CN106467442A - Preparation and treatment methods and application of fermentation liquor of 1, 3-propylene glycol, preparation method of water-soluble fertilizer and water-soluble fertilizer - Google Patents
Preparation and treatment methods and application of fermentation liquor of 1, 3-propylene glycol, preparation method of water-soluble fertilizer and water-soluble fertilizer Download PDFInfo
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- CN106467442A CN106467442A CN201610807609.9A CN201610807609A CN106467442A CN 106467442 A CN106467442 A CN 106467442A CN 201610807609 A CN201610807609 A CN 201610807609A CN 106467442 A CN106467442 A CN 106467442A
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- thalline
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- underflow
- fermentation
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- 108010009355 microbial metalloproteinases Proteins 0.000 description 1
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 229960003104 ornithine Drugs 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical group CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 239000005413 snowmelt Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229960004799 tryptophan Drugs 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 229960004295 valine Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000036642 wellbeing Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/80—Soil conditioners
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D1/00—Fertilisers containing potassium
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F7/00—Fertilisers from waste water, sewage sludge, sea slime, ooze or similar masses
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Fertilizers (AREA)
Abstract
The invention relates to the field of 1, 3-propylene glycol fermentation, and discloses a preparation method of 1, 3-propylene glycol fermentation liquor, a treatment method of the 1, 3-propylene glycol fermentation liquor, application of solid containing organic acid potassium salt and inorganic salt and thallus degradation clear liquid obtained by the treatment method in preparation of a water-soluble fertilizer, a preparation method of the water-soluble fertilizer, and the water-soluble fertilizer obtained by the method. The 1, 3-propanediol fermentation liquor is obtained by fermenting glycerol with microorganisms, and in the fermentation process, a neutralizing agent is used for adjusting the pH value of the fermentation liquor, wherein the neutralizing agent contains more than 50 wt% of potassium hydroxide. The method for treating the 1, 3-propylene glycol fermentation liquor comprises the step of treating the 1, 3-propylene glycol fermentation liquor. The method provided by the invention eliminates the direct or indirect pollution of byproducts to the environment and reduces the production cost of the fertilizer under the condition of ensuring the 1, 3-propylene glycol produced by microbial fermentation.
Description
Technical field
A kind of the present invention relates to 1,3-PD fermentation arts, in particular it relates to preparation of the fermentation liquid of 1,3-PD
Method, a kind of processing method of 1,3- propanediol fermentation liquor, by aforementioned processing methods obtain containing organic acid potassium salt and inorganic
The solid of salt and thalline are degraded application in preparation Water soluble fertilizer for the clear liquid, a kind of preparation method of Water soluble fertilizer and obtained by the method
The Water soluble fertilizer arriving.
Background technology
1,3-PD (1,3-propanediol) is a kind of important industrial chemicals, can be used for material, solvent, lubrication
The industry such as agent and antifreeze, especially in materials industry, 1,3-PD can be used for synthesizing PTT
(PTT).PTT is a kind of biodegradable polyester material of excellent performance, has good ductility and washing property, is spinning
Knit, the aspect such as plastics has broad application prospects, the market demand is huge.
1,3- propylene glycol can prepare in several ways.Wherein, microbial method fermentation glycerol produces 1,3- the third two
The method mild condition of alcohol and efficiently, receives more and more attention.The process of fermentable glycerol production 1,3- propylene glycol
In, in addition to generating 1,3-PD, also can generate the organic acid by-product such as lactic acid, acetic acid and succinic acid.Accordingly, it would be desirable to use
Nertralizer adjusts the pH of fermentation liquid.The method of current 1,3-propanediol produced by microbial fermentation, the nertralizer of use mostly is hydrogen
Sodium oxide (CN1763210A；CN101182552A；CN102443608A).Adjust the pH of fermentation liquid using sodium hydroxide, can make
Organic acid in fermentation liquid generates organic acid sodium salt, and its concentration is generally 20-50g/L.1,3- propylene glycol is extracted from fermentation liquid
Afterwards, can remaining substantial amounts of byproduct organic acids sodium salt in fermented waste fluid.The method processing organic acid sodium salt at present mainly has two kinds：
First method is to make Snow Agent, but the organic acid sodium salt spraying can enter water body with snow melt, and environment is caused with secondary dirt
Dye；Second method is organic acid sodium salt to be filled or burns, costly, inadequate environmental protection.Both approaches are not all inconsistent
Close the demand of sustainable development, at present, also there is no the organic acid sodium salt processing method of environment-protecting clean.In addition, fermentable is sweet
During oil produces 1,3-PD, also can obtain another kind of by-product-thalline, its dry weight is generally 2-10g/L.From fermentation
After extracting 1,3-PD in liquid, substantial amounts of thalline underflow can be obtained.Due to lacking effective process and Application way, thalline is dense
Another difficult problem being treated as in fermentable glycerol production 1,3- propylene glycol technique of slurry.
