CN108176226A - The membrane filtration method for concentration of gibberellic acid and membrane filtration concentration systems - Google Patents
The membrane filtration method for concentration of gibberellic acid and membrane filtration concentration systems Download PDFInfo
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- CN108176226A CN108176226A CN201810048383.8A CN201810048383A CN108176226A CN 108176226 A CN108176226 A CN 108176226A CN 201810048383 A CN201810048383 A CN 201810048383A CN 108176226 A CN108176226 A CN 108176226A
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- 238000005374 membrane filtration Methods 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 43
- IXORZMNAPKEEDV-UHFFFAOYSA-N gibberellic acid GA3 Natural products OC(=O)C1C2(C3)CC(=C)C3(O)CCC2C2(C=CC3O)C1C3(C)C(=O)O2 IXORZMNAPKEEDV-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000005980 Gibberellic acid Substances 0.000 title claims abstract description 28
- IXORZMNAPKEEDV-OBDJNFEBSA-N gibberellin A3 Chemical compound C([C@@]1(O)C(=C)C[C@@]2(C1)[C@H]1C(O)=O)C[C@H]2[C@]2(C=C[C@@H]3O)[C@H]1[C@]3(C)C(=O)O2 IXORZMNAPKEEDV-OBDJNFEBSA-N 0.000 title claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 75
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 71
- 238000001728 nano-filtration Methods 0.000 claims abstract description 53
- 239000012141 concentrate Substances 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 15
- 229930191978 Gibberellin Natural products 0.000 claims abstract description 11
- 239000003448 gibberellin Substances 0.000 claims abstract description 11
- 238000000605 extraction Methods 0.000 claims description 49
- 238000001914 filtration Methods 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 239000012528 membrane Substances 0.000 claims description 26
- 239000012071 phase Substances 0.000 claims description 26
- 230000008676 import Effects 0.000 claims description 25
- 239000003125 aqueous solvent Substances 0.000 claims description 12
- 239000012074 organic phase Substances 0.000 claims description 12
- 239000012530 fluid Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 6
- 238000013517 stratification Methods 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
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- 239000000463 material Substances 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 7
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- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000002779 inactivation Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 22
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- 238000002425 crystallisation Methods 0.000 description 15
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- 230000008025 crystallization Effects 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- 239000012452 mother liquor Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
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- 238000004064 recycling Methods 0.000 description 5
- 238000009834 vaporization Methods 0.000 description 5
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
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- 125000003118 aryl group Chemical group 0.000 description 4
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- 238000001704 evaporation Methods 0.000 description 4
- 210000003608 fece Anatomy 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000010871 livestock manure Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
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- 239000007787 solid Substances 0.000 description 4
- 238000000638 solvent extraction Methods 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
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- 206010013786 Dry skin Diseases 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- 229920002492 poly(sulfone) Polymers 0.000 description 2
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- 238000007670 refining Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 241000228245 Aspergillus niger Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000009917 Crataegus X brevipes Nutrition 0.000 description 1
- 235000013204 Crataegus X haemacarpa Nutrition 0.000 description 1
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- 235000009444 Crataegus X rubrocarnea Nutrition 0.000 description 1
- 235000009486 Crataegus bullatus Nutrition 0.000 description 1
- 235000017181 Crataegus chrysocarpa Nutrition 0.000 description 1
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- 235000004423 Crataegus monogyna Nutrition 0.000 description 1
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- 235000002313 Crataegus paludosa Nutrition 0.000 description 1
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- 239000004425 Makrolon Substances 0.000 description 1
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- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 235000006029 Prunus persica var nucipersica Nutrition 0.000 description 1
- 244000017714 Prunus persica var. nucipersica Species 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 240000008866 Ziziphus nummularia Species 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000007599 discharging Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 230000005078 fruit development Effects 0.000 description 1
- 230000008774 maternal effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000010152 pollination Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229930000044 secondary metabolite Natural products 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
- B01D61/145—Ultrafiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D1/00—Evaporating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
-
- 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
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/06—Tubular membrane modules
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/93—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems condensed with a ring other than six-membered
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention provides a kind of membrane filtration method for concentration of gibberellic acid, including：S1 Ferment of Gibberellin Acid liquid) is obtained into tubular type membrane filtration clear liquid and tubular type membrane filtration raffinate through tubular type membrane filtration；S2 the tubular type membrane filtration clear liquid) is subjected to ultrafiltration, obtains ultrafiltration clear liquid and ultrafiltration raffinate；S3 the ultrafiltration clear liquid) is subjected to nanofiltration, obtains concentrate.Compared with prior art, the present invention is concentrated successively using tubular type membrane filtration, ultrafiltration and nanofiltration, with short production cycle, reduce energy consumption, the problem of improving concentration yield, while also avoiding gibberellic acid product heat-sensitive materials active ingredient inactivation, improves product quality.
