutoff solution is protein, and the cutoff solution is subjected to spray drying to obtain the recovered protein.
Based on the method, the invention also provides a coenzyme Q10 extraction device, which comprises the following steps:
the raw material tank 1 is used for preliminarily dissolving a coenzyme Q10 crude product;
the nonpolar solvent adding tank 2 is connected to the raw material tank 1 and is used for adding a nonpolar solvent into the raw material tank 1;
the small-aperture ceramic membrane 3 is connected to the raw material tank 1 and is used for filtering and removing impurities from the coenzyme Q10 solution dissolved by the nonpolar solvent to remove insoluble impurities and high molecular weight impurities;
a saponification reactor 7 connected to the permeation side of the small-pore ceramic membrane 3 for performing saponification on the permeation liquid of the small-pore ceramic membrane 3;
an alkali solution inlet 5 connected to the saponification reactor 7 for adding an alkali solution to the saponification reactor 7;
a reaction liquid tank 6 connected to the saponification reactor 7 for mixing the saponification reaction liquid with a solvent;
a methanol tank 7, an ethanol tank 8 and a water tank 9 which are respectively connected with the reaction liquid tank 6 and are respectively used for adding methanol, ethanol and water into the reaction liquid tank 6;
the ceramic microfiltration membrane 10 is connected to the reaction liquid tank 6 and is used for separating the organic solvent from water of the feed liquid in the reaction liquid tank 6;
and the dryer 11 is connected to the concentration side of the ceramic microfiltration membrane 10 and is used for evaporating the solvent of the concentrated solution of the ceramic microfiltration membrane 10 to dryness to obtain a finished coenzyme Q10 product.
In one embodiment, further comprising:
a nanofiltration membrane 12 connected to the permeation side of the ceramic microfiltration membrane 10 and used for performing nanofiltration treatment on the permeation liquid of the ceramic microfiltration membrane 10 to intercept protein;
and a spray dryer 13 connected to the concentration side of the nanofiltration membrane 12, for spray drying the concentrated solution of the nanofiltration membrane 12.
In one embodiment, the small pore ceramic membrane 3 has an average pore size of 1 to 100 nm.
In one embodiment, the small pore ceramic membrane 3 has an average pore size of 5 to 10 nm.
In one embodiment, the average pore size of the ceramic microfiltration membrane 10 is in the range of 50 to 500 nm.
In one embodiment, the water droplet contact angle of the surface of the ceramic microfiltration membrane 10 is in the range of 100-160 °.
In one embodiment, the molecular weight cut-off of the nanofiltration membrane 12 is 200-.
The coenzyme Q10 raw material used in the following examples is a crude product obtained in coenzyme Q10 production by a fermentation method, and is mainly obtained by crushing thalli, extracting obtained bacterial powder by using a solvent and evaporating to dryness; the solvent can adopt tetrahydrofuran-methanol, ethyl acetate-methanol and ethyl acetate-ethanol mixed solvent. The specific crude product is obtained by reference to the prior art.
Example 1
A method for efficiently purifying coenzyme Q10 from fermentation liquor comprises the following steps:
(1) taking 50kg of a coenzyme Q10 crude product obtained by fermentation, continuously adding 200kg of normal hexane, filtering by using an 8nm ceramic membrane to remove solid impurities and macromolecular impurities in the normal hexane to obtain 230kg of filtrate;
(2) adding 115kg of 5wt% KOH solution into the filtrate obtained in the step (1), heating and saponifying, sequentially and continuously adding 150kg of methanol, 300kg of ethanol and 300kg of pure water into the reaction solution, and filtering by using 500nm ceramic membranes respectively to enable the polar solvent to permeate the ceramic membranes and retain the organic solvent. The addition of methanol, ethanol and water can play a role in dialysis, so that more impurities are dissolved in the polar solvent and permeate the ceramic membrane.
(3) After filtering, respectively passing the three sections of filtrate obtained in the step (2) through 200Da organic membranes to obtain an alcoholic solution, and returning to the step (2) for reuse, wherein trapped liquid is evaporated to obtain a protein byproduct;
(4) and (3) further evaporating the trapped fluid in the step (2) to remove the solvent to obtain the purified coenzyme Q10.