The difficult treatment of byproduct organic acids sodium salt and thalline and energy consumption are big, increased the cost of 1,3-PD production,
Also the environmental protection restraining factors of 1,3-PD production are become, current production technology is it is difficult to realize the cleaning life of 1,3-PD
Produce.Therefore, a kind of preparation of fermentation liquid of the exploitation efficient 1,3-PD of environmental protection and processing method are very important.
Content of the invention
The purpose of the present invention be overcome in existing 1,3- propylene glycol production technology the inadequate environmental protection of processing method of fermentation liquid and
Thoroughly defect, there is provided a kind of preparation method of the fermentation liquid of 1,3-PD, a kind of process of 1,3-PD fermentation liquid
Method, a kind of preparation method of Water soluble fertilizer and the Water soluble fertilizer being obtained by the method.
In a first aspect, the invention provides a kind of preparation method of the fermentation liquid of 1,3-PD, this fermentation liquid passes through micro-
Biofermentation glycerol obtains, and during the fermentation, adjusts the pH value of fermentation liquid using nertralizer, and described nertralizer contains 50 weights
The potassium hydroxide of amount more than %.
Second aspect, the invention provides a kind of processing method of the fermentation liquid of 1,3-PD, the method includes following
Step：
1) fermentation liquid of 1,3-PD obtained above is carried out the first solid-liquid separation, obtain in thalline underflow and fermentation
The step of clear liquid；
2) from step 1) separate the fermented supernatant fluid that obtains and obtain 1,3- propylene glycol and containing organic acid potassium salt and no
The step of the solid of machine salt；
3) by step 1) the thalline underflow that obtains degraded, and obtain thalline and degrade the step of underflow；
4) by step 3) the described thalline degraded underflow that obtains carries out the second solid-liquid separation, obtains thalline degraded clear liquid and filter
The step of slag；
5) by step 2) solid containing organic acid potassium salt and inorganic salt that obtains and step 4) the described filtering residue that obtains mixes
Close, for the step of solid organic fertilizer or the production of soil conditioner.
The third aspect, the invention provides a kind of by above-mentioned processing method obtain containing organic acid potassium salt and inorganic salt
The application in preparation Water soluble fertilizer of solid and thalline degraded clear liquid.
Fourth aspect, the invention provides a kind of preparation method of Water soluble fertilizer, the method includes the process using the present invention
The solid containing organic acid potassium salt and inorganic salt in method and thalline degrade clear liquid as the preparing raw material of Water soluble fertilizer, according to
The factory formula preparation Water soluble fertilizer of Water soluble fertilizer.
5th aspect, the invention provides the Water soluble fertilizer being prepared by above-mentioned preparation method.