Description
Technical field
The invention belongs to gibberellic acid preparing technical field more particularly to a kind of membrane filtration method for concentration of gibberellic acid and film mistakes
Filter concentration systems.
Background technology
Gibberellic acid is a kind of secondary metabolite being metabolized by a kind of fermentation of Aspergillus niger culture, is detached, identified
There are 116 kinds with one kind of name, wherein most widely used in agricultural is exactly GA3, played in China's agricultural production huge
Big effect.
GA3Activity is adjusted with very high plant, there is apparent adjusting to the growth and development of various crops
Effect.In the north, GA3It is mainly used on the industrial crops such as grape, jujube, hawthorn, nectarine, it is red in spray in bloom stage a certain concentration
Mould acid solution can effectively improve the fruit-setting rate of fruit tree, promote fruit development, and output of the fruit tree improves 20%~30% or so.
In south, gibberellic acid is mainly used on breeding of hybrid rice, is adjusted rice Parent and is bloomed in the same time, makes maternal pollination
Rate greatly improves, and further improves the yield of hybrid rice seeds, reduces the production cost of seed, is alleviated for peasant negative
Load.
For the filtering and concentrating technique of existing gibberellic acid generally using vacuum film concentration technology, the consumption of the method water power vapour is big,
Production cycle is long, gibberellic acid product heat-sensitive substance active ingredient is caused to inactivate, product quality is poor, and yield is low.
Invention content
In view of this, the technical problem to be solved in the present invention is to provide a kind of membrane filtration method for concentration of gibberellic acid and film
Filtering and concentrating system, the gibberellic acid product quality that this method obtains are higher.
The present invention provides a kind of membrane filtration method for concentration of gibberellic acid, including：
S1 Ferment of Gibberellin Acid liquid) is obtained into tubular type membrane filtration clear liquid and tubular type membrane filtration raffinate through tubular type membrane filtration；
S2 the tubular type membrane filtration clear liquid) is subjected to ultrafiltration, obtains ultrafiltration clear liquid and ultrafiltration raffinate；
S3 the ultrafiltration clear liquid) is subjected to nanofiltration, obtains concentrate.
Preferably, the specification of the tubular membrane is 30~50KD.
Preferably, the tubular membrane is selected from metal film, ceramic membrane, natural macromolecule membrane or synthetic polymeric membrane.
Preferably, the step S1) be specially：
By Ferment of Gibberellin Acid liquid through 0.2~0.6 times that tubular type membrane filtration to supernatant volume is fermentating liquid volume, then continuously
Aqueous solvent is added in 1~2.5 times that supernatant volume is fermentating liquid volume, tubular type membrane filtration clear liquid is obtained and tubular type membrane filtration is residual
Liquid.
Preferably, the molecular cut off of the film of the ultrafiltration is 4000~6000.
Preferably, it further includes：
S4) concentrate with extractant is extracted, obtains extract liquor；
S5) by the extract liquor condensing crystallizing, gibberellic acid is obtained
Preferably, the step S4) be specially：After the concentrate is mixed with extractant, with adjusting pH value to 2~3,
It is extracted, stratification obtains extract liquor and water phase；
The water phase and organic solvent are subjected to continuous extraction, obtain extractant of the organic phase as concentrate.