Example 2
A method for efficiently purifying coenzyme Q10 from fermentation liquor comprises the following steps:
(1) taking 50kg of a coenzyme Q10 crude product obtained by fermentation, continuously adding 180kg of petroleum ether, filtering by a 20nm ceramic membrane to remove solid impurities and macromolecular impurities in the product, and obtaining 210kg of filtrate;
(2) and (2) adding 100kg of 5wt% NaOH solution into the filtrate obtained in the step (1), heating and saponifying, sequentially and continuously adding 50kg of methanol, 250kg of ethanol and 300kg of pure water into the reaction solution, respectively, filtering by using a 200nm ceramic membrane, allowing the polar solvent to permeate through the ceramic membrane, and intercepting the organic solvent. The addition of methanol, ethanol and water can play a role in dialysis, so that more impurities are dissolved in the polar solvent and permeate the ceramic membrane.
(3) After filtering, respectively passing the three sections of filtrate obtained in the step (2) through 500Da organic membranes to obtain an alcoholic solution, and returning to the step (2) for reuse, wherein trapped liquid is evaporated to obtain a protein byproduct;
(4) and (3) further evaporating the trapped fluid in the step (2) to remove the solvent to obtain the purified coenzyme Q10.
Example 3
A method for efficiently purifying coenzyme Q10 from fermentation liquor comprises the following steps:
(1) taking 50kg of a coenzyme Q10 crude product obtained by fermentation, continuously adding 200kg of normal hexane, and filtering through a 5nm ceramic membrane to obtain 230kg of filtrate;
(2) adding 115kg of 5wt% KOH solution into the filtrate obtained in the step (1), heating and saponifying, sequentially and continuously adding 50kg of methanol, 300kg of ethanol and 300kg of pure water into the reaction solution, and filtering by adopting a 200nm ceramic membrane to enable the polar solvent to permeate the ceramic membrane, so that the organic solvent is intercepted. The addition of methanol, ethanol and water can play a role in dialysis, so that more impurities are dissolved in the polar solvent and permeate the ceramic membrane.
(3) After filtering, respectively passing the three sections of filtrate obtained in the step (2) through 200Da organic membranes to obtain an alcoholic solution, and returning to the step (2) for reuse, wherein trapped liquid is evaporated to obtain a protein byproduct;
(4) and (3) further evaporating the trapped fluid in the step (2) to remove the solvent to obtain the purified coenzyme Q10.
Example 4
The differences from example 1 are: the hydrophobic ceramic membrane with the surface subjected to KH570 graft modification is used for separating the organic solvent and the polar solvent of the saponification solution, and the water drop contact angle of the membrane surface ranges from about 145 degrees.
A method for efficiently purifying coenzyme Q10 from fermentation liquor comprises the following steps:
(1) taking 50kg of a coenzyme Q10 crude product obtained by fermentation, continuously adding 200kg of normal hexane, filtering by using an 8nm ceramic membrane to remove solid impurities and macromolecular impurities in the normal hexane to obtain 230kg of filtrate;
(2) adding 115kg of 5wt% KOH solution into the filtrate obtained in the step (1), heating and saponifying, sequentially and continuously adding 150kg of methanol, 300kg of ethanol and 300kg of pure water into the reaction solution, and filtering by using a 500nm surface hydrophobic modified ceramic membrane respectively to enable the polar solvent to permeate the ceramic membrane and the organic solvent to be intercepted. The addition of methanol, ethanol and water can play a role in dialysis, so that more impurities are dissolved in the polar solvent and permeate the ceramic membrane.
(3) After filtering, respectively passing the three sections of filtrate obtained in the step (2) through 200Da organic membranes to obtain an alcoholic solution, and returning to the step (2) for reuse, wherein trapped liquid is evaporated to obtain a protein byproduct;
(4) and (3) further evaporating the trapped fluid in the step (2) to remove the solvent to obtain the purified coenzyme Q10.
Example 5
The differences from example 2 are: the hydrophobic ceramic membrane with the surface subjected to KH570 graft modification is used for separating the organic solvent and the polar solvent of the saponification solution, and the water drop contact angle of the membrane surface ranges from about 145 degrees.
A method for efficiently purifying coenzyme Q10 from fermentation liquor comprises the following steps:
(1) taking 50kg of a coenzyme Q10 crude product obtained by fermentation, continuously adding 180kg of petroleum ether, filtering by a 20nm ceramic membrane to remove solid impurities and macromolecular impurities in the product, and obtaining 210kg of filtrate;
(2) and (2) adding 100kg of 5wt% NaOH solution into the filtrate obtained in the step (1), heating and saponifying, sequentially and continuously adding 50kg of methanol, 250kg of ethanol and 300kg of pure water into the reaction solution, and filtering by using a 200nm surface hydrophobic modified ceramic membrane to enable the polar solvent to permeate the ceramic membrane and retain the organic solvent. The addition of methanol, ethanol and water can play a role in dialysis, so that more impurities are dissolved in the polar solvent and permeate the ceramic membrane.