The present invention, in the technique of traditional fermentable glycerol production 1,3-PD, substitutes hydrogen using potassium hydroxide
Sodium oxide adjusts the pH of fermentation liquid so that the by-product generating during producing 1,3-PD is by organic acid sodium as nertralizer
Organic acid potassium salt changed into by salt, and organic acid potassium salt contains the nutrients such as abundant potassium, phosphorus and water soluble organic substance, can be solid as producing
State fertilizer and the supplementary material of acid soil improving agent, while reducing Chemical Potassium use, reduce production cost, increase
Fertilizer efficiency, the raising to happiness potassium crop quality has positive effect, can improve peasant income；The alkalescence of organic acid potassium salt is permissible
Reduce the acidity of acid ground or the increase slowing down acidity to a certain extent；Although organic acid sodium salt can be used as Snow Agent, obtain
Obtain economic well-being of workers and staff necessarily, but secondary pollution can be caused to environment；After adopting new technology, secondary pollution will not be produced.Another
Plant by-product thalline after enzymolysis or acidolysis process and filter new technology, the thalline degraded rich in soluble amino acid can be obtained
Clear liquid and the filtering residue rich in tropina；Organic acid potassium salt and phosphate can be dissolved by thalline degraded clear liquid, water-soluble as producing
Fertile supplementary material, except can be greatly decreased Chemical Potassium and high price aminoacid using in addition to, its completely water solublity, still prevent
Water soluble fertilizer blocks spray orifice during spraying；Filtering residue rich in tropina can be individually or together with organic acid potassium salt, as life
Produce the supplementary material of solid organic fertilizer and acid soil improving agent.
In sum, the present invention, under conditions of ensureing fermentable glycerol production 1,3-PD, eliminates by-product
The direct or indirect pollution to environment for the thing, decreases fertilizer, acid soil improvement is fertile and Water soluble fertilizer produces to Chemical Potassium
Demand, significantly reduce the production cost of fertilizer, improve soil fertility, quality of agricultural product and peasant income.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with following tool
Body embodiment is used for explaining the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the preparation of the fermentation liquid of 1,3- propylene glycol of present invention offer and a kind of preferred embodiment party of processing method
Formula.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that it is described herein concrete
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
Herein the end points of disclosed scope and any value are not limited to this accurate scope or value, these scopes or
Value should be understood to comprise the value close to these scopes or value.For numerical range, between the endpoint value of each scope, respectively
Between the endpoint value of individual scope and single point value, and can be obtained one or more between single point value with combination with one another
New numerical range, these numerical rangies should be considered herein specifically to disclose.
The invention provides a kind of preparation method of the fermentation liquid of 1,3-PD, it is sweet that this fermentation liquid passes through fermentable
Oil obtains, wherein, during the fermentation, using nertralizer adjust fermentation liquid pH value, described nertralizer contain 50 weight % with
On potassium hydroxide.
In the present invention, described nertralizer can be the conventional sense of this area, refer to for adjusting in sweat
The material of fermentation liquid pH value.Due to during fermentable glycerol production 1,3-PD, except generating 1,3- the third two
Outside alcohol, also can generate the organic acid by-product such as lactic acid, acetic acid and succinic acid, so needing nertralizer to be beneficial to fermentation adjusting pH
Be smoothed out.In order that acylate more advantageously carries out the process of follow-up environmental protection it is preferable that described nertralizer contains
There are the potassium hydroxide of 50-100 weight % and the sodium hydroxide of 0-50 weight %.
In the present invention, the step of described fermentable glycerol and condition can be that the conventional of this area selects.According to
One kind of the present invention preferred embodiment, by microbial inoculant to glycerol fermentation culture medium, is fermented in fermentation tank, is made
Adjust the pH of fermentation liquid with nertralizer, stop fermentation when the 1,3-PD concentration in fermentation liquid no longer rises, obtain 1,3-
The fermentation liquid of propylene glycol.The condition of described fermentable glycerol includes：Temperature can be 30-37 DEG C, and fermentation liquid pH can be
6-7, mixing speed can be 150-250rpm, and ventilation can be 0.5-2.0VVM.In fermenting and producing, typically with ventilation ratio
To represent ventilation, generally to be represented (V/V min) with the interior volume of air ratio by unit volume culture fluid per minute, letter
It is written as VVM.