The present invention also provides a kind of membrane filtration concentration systems of gibberellic acid, including：
Tubular type membrane filtration system；The tubular type membrane filtration system is provided with zymotic fluid import, aqueous solvent import, crosses cleaner liquid
Outlet and the outlet of filtering raffinate；
Ultrafiltration system；The ultrafiltration system is provided with ultrafiltration system import and ultrafiltration purified liquor outlet；The ultrafiltration system into
Mouth is connected with the filtering purified liquor outlet of the tubular type membrane filtration system；
Nanofiltration system；The nanofiltration system is provided with nanofiltration system import and concentrated solution outlet；The nanofiltration system import
It is connected with ultrafiltration purified liquor outlet.
Preferably, plate-frame filtering system is further included；The plate-frame filtering system is provided with import and sheet frame purified liquor outlet；Institute
The import for stating plate-frame filtering system is connected with the outlet of the filtering raffinate of the tubular type membrane filtration system；The sheet frame clear liquid goes out
Mouth is connected with the aqueous solvent import of the tubular type membrane filtration system.
Preferably, extracting system is further included；The extracting system includes single-stage extraction system and continuous extraction system；It is described
Single-stage extraction system is provided with extractant entrance, concentrate entrance, organic phase outlet and water phase and exports；The concentrate entrance with
The concentrated solution outlet of the nanofiltration system is connected；The continuous extraction system setting organic solvent entrance, water phase entrance are with having
Machine mutually exports；The water phase entrance of the continuous extraction system is connected with the water phase entrance of single-stage extraction system；The continuous extraction
The organic phase outlet of system is taken to be connected with the extractant entrance of the single-stage extraction system.
The present invention provides a kind of membrane filtration method for concentration of gibberellic acid, including：S1) by Ferment of Gibberellin Acid liquid through tubular membrane
Filtering, obtains tubular type membrane filtration clear liquid and tubular type membrane filtration raffinate；S2 the tubular type membrane filtration clear liquid) is subjected to ultrafiltration, is obtained
Ultrafiltration clear liquid and ultrafiltration raffinate；S3 the ultrafiltration clear liquid) is subjected to nanofiltration, obtains concentrate.Compared with prior art, it is of the invention
It is concentrated successively using tubular type membrane filtration, ultrafiltration and nanofiltration, it is with short production cycle, reduce energy consumption, improve concentration yield, together
When also avoid gibberellic acid product heat-sensitive materials active ingredient inactivation the problem of, improve product quality.
Description of the drawings
Fig. 1 is the flow diagram of the embodiment of the present invention 1.
Specific embodiment
Below in conjunction with the embodiment of the present invention, the technical solution in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only part of the embodiment of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, those of ordinary skill in the art's all other embodiments obtained without making creative work, all
Belong to the scope of protection of the invention.
The present invention provides a kind of membrane filtration method for concentration of gibberellic acid, including：
S1 Ferment of Gibberellin Acid liquid) is obtained into tubular type membrane filtration clear liquid and tubular type membrane filtration raffinate through tubular type membrane filtration；
S2 the tubular type membrane filtration clear liquid) is subjected to ultrafiltration, obtains ultrafiltration clear liquid and ultrafiltration raffinate；
S3 the ultrafiltration clear liquid) is subjected to nanofiltration, obtains concentrate.
Wherein, the present invention is not particularly limited the source of all raw materials, is commercially available.