(3) After filtering, respectively passing the three sections of filtrate obtained in the step (2) through 500Da organic membranes to obtain an alcoholic solution, and returning to the step (2) for reuse, wherein trapped liquid is evaporated to obtain a protein byproduct;
(4) and (3) further evaporating the trapped fluid in the step (2) to remove the solvent to obtain the purified coenzyme Q10.
Comparative example 1
The difference from example 1 is that: the saponification liquid is not filtered by a ceramic microfiltration membrane, but the organic phase and the water phase in the saponification liquid are extracted and separated by a traditional standing and layering method.
A method for efficiently purifying coenzyme Q10 from fermentation liquor comprises the following steps:
(1) taking 50kg of a coenzyme Q10 crude product obtained by fermentation, continuously adding 200kg of normal hexane, filtering by using an 8nm ceramic membrane to remove solid impurities and macromolecular impurities in the normal hexane to obtain 230kg of filtrate;
(2) adding 115kg of 5wt% KOH solution into the filtrate obtained in the step (1), heating and saponifying, sequentially and continuously adding 150kg of methanol, 300kg of ethanol and 300kg of pure water into the reaction solution, standing and layering to obtain a water phase and an organic phase.
(3) Passing the water phase in the step (2) through a 200Da organic membrane to obtain an alcoholic solution, returning to the step (2) for reuse, and evaporating trapped liquid to obtain a protein byproduct;
(4) and (3) further evaporating the organic phase in the step (2) to remove the solvent to obtain the purified coenzyme Q10.
Comparative example 2
The difference from example 1 is that: when the organic solvent and the polar solvent of the saponification solution are separated by using a ceramic microfiltration membrane, no dialysis operation is performed by using ethanol and methanol.
A method for efficiently purifying coenzyme Q10 from fermentation liquor comprises the following steps:
(1) taking 50kg of a coenzyme Q10 crude product obtained by fermentation, continuously adding 200kg of normal hexane, filtering by using an 8nm ceramic membrane to remove solid impurities and macromolecular impurities in the normal hexane to obtain 230kg of filtrate;
(2) adding 115kg of 5wt% KOH solution into the filtrate obtained in the step (1), heating and saponifying, and filtering the reaction solution by using a 500nm ceramic membrane to enable the polar solvent to permeate the ceramic membrane, so that the organic solvent is intercepted.
(3) After filtering, respectively passing the three sections of filtrate obtained in the step (2) through 200Da organic membranes to obtain an alcoholic solution, and returning to the step (2) for reuse, wherein trapped liquid is evaporated to obtain a protein byproduct;
(4) and (3) further evaporating the trapped fluid in the step (2) to remove the solvent to obtain the purified coenzyme Q10.
The purity of the finished product obtained by the above procedure is shown in the following table:
as can be seen from the table, the coenzyme Q10 product with higher purity can be obtained by the continuous separation mode of the ceramic membrane in the invention; the ceramic membrane with the surface subjected to hydrophobic treatment is adopted in the embodiments 4 and 5, so that the saponification reaction liquid containing normal hexane and a polar solvent can be more effectively separated, impurities dissolved in the polar solvent can be more effectively permeated and an organic phase can be intercepted due to the surface subjected to hydrophobic treatment, the separation effect of the ceramic membrane is better, and the purity of the coenzyme Q10 is improved; in addition, by comparing example 1 with example 1, it can be seen that the separation mode of the ceramic membrane adopted by the invention has far better saponification liquid separation effect than the traditional standing layering extraction separation mode, the separation precision is higher, and the purity of the coenzyme Q10 product is improved; furthermore, it can be seen from the examples 1 and the comparative examples 2 that, when the ceramic microfiltration membrane is used for separation, dialysis operation is also performed by using a polar solvent such as ethanol, so that impurities dissolved in the polar solvent in the saponified solution can be effectively taken away, and the impurities can permeate the ceramic membrane, thereby improving the product purity.
Claims (10)
1. A method for extracting coenzyme Q10 is characterized by comprising the following steps:
step 1, adding a nonpolar solvent into a crude coenzyme Q10 product prepared by a fermentation method to dissolve coenzyme Q10;
step 2, filtering the solution obtained in the step 1 by using a small-aperture ceramic membrane to remove insoluble impurities and high-molecular-weight impurities;
step 3, adding alkali liquor into the filtrate obtained in the step 2 to perform saponification reaction;
step 4, sequentially adding methanol, ethanol and water into the saponification reaction liquid, simultaneously filtering by using a ceramic microfiltration membrane, and distilling the concentrated solution of the ceramic microfiltration membrane under reduced pressure to remove the solvent to obtain coenzyme Q10;
and 5, filtering the filtrate of the ceramic microfiltration membrane in the step 4 by using a nanofiltration membrane, wherein the filtrate is an alcohol aqueous solution, the trapped fluid is protein, and the trapped fluid is spray-dried to obtain the recovered protein.