In the present invention, the composition of described glycerol fermentation culture medium can be that 1,3- the third two are prepared in the various fermentations of this area
The fermentation medium of alcohol, for example can be for disclosed in the patent application such as CN1763210A, CN101182552A, CN102443608A
Fermentation medium.According to a kind of specific embodiment of the present invention, the consisting of of the fermentation medium used in the present invention：
Glycerol 40g, K2HPO4·3H2O 3.20g, KH2PO41.20g, NH4Cl 2.85g, Na2SO40.28g, MgSO4·7H2O
0.10g, citric acid 0.42g, yeast extract 2.00g, trace element 0.3mL, complement to 1L using distilled water.The composition of trace element
For：ZnCl27.56g, FeCl3·6H2O 15.65g, MnCl2·4H2O 6.28g, CuCl2·2H2O 1.32g, CoCl2·
6H2O 6.42g, H3BO30.48g, Na2MoO4·2H2O 3.22g, complements to 1L using distilled water.
In the present invention, the microorganism fermented can be the conventional selection of this area.For example, described microorganism is permissible
For Klebsiella pneumoniae (Klebsiella), Freund Fructus Citri Limoniae bacterium (Citrobacter) and clostridium butyricum
One or more of (Clostridium).
Present invention also offers a kind of processing method of the fermentation liquid of 1,3-PD, wherein, the method includes following step
Suddenly：
1) fermentation liquid of 1,3-PD obtained above is carried out the first solid-liquid separation, obtain in thalline underflow and fermentation
The step of clear liquid；
2) from step 1) separate the fermented supernatant fluid that obtains and obtain 1,3- propylene glycol and containing organic acid potassium salt and no
The step of the solid of machine salt；
3) by step 1) the thalline underflow that obtains degraded, and obtain thalline and degrade the step of underflow；
4) by step 3) the described thalline degraded underflow that obtains carries out the second solid-liquid separation, obtains thalline degraded clear liquid and filter
The step of slag；
5) by step 2) solid containing organic acid potassium salt and inorganic salt that obtains and step 4) the described filtering residue that obtains mixes
Close, for the step of solid organic fertilizer or the production of soil conditioner.
According to the present invention, the mode of described first solid-liquid separation and the second solid-liquid separation can be the conventional choosing of this area
Select.The mode of described first solid-liquid separation and described second solid-liquid separation can be identical or different, described first solid-liquid separation
Mode for filtering and/or can be centrifuged, and the mode of described second solid-liquid separation for filtering and/or can be centrifuged.Described filtration can
To be carried out by purpose ceramic-film filter, described centrifugation can be carried out using disc centrifuge.
According to the present invention, in step 2) in, separate from fermented supernatant fluid and obtain 1,3-PD and contain organic acid
The separation method of the solid of potassium salt and inorganic salt can be the conventional selection of this area.For example can be for carrying out successively concentrating, removing
Salt and rectification.According to one kind of the present invention preferred embodiment, described fermented supernatant fluid carries out detached method and includes following step
Suddenly：By being concentrated described fermented supernatant fluid, then it is fed to scrapper thin film evaporator, obtain containing 1,3- third from tower top
Glycol and the liquid of 2,3-butanediol, G ＆ W, obtain the solid containing organic acid potassium salt and inorganic salt from bottom of towe.Will be upper
State the liquid containing 1,3-PD and 2,3-butanediol, G ＆ W and carry out rectification, obtain 1,3-PD.
In the present invention, described inorganic salt can be nitrogen salt and/or microcosmic salt, and specific species and content can be according to fermentation
The component of culture medium is determined.
In the present invention, described step 3) in degraded mode there is no particular limitation, as long as can drop thalline underflow
Solution simultaneously can be utilized.According to one kind of the present invention preferred embodiment, step 3) in degraded mode be acidolysis and/or
Enzymolysis.Described acidolysis includes being contacted described thalline underflow with acid, and described enzymolysis includes entering described thalline underflow with enzyme
Row contact.