By Ferment of Gibberellin Acid liquid through tubular type membrane filtration, ultrafiltration clear liquid and ultrafiltration raffinate are obtained；The Ferment of Gibberellin Acid liquid is
Ferment of Gibberellin Acid liquid well known to those skilled in the art, there is no any restrictions；The specification of the tubular membrane is preferably
30~50KD, more preferably 40KD；The material of the tubular membrane is preferably metal film, ceramic membrane, natural macromolecule membrane or synthesis
Polymeric membrane.According to the present invention, which is preferably specially：By Ferment of Gibberellin Acid liquid through tubular type membrane filtration to supernatant volume to send out
0.2~0.6 times of zymotic fluid volume, more preferably 0.3~0.5 times are further preferably 0.35~0.5 times, most preferably 0.375~
0.5 times, it is 1~2.5 times of fermentating liquid volume to be then continuously added to aqueous solvent to supernatant volume, more preferably 1.5~2.2 times,
It is further preferably 1.5~1.8 times, most preferably 1.5~1.75 times, obtains tubular type membrane filtration clear liquid and tubular type membrane filtration raffinate；Institute
It can be the water that clear water is alternatively recycling to state aqueous solvent.
The tubular type membrane filtration raffinate preferably carries out plate-frame filtering, obtains plate-frame filtering clear liquid and filter residue；The sheet frame mistake
The specification of the film of filter is preferably 600~900B, more preferably 700~800B, is further preferably 750B；Material is preferably polypropylene.
The clear liquid of the plate-frame filtering can be used as aqueous solvent to be used for tubular type membrane filtration；The filter residue can be used for producing bacterial manure after drying.
The tubular type membrane filtration clear liquid is subjected to ultrafiltration, obtains ultrafiltration clear liquid and ultrafiltration raffinate；The film of the ultrafiltration is cut
It is preferably 4000~6000 to stay molecular weight, and more preferably 4500~5500, it is further preferably 5000；The material of the film of the ultrafiltration is excellent
It is selected as organic film, more preferably cellulose and its derivates, makrolon, polyvinyl chloride, Kynoar, polysulfones, polypropylene
One kind in nitrile, polyamide, polysulfonamides, sulfonated polysulfone, the polyvinyl alcohol of interlinkage, modified acrylic polymer；The ultrafiltration
Method for method well known to those skilled in the art, have no special limitation, preferably continuous ultrafiltration in the present invention；Institute
The preferably agitated rear progress plate-frame filtering of ultrafiltration raffinate is stated, obtains plate-frame filtering clear liquid and filter residue.The clear liquid of the plate-frame filtering
Aqueous solvent can be used as to be used for tubular type membrane filtration；The filter residue can be used for producing bacterial manure after drying.
The ultrafiltration clear liquid is subjected to nanofiltration, obtains concentrate；The method of the nanofiltration is known to those skilled in the art
Method, have no special limitation, preferably carry out first time nanofiltration and second of nanofiltration in the present invention successively；Described
Nanofiltration is preferably the continuous nanofiltration concentration of level Four, obtains concentrate and discharges water with level Four；The first order is discharged water and is arranged with the second level
The preferred recycling of water outlet, third level discharge water and fourth stage discharge water second of nanofiltration concentration of preferred progress, obtain concentrate
With discharging water；Second of nanofiltration concentration is preferably high power nanofiltration concentration；The concentrate that nanofiltration twice is obtained merges, and second
The discharge water that secondary nanofiltration obtains recycles；The specification of the film of the first time nanofiltration is preferably 80~200D, and more preferably 100
~150D is further preferably 100D；The material of the film of the first time nanofiltration is preferably aromatic series and polyacids hydrogen species composite nanometer filtering film；
The specification of the film of second of nanofiltration is preferably 80~200D, more preferably 100~150D, is further preferably 100D；Described
The material of the film of secondary nanofiltration is preferably aromatic series and polyacids hydrogen species composite nanometer filtering film.