2. The method for extracting coenzyme Q10 according to claim 1, wherein in one embodiment, the crude coenzyme Q10 is obtained by extracting fermented bacterial powder with a solvent and evaporating to dryness; the solvent can adopt tetrahydrofuran-methanol, ethyl acetate-methanol and ethyl acetate-ethanol mixed solvent; in one embodiment, the non-polar solvent is selected from one of pentane, n-hexane, petroleum ether, or heptane.
3. The method of claim 1, wherein the small-pore ceramic membrane of step 2 has an average pore size of 1 to 100nm, preferably 5 to 10 nm; in one embodiment, in the step 3, the alkali solution is sodium hydroxide, potassium hydroxide or sodium bicarbonate solution, the concentration of the alkali solution is 5-10wt%, the addition amount of the alkali solution is 0.4-1 times of the filtrate, and the temperature is controlled to be 20-50 ℃.
4. The method of claim 1, wherein the microfiltration membrane used in the step 4 has an average pore size in the range of 50 to 500 nm; the surface of the microfiltration membrane is subjected to hydrophobic modification treatment, and the water drop contact angle of the surface of the microfiltration membrane is in the range of 100-160 degrees; in one embodiment, the nanofiltration membrane in step 5 has a molecular weight cut-off of 200-.
5. The method of claim 1, wherein the total volume of methanol and ethanol added is controlled to be 5 to 8 times the volume of the saponification reaction solution, and the amount of water washing is controlled to be 1 to 3 times the volume of the saponification reaction solution.
6. An extraction device of coenzyme Q10, comprising:
the raw material tank (1) is used for preliminarily dissolving a coenzyme Q10 crude product;
the nonpolar solvent adding tank (2) is connected to the raw material tank (1) and is used for adding the nonpolar solvent into the raw material tank (1);
the small-aperture ceramic membrane (3) is connected to the raw material tank (1) and is used for filtering and removing impurities from the coenzyme Q10 solution dissolved by the nonpolar solvent to remove insoluble impurities and high-molecular-weight impurities;
a saponification reactor (7) connected to the permeation side of the small-aperture ceramic membrane (3) and used for performing saponification reaction on the permeation liquid of the small-aperture ceramic membrane (3);
an alkali solution inlet (5) connected to the saponification reactor (7) for adding an alkali solution to the saponification reactor (7);
a reaction liquid tank (6) connected to the saponification reactor (7) for mixing the saponification reaction liquid with the solvent;
the methanol tank (7), the ethanol tank (8) and the water tank (9) are respectively connected with the reaction liquid tank (6) and are respectively used for adding methanol, ethanol and water into the reaction liquid tank (6);
the ceramic microfiltration membrane (10) is connected to the reaction liquid tank (6) and is used for separating the organic solvent from water of the feed liquid in the reaction liquid tank (6);
and the dryer (11) is connected to the concentration side of the ceramic microfiltration membrane (10) and is used for carrying out solvent evaporation treatment on the concentrated solution of the ceramic microfiltration membrane (10) to obtain a finished product coenzyme Q10.
7. The apparatus for extracting coenzyme Q10 of claim 6, further comprising:
the nanofiltration membrane (12) is connected to the permeation side of the ceramic microfiltration membrane (10) and is used for performing nanofiltration treatment on the permeation liquid of the ceramic microfiltration membrane (10) so as to intercept protein;
and a spray dryer (13) which is connected to the concentration side of the nanofiltration membrane (12) and is used for spray drying the concentrated solution of the nanofiltration membrane (12).
8. The apparatus for extracting coenzyme Q10 according to claim 6, wherein, in one embodiment, the small-pore ceramic membrane (3) has an average pore size of 1-100 nm; in one embodiment, the small pore ceramic membrane (3) has an average pore size of 5 to 10 nm.
9. The apparatus for extracting coenzyme Q10 according to claim 6, wherein in one embodiment, the average pore size of the ceramic microfiltration membrane (10) is in the range of 50-500 nm; in one embodiment, the water droplet contact angle of the surface of the ceramic microfiltration membrane (10) is in the range of 100-; in one embodiment, the molecular weight cut-off of the nanofiltration membrane (12) is 200-.
10. The ceramic microfiltration membrane is applied to the separation of the saponification reaction liquid of the coenzyme Q10.
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