According to the present invention, the mode of described acidolysis and enzymolysis can be the conventional selection of this area, for example, described acidolysis institute
The acid using can be one or more of sulphuric acid, hydrochloric acid and nitric acid.Preferably, the acid that acidolysis is used is concentrated sulphuric acid.More
Preferably, the acid that acidolysis is used is the concentrated sulphuric acid of 80-98 weight %.There is no particular limitation for the consumption of described concentrated sulphuric acid, only
Thalline underflow can be degraded.In order to obtain more preferable degradation effect it is preferable that thalline with respect to 100 weight portions
Underflow, with H2SO4The consumption of the concentrated sulphuric acid of meter is 3-5 weight portion.There is no particular limitation for the condition of described acidolysis, can be this
The conventional selection in field.For example, the condition of described acidolysis includes：Temperature can be 60-120 DEG C, preferably 80-100 DEG C；Time
Can be 10-60 hour, preferably 26-48 hour.According to one kind of the present invention preferred embodiment, described enzymolysis is in stirring
Under the conditions of carry out.There is no particular limitation for the rotating speed of described stirring, for example, can be 50-200rpm, preferably 100-200rpm.
There is no particular limitation for the species of the enzyme that the present invention is used for described enzymolysis, can be various use in this area
Enzyme come thalline of degrading.For example, the used enzyme of enzymolysis can be protease, is specifically as follows acid protease, neutral protein
One or more of enzyme and alkaline protease, preferably papain, bromelain, papain, hydrolyzed protein
In enzyme Alcalase (Novi's letter), neutral protease Neutrase (Novi's letter) and compound protease Protamex (Novi's letter)
One or more.
In the present invention, there is no particular limitation for the consumption of described protease, as long as can fully digest thalline.
For example, the thalline underflow with respect to 1kg, the consumption of described protease can be 500,000-500 ten thousand U, preferably 1,000,000-300 ten thousand
U.Wherein, " U " is unit of enzyme activity, and concrete meaning is well known to those skilled in the art.Specifically, the definition of unit of enzyme activity
For：Under given conditions, 1min can convert the enzyme amount of 1 μ g substrate, i.e. 1U=1 μ g/min.
There is no particular limitation for the condition digesting for the present invention, can be the various conditions of conventional protease hydrolyzed.
For example, the condition of described enzymolysis includes：PH can be 6.5-7.5, preferably 6.5-7；Temperature can be 40-60 DEG C, preferably
50-55 DEG C, the time can be 24-48 hour, preferably 24-36 hour.According to one kind of the present invention preferred embodiment, described
Enzymolysis is carried out under conditions of stirring.There is no particular limitation for the rotating speed of described stirring, for example, can be 50-200rpm, preferably
For 100-200rpm.
In the present invention, step 4) it is rich in soluble amino acid, described solubility in the described thalline degraded clear liquid that obtains
Aminoacid can include but is not limited to, aspartic acid, threonine, serine, agedoite, glutamic acid, alpha-Aminoadipic acid, sweet
Propylhomoserin, alanine, citrulline, L-Valine, cysteine, methionine, cystathionie, isoleucine, leucine, tyrosine, benzene
Alanine, Beta-alanine, B-AIB, γ-aminobutyric acid, tryptophan, ornithine, lysine, histidine and arginine
One or more of.The species of above-mentioned aminoacid and concentration (for example can be purchased from Hitachi, board by aminoacid detector
Number be L-8900) detected.
In the present invention, step 4) the described filtering residue that obtains is rich in tropina.Process in accordance with the present invention 5), will contain
The solid of organic acid potassium salt and inorganic salt and step 4) the described filtering residue that obtains mixes.The mode of described mixing and condition do not have spy
Other restriction, as long as can be by both mix homogeneously.For example, it is possible to heating or and/or stirring under conditions of mix, mix
Obtain after conjunction mixing underflow.This mixing underflow can as the raw and auxiliary material producing solid organic fertilizer or soil conditioner,
Production for solid organic fertilizer or soil conditioner.Other raw materials specific and proportioning are according to solid organic fertilizer or soil
The production technology of modifying agent is carried out, and will not be described here.Wherein, because the solid containing organic acid potassium salt and inorganic salt contains
The nutritional labelings such as potassium, phosphorus and water soluble organic substance, can subtract as the supplementary material producing solid organic fertilizer and soil conditioner
While few Chemical Potassium uses, reduce cost.In addition, the alkalescence of organic acid potassium salt, acid can be reduced to a certain extent
Property soil acidity or alleviate acidity increase.Therefore described soil conditioner is preferably acid soil improving agent.