According to the present invention, preferably the concentrate of merging with extractant is extracted, obtains extract liquor；This step is preferably specific
For：After the concentrate is mixed with extractant, with pH value is adjusted to 2~3, extracted, stratification, obtain extract liquor with
Water phase；The water phase and organic solvent are subjected to continuous extraction, obtain extractant of the organic phase as concentrate.The concentrate
Volume ratio with extractant is preferably 1：(0.8~1.5), more preferably 1：(0.9~1.2) is further preferably 1:1；The adjusting
PH value is preferably adjusted using sulfuric acid；The pH value is preferably 2.5~3, and more preferably 2.8~3, it is further preferably 2.8；It is described
Organic solvent is organic solvent well known to those skilled in the art, has no special limitation, is preferably acetic acid in the present invention
Ethyl ester；The method of the continuous extraction is method well known to those skilled in the art, special limitation is had no, in of the invention
Preferably cross current solvent extraction, more preferably six grades of cross current solvent extractions；The content of target product in water phase is down to by continuous extraction
Below 100ppm.Water phase after continuous extraction is discharged into Sewage Disposal processing preferably after evaporating recycling design.
By the extract liquor condensing crystallizing, gibberellic acid is obtained；The method of the condensing crystallizing is ripe for those skilled in the art
The method known has no special limitation, is crystallized in the present invention preferably through the process of twice evaporation concentration, i.e., first
It is evaporated under reduced pressure and concentrates through extract liquor, be concentrated into 2nd/1st to three/3rd of original volume, after cooling filters, then carry out second
Concentration stops concentration after being concentrated into crystallization, and crystallisation by cooling after filtering, obtains gibberellic acid；The mother liquor of the primary crystallization is preferred
Reduction vaporization concentration is carried out again, is stopped after being concentrated into crystallization, crystallisation by cooling after filtering, obtains gibberellic acid.
According to the present invention, obtained gibberellic acid will be preferably crystallized by dry, pulverize.The drying is preferably dry using boiling
It is dry；The crushing is preferably carried out using pulverizing mill.
The present invention is concentrated successively using tubular type membrane filtration, ultrafiltration and nanofiltration, with short production cycle, is reduced energy consumption, is carried
High concentration yield, while the problem of also avoid gibberellic acid product heat-sensitive materials active ingredient inactivation, improve product quality.
The present invention also provides the membrane filtration concentration systems of another gibberellic acid, including：
Tubular type membrane filtration system；The tubular type membrane filtration system is provided with zymotic fluid import, aqueous solvent import, crosses cleaner liquid
Outlet and the outlet of filtering raffinate；
Ultrafiltration system；The ultrafiltration system is provided with ultrafiltration system import and ultrafiltration purified liquor outlet；The ultrafiltration system into
Mouth is connected with the filtering purified liquor outlet of the tubular type membrane filtration system；
Nanofiltration system；The nanofiltration system is provided with nanofiltration system import and concentrated solution outlet；The nanofiltration system import
It is connected with ultrafiltration purified liquor outlet；In the present invention, the nanofiltration system preferably includes the first nanofiltration system and the second nanofiltration system；
The entrance of first nanofiltration system is connected with the ultrafiltration purified liquor outlet of the ultrafiltration system；The first nanofiltration system setting
There are concentrated solution outlet and discharge water out；The discharge water out of first nanofiltration system preferably with second nanofiltration system
Entrance is connected.
According to the present invention, plate-frame filtering system is preferably further included；It is clear with sheet frame that the plate-frame filtering system is provided with import
Liquid exports；The import of the plate-frame filtering system is connected with the filtering raffinate outlet of the tubular type membrane filtration system；The plate
The outlet of frame clear liquid is connected with the aqueous solvent import of the tubular type membrane filtration system.
According to the present invention, extracting system is preferably further included；The extracting system includes single-stage extraction system and continuous extraction
System；The single-stage extraction system is provided with extractant entrance, concentrate entrance, organic phase outlet and water phase and exports；It is described dense
Contracting liquid entrance is connected with the concentrated solution outlet of the nanofiltration system；The continuous extraction system setting organic solvent entrance, water
Phase entrance and organic phase outlet；The water phase entrance of the continuous extraction system is connected with the water phase entrance of single-stage extraction system；
The organic phase outlet of the continuous extraction system is connected with the extractant entrance of the single-stage extraction system.
According to the present invention, condensing crystallizing system is preferably further included；The entrance of the condensing crystallizing system and nitrogen base extraction system
The organic phase outlet of system is connected.