Present invention also offers the solid containing organic acid potassium salt and inorganic salt being obtained by above-mentioned processing method and bacterium
Application in preparation Water soluble fertilizer for the body degraded clear liquid.
Present invention also offers a kind of preparation method of Water soluble fertilizer, the method includes containing organic acid potassium salt using above-mentioned
Clear liquid degrade with the solid of inorganic salt and thalline as the preparing raw material of Water soluble fertilizer, the factory formula according to Water soluble fertilizer prepares water
Molten fertilizer.
According to one kind preferred embodiment, will mix with thalline degraded clear liquid containing organic acid potassium salt and inorganic salt solid
Obtain mixed solution, this mixed solution as produce Water soluble fertilizer raw and auxiliary material, for the production of Water soluble fertilizer.The side of described mixing
There is no particular limitation for formula and condition, as long as can be by both mix homogeneously.For example, it is possible in heating or and/or stirring
Under conditions of mix.Other raw materials specific of Water soluble fertilizer and proportioning are carried out according to the production technology of Water soluble fertilizer.
The preparation of fermentation liquid of the 1,3- propylene glycol of present invention offer is provided below according to Fig. 1 and one kind of processing method is excellent
The embodiment of choosing.As shown in figure 1, fermentation medium carries out fermenting obtains the fermentation liquid of 1,3-PD, make in sweat
Adjust the pH of fermentation liquid with potassium hydroxide as nertralizer.Described 1,3- propanediol fermentation liquor obtains bacterium by the first solid-liquid separation
Body underflow and fermented supernatant fluid.Described fermented supernatant fluid carries out concentrating desalination and distillation process obtains containing organic acid potassium salt and nothing
The solid of machine salt and 1,3- propylene glycol.Thalline underflow is degraded, is obtained thalline degraded underflow.Thalline degraded underflow is carried out
Second solid-liquid separation, obtains thalline degraded clear liquid and filtering residue.Solid containing organic acid potassium salt and inorganic salt and filtering residue are mixed,
Production for solid organic fertilizer or soil conditioner.Will be clear with thalline degraded for the solid containing organic acid potassium salt and inorganic salt
Liquid mixes, for the production of Water soluble fertilizer.
Present invention also offers the Water soluble fertilizer being prepared by said method.
Hereinafter will be described the present invention by embodiment.
In the examples below,
The described composition containing organic acid potassium salt and the solid of inorganic salt is entered using the relevant criterion that country or industry are announced
Row analysis measures.Wherein, nitrogen content adopts the method in standard HJ 535-2009 to measure；Phosphorus content adopts standard GB/T
Method in 17767.2-2010 measures；Potassium content adopts the method in standard NY/T 1977-2010 to measure；Total amount of organic
Measured using the method in standard NY/T 304-1995.It should be noted that the process that analysis measures is that element is examined
Survey, in addition to nitrogen content is in terms of nitrogen, other elements cubage is then the form of the particular compound according to element
Meter, in terms of phosphorus pentoxide, potassium content is in terms of potassium oxide for phosphorus content.
Purpose ceramic-film filter is purchased from Novartis and matches；Disc centrifuge is purchased from Alfa Laval, and the trade mark is LAPX404；Protease
Biological, the specially papain purchased from Nanning Pang Bo；Aminoacid detector is purchased from Hitachi, and the trade mark is L-8900.