In order to further illustrate the present invention, it is dense to a kind of membrane filtration of gibberellic acid provided by the invention with reference to embodiments
Contracting method and membrane filtration concentration systems are described in detail.
Reagent used in following embodiment is commercially available.
Embodiment 1
1.1 tubular type membrane filtrations：
120t zymotic fluids sterilize after fermentation, are then transferred to storage tank, then directly start tubular type membrane filtration and (do not adjust
pH).Tap water is continuously added to after the clear liquid for filtering out zymotic fluid 45T or so, when the clear liquid for filtering out 260T or so stops pipe
Formula membrane filtration.The specification of tubular membrane：40KD, material：Ceramic membrane)
Membrane filtration clear liquid enters lower one of master operation (ultrafiltration), and raffinate enters lower attached process (plate-frame filtering) together.
1.2 plate-frame filtering：
After tubular type membrane filtration the raffinate of 55T or so directly carry out plate-frame filtering (specification of plate-frame filtering film be 750B, material
Polypropylene), cleaner liquid is crossed for next tank tubular type membrane filtration, and filter residue produces bacterial manure after being dried.
1.3 ultrafiltration：
Clear liquid after tubular membrane carries out ultrafiltration, and what ultrafiltration was selected is the organic material film of 5,000 molecular weight, and membrane material is poly- inclined
Vinyl fluoride.Ultrafiltration is continuous ultrafiltration, and ultrafiltration clear liquid enters next process, and raffinate enters filter residue agitator tank, into plate-frame filtering.
1.4 nanofiltration
Clear liquid after ultrafiltration carries out nanofiltration concentration, and what nanofiltration concentration was taken is 2 concentrations, and concentration is continuous for 4 grades for the first time
Concentration, concentrate enter next process, and 1-2 grades of discharge water recycle, and 3-4 grades of discharge water carry out high power concentration (concentrate
Into next process, discharge water recycles).What is taken during production is a sub-high pressure NF membrane.(the specification of NF membrane
100D, material aromatic series and polyacids hydrogen species composite nanometer filtering film)
1.5 extraction
Nanofiltration concentrate, which is transferred to after refining plant, to be added in isometric continuous extraction solvent (this solvent is by 6 cascades
Solvent after continuous extraction, contains a certain amount of target product), sulphur acid for adjusting pH value is then added in 2.8, carries out single batch of extraction.
Stratification after the completion of extraction.Upper strata solvent mutually enters next process after layering.
Lower floor's water phase carries out continuous 6 grades of cross current solvent extractions again with fresh solvent (ethyl acetate) after layering, by target in water phase
The content of product drops to below 100ppm.
Water phase is discharged into after recycling partial solvent therein using a film scraper evaporator at sewage after continuous extraction
Manage station processing.
Solvent is mutually transferred to storage tank and keeps in after continuous extraction, for single batch of extraction of next batch.
The concentration of 1.6 2000L evaporators does not crystallize
Solvent after single batch of extraction mutually carries out reduction vaporization concentration, and temperature is 45 DEG C, when concentration and evaporation goes out returning for 2T or so
Solvent is received, crystallizing tank cooling is put into, is filtered, into next process.
1.7 5000L evaporator condensing crystallizings
Liquid after 2000L concentrations carries out reduction vaporization concentration, and temperature is 50 DEG C, and crystallizing tank is put into after being concentrated to crystallization
Crystallisation by cooling again.Then it is filtered, solid enters next process as product.One time mother liquor is evaporated under reduced pressure again
Concentration is put into crystallizing tank crystallisation by cooling again after being concentrated to crystallization.Then it is filtered, solid enters lower one as product
Process.Liquid enters mother liquor holding tank as final mother liquor, is then configured to cream preparation.
1.8 dryings crush
By dry, crushing, (drying using boiling drier, crushes at present using omnipotent micro mist product at present after crystallization
Machine) afterwards packing obtain final products, performance test results are shown in Table 1.