The consisting of of fermentation medium used in embodiment：Glycerol (glycerol) 40g, K2HPO4·3H2O 3.20g,
KH2PO41.20g, NH4Cl 2.85g, Na2SO40.28g, MgSO4·7H2O 0.10g, citric acid 0.42g, yeast extract
2.00g, trace element 0.3mL, complement to 1L using distilled water.The consisting of of trace element：ZnCl27.56g, FeCl3·
6H2O 15.65g, MnCl2·4H2O 6.28g, CuCl2·2H2O 1.32g, CoCl2·6H2O 6.42g, H3BO30.48g,
Na2MoO4·2H2O 3.22g, complements to 1L using distilled water.Fermentation culture is based on 121 DEG C and sterilizes 20 minutes.All reagent are equal
For commercially available.
Embodiment 1
The present embodiment is used for the preparation of the fermentation liquid of 1,3- propylene glycol and processing method and the application that the present invention provides is described
And the preparation method of Water soluble fertilizer and Water soluble fertilizer
(1-1) preparation method of the fermentation liquid of 1,3- propylene glycol
Klebsiella pneumoniae (Klebsiella) is aseptically seeded to the fermentation filling fermentation medium
In tank, fermented, fermentation temperature is 30 DEG C, mixing speed is 250rpm, ventilation is 2.0VVM.Whole using potassium hydroxide
(100 weight %) replaces the pH that sodium hydroxide adjusts fermentation liquid is 6.5, when the concentration of 1,3-PD in fermentation liquid no longer rises
When, stop fermentation, obtain 1,3-PD fermentation liquid, its composition is listed in Table 1 below.
(1-2) processing method of 1,3- propanediol fermentation liquor
1,3-PD fermentation liquid obtained in the previous step is filtered using purpose ceramic-film filter, it is dense that separation obtains thalline
Slurry and fermented supernatant fluid.This fermented supernatant fluid is concentrated, is then fed to scrapper thin film evaporator, is contained from tower top
1,3-PD and the liquid of 2,3-butanediol, G ＆ W, obtain consolidating containing organic acid potassium salt and inorganic salt from bottom of towe
Body.
Carry out component analyses by obtaining the solid containing organic acid potassium salt and inorganic salt, concrete operation step is：Take 1kg
The above-mentioned solid containing organic acid potassium salt and inorganic salt is dissolved in 20kg water, the saline solution obtaining is analyzed measuring, obtains
To in the solid containing organic acid potassium salt and inorganic salt, the content of nitrogen, phosphorus, potassium and total amount of organic, is specifically listed in Table 2 below.
The thalline obtaining in previous step underflow is carried out component analyses, is specifically listed in Table 3 below.
Thalline underflow is digested：According to 1kg thalline underflow in thalline underflow：The ratio of 1000000 U adds albumen
Enzyme, reaction condition includes：PH is 7.0, and temperature is 55 DEG C, speed of agitator 100rpm, and the time is 24 hours, obtains thalline degraded dense
Slurry.
Thalline obtained in the previous step degraded underflow is filtered, obtains thalline degraded clear liquid and filtering residue.Detected using aminoacid
Instrument detects the species of aminoacid and the concentration that thalline is degraded in clear liquid, is specifically listed in Table 4 below.
The solid containing organic acid potassium salt and inorganic salt that above-mentioned steps are obtained is mixed with filtering residue heating, obtains mixing dense
Slurry, is mixed with other raw materials as raw and auxiliary material, according to the factory formula of solid organic fertilizer or acid soil improving agent, uses
Production in solid organic fertilizer or acid soil improving agent.
(1-3) preparation method of Water soluble fertilizer and Water soluble fertilizer
The solid containing organic acid potassium salt and inorganic salt that obtain above-mentioned steps and thalline degraded clear liquid heating mixing, obtain
To mixed solution, mix with other raw materials as raw and auxiliary material, the factory formula according to Water soluble fertilizer is used for the life of Water soluble fertilizer
Produce.