The performance test results of crystalline product obtained in 1 embodiment 1 of table
| Serial number | Inspection project | Quality standard |
| 1 | Content | >=90% |
| 2 | Moisture | ≤ 0.5% |
| 3 | Specific rotatory power | + 80 ° of ＞ |
| 4 | Yield | >=70% |
The flow diagram of embodiment 1 is as shown in Figure 1.
Embodiment 2
2.1 tubular type membrane filtrations：
120t zymotic fluids sterilize after fermentation, are then transferred to storage tank, then directly start tubular type membrane filtration and (do not adjust
pH).Tap water is continuously added to after the clear liquid for filtering out zymotic fluid 45T or so, when the clear liquid for filtering out zymotic fluid 260T or so
Stop tubular type membrane filtration.(the specification of tubular membrane：4KD, material：Metal film)
Membrane filtration clear liquid enters lower one of master operation (ultrafiltration), and raffinate enters lower attached process (plate-frame filtering) together.
2.2 plate-frame filtering：
The raffinate of 55T or so directly carries out plate-frame filtering after tubular type membrane filtration, and the specification of plate-frame filtering film is 750B, material
Polypropylene crosses cleaner liquid for next tank tubular type membrane filtration, and filter residue produces bacterial manure after being dried.
1.3 ultrafiltration：
Clear liquid after tubular membrane carries out ultrafiltration, and what ultrafiltration was selected is the organic material film of 5,000 molecular weight, and membrane material is poly- carbon
Acid esters.Ultrafiltration is continuous ultrafiltration, and ultrafiltration clear liquid enters next process, and raffinate enters filter residue agitator tank, into plate-frame filtering.
2.4 nanofiltration
Clear liquid after ultrafiltration carries out nanofiltration concentration, and what nanofiltration concentration was taken is 2 concentrations, and concentration is continuous for 4 grades for the first time
Concentration, concentrate enter next process, and 1-2 grades of discharge water recycle, and 3-4 grades of discharge water carry out high power concentration (concentrate
Into next process, discharge water recycles).What is taken during production is a sub-high pressure NF membrane.The specification 100D of NF membrane
And material aromatic series and polyacids hydrogen species composite nanometer filtering film
2.5 extraction
Nanofiltration concentrate, which is transferred to after refining plant, to be added in isometric continuous extraction solvent (this solvent is by 6 cascades
Solvent after continuous extraction, contains a certain amount of target product), sulphur acid for adjusting pH value is then added in 2.8, carries out single batch of extraction.
Stratification after the completion of extraction.Upper strata solvent mutually enters next process after layering.
Lower floor's water phase carries out continuous 6 grades of cross current solvent extractions again with fresh solvent (ethyl acetate) after layering, by target in water phase
The content of product drops to below 100ppm.
Water phase is discharged into after recycling partial solvent therein using a film scraper evaporator at sewage after continuous extraction
Manage station processing.
Solvent is mutually transferred to storage tank and keeps in after continuous extraction, for single batch of extraction of next batch.
The concentration of 2.6 2000L evaporators does not crystallize
Solvent after single batch of extraction mutually carries out reduction vaporization concentration, and temperature is 45 DEG C, when concentration and evaporation goes out returning for 2T or so
Solvent is received, crystallizing tank cooling is put into, is filtered, into next process.
2.7 5000L evaporator condensing crystallizings
Liquid after 2000L concentrations carries out reduction vaporization concentration, and temperature is 50 DEG C, and crystallizing tank is put into after being concentrated to crystallization
Crystallisation by cooling again.Then it is filtered, solid enters next process as product.One time mother liquor is evaporated under reduced pressure again
Concentration is put into crystallizing tank crystallisation by cooling again after being concentrated to crystallization.Then it is filtered, solid enters lower one as product
Process.Liquid enters mother liquor holding tank as final mother liquor, is then configured to cream preparation.
2.8 dryings crush
By dry, crushing, (drying using boiling drier, crushes at present using omnipotent micro mist product at present after crystallization
Machine) afterwards packing obtain final products, performance test results are shown in Table 2.
The performance test results of crystalline product obtained in 2 embodiment 2 of table
| Serial number | Inspection project | Quality standard |
| 1 | Content | >=90% |
| 2 | Moisture | ≤ 0.5% |
| 3 | Specific rotatory power | + 80 ° of ＞ |
| 4 | Yield | >=70% |
Claims (10)
1. a kind of membrane filtration method for concentration of gibberellic acid, which is characterized in that including：
S1 Ferment of Gibberellin Acid liquid) is obtained into tubular type membrane filtration clear liquid and tubular type membrane filtration raffinate through tubular type membrane filtration；
S2 the tubular type membrane filtration clear liquid) is subjected to ultrafiltration, obtains ultrafiltration clear liquid and ultrafiltration raffinate；
S3 the ultrafiltration clear liquid) is subjected to nanofiltration, obtains concentrate.
2. membrane filtration method for concentration according to claim 1, which is characterized in that the specification of the tubular membrane for 30~
50KD。
3. membrane filtration method for concentration according to claim 1, which is characterized in that the tubular membrane is selected from metal film, ceramics
Film, natural macromolecule membrane or synthetic polymeric membrane.
4. membrane filtration method for concentration according to claim 1, which is characterized in that the step S1) be specially：
By Ferment of Gibberellin Acid liquid through 0.2~0.6 times that tubular type membrane filtration to supernatant volume is fermentating liquid volume, then it is continuously added to
Aqueous solvent obtains tubular type membrane filtration clear liquid and tubular type membrane filtration raffinate to 1~2.5 times that supernatant volume is fermentating liquid volume.
5. membrane filtration method for concentration according to claim 1, which is characterized in that the molecular cut off of the film of the ultrafiltration is
4000~6000.
6. membrane filtration method for concentration according to claim 1, which is characterized in that further include：
S4) concentrate with extractant is extracted, obtains extract liquor；
S5) by the extract liquor condensing crystallizing, gibberellic acid is obtained.
7. membrane filtration method for concentration according to claim 6, which is characterized in that the step S4) be specially：It will be described dense
After contracting liquid is mixed with extractant, with pH value is adjusted to 2~3, extracted, stratification obtains extract liquor and water phase；
The water phase and organic solvent are subjected to continuous extraction, obtain extractant of the organic phase as concentrate.
8. a kind of membrane filtration concentration systems of gibberellic acid, which is characterized in that including：
Tubular type membrane filtration system；The tubular type membrane filtration system is provided with zymotic fluid import, aqueous solvent import, filtering purified liquor outlet
With the outlet of filtering raffinate；
Ultrafiltration system；The ultrafiltration system is provided with ultrafiltration system import and ultrafiltration purified liquor outlet；The ultrafiltration system import with
The filtering purified liquor outlet of the tubular type membrane filtration system is connected；
Nanofiltration system；The nanofiltration system is provided with nanofiltration system import and concentrated solution outlet；The nanofiltration system import is with surpassing
Cleaner liquid outlet is connected.
9. membrane filtration concentration systems according to claim 8, which is characterized in that further include plate-frame filtering system；The plate
Frame filtration system is provided with import and sheet frame purified liquor outlet；The import of the plate-frame filtering system and the tubular type membrane filtration system
Filtering raffinate outlet be connected；The outlet of the sheet frame clear liquid is connected with the aqueous solvent import of the tubular type membrane filtration system
It is logical.
10. membrane filtration concentration systems according to claim 8, which is characterized in that further include extracting system；The extraction system
System includes single-stage extraction system and continuous extraction system；The single-stage extraction system be provided with extractant entrance, concentrate entrance,
Organic phase outlet is exported with water phase；The concentrate entrance is connected with the concentrated solution outlet of the nanofiltration system；It is described continuous
Extracting system setting organic solvent entrance, water phase entrance and organic phase outlet；The water phase entrance and list of the continuous extraction system
The water phase entrance of grade extracting system is connected；The organic phase outlet of the continuous extraction system and the extraction of the single-stage extraction system
Agent entrance is taken to be connected.
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