Table 1
| Composition (g/L) | Embodiment 1 | Comparative example 1 |
| Dry cell weight | 3.2 | 3.0 |
| 1,3- propylene glycol | 80.7 | 80.2 |
| 2,3- butanediol | 15.2 | 15.7 |
| Ethanol | 2.1 | 2.3 |
| Glycerol | 5.5 | 6.3 |
| Lactate | 18.8 | 16.5 |
| Acetate | 5.4 | 4.4 |
| Succinate | 3.6 | 3.0 |
Table 2
| Composition | Nitrogen | Phosphorus | Potassium | Total amount of organic |
| Concentration (g/g) | 0.0053 | 0.0432 | 0.28 | 0.4315 |
Table 3
| Composition | Concentration (g/L) | Composition | Concentration (g/L) |
| Dry cell weight | 98 | Glycerol | 6.2 |
| 1,3- propylene glycol | 82.5 | Lactate | 18.5 |
| 2,3- butanediol | 16.1 | Acetate | 5.1 |
| Ethanol | 1.9 | Succinate | 3.8 |
Table 4
Comparative example 1
Step (1-1) according to embodiment 1 is carried out, and except for the difference that, nertralizer is all using sodium hydroxide.The 1,3- of gained
The composition of propanediol fermentation liquor is listed in Table 1 below.
From table 1 it follows that no matter being used potassium hydroxide or sodium hydroxide to adjust the pH of fermentation liquid as nertralizer,
In obtained 1,3- propanediol fermentation liquor, the production concentration such as dry cell weight, 1,3- propylene glycol, 2,3- butanediol and ethanol is close.
And because the relative atomic mass of potassium is higher than sodium, therefore substitute, using potassium hydroxide, the 1,3-PD that sodium hydroxide obtains completely
The concentration of the acylate in fermentation liquid is slightly above the concentration of the acylate being used sodium hydroxide to obtain as nertralizer.
The nertralizer that can be seen that due to using from the result of comparative example 1 is sodium hydroxide, so obtaining for organic acid sodium
Salt.Understand, the inadequate environmental protection of subsequent treatment of organic acid sodium salt is effective according to the record in background of invention.
Embodiment 2
The present embodiment is used for the preparation of the fermentation liquid of 1,3- propylene glycol and processing method and the application that the present invention provides is described
And the preparation method of Water soluble fertilizer and Water soluble fertilizer
(2-1) preparation method of the fermentation liquid of 1,3- propylene glycol
Klebsiella pneumoniae (Klebsiella) is aseptically seeded to the fermentation filling fermentation medium
In tank, fermented, fermentation temperature is 37 DEG C, mixing speed is 150rpm, ventilation is 1.0VVM.Using potassium hydroxide part
(potassium hydroxide accounts for nertralizer 75 weight %) replaces the pH that sodium hydroxide adjusts fermentation liquid is 6, when 1,3-PD in fermentation liquid
Concentration when no longer rising, stop fermentation, obtain 1,3-PD fermentation liquid, its composition is listed in Table 5 below.
(2-2) processing method of 1,3- propanediol fermentation liquor
1,3-PD fermentation liquid obtained in the previous step is centrifuged using disc centrifuge, separate obtain thalline underflow and
Fermented supernatant fluid.This fermented supernatant fluid is concentrated, is then fed to scrapper thin film evaporator, obtained containing 1,3- from tower top
Propylene glycol and the liquid of 2,3-butanediol, G ＆ W, obtain the solid containing organic acid potassium salt and inorganic salt from bottom of towe.
Carry out component analyses by obtaining the solid containing organic acid potassium salt and inorganic salt, concrete operation step is：Take 1kg
The above-mentioned solid containing organic acid potassium salt and inorganic salt is dissolved in 20kg water, the saline solution obtaining is analyzed measuring, obtains
To in the solid containing organic acid potassium salt and inorganic salt, the content of nitrogen, phosphorus, potassium and total amount of organic, is specifically listed in Table 6 below.
The thalline obtaining in previous step underflow is carried out component analyses, is specifically shown in Table 7.
Thalline underflow is digested：According to 1kg thalline underflow in thalline underflow：The ratio of 2000000 U adds albumen
Enzyme, reaction condition includes：PH is 6.5, and temperature is 50 DEG C, speed of agitator 120rpm, and the time is 36 hours, obtains thalline degraded dense
Slurry.
Thalline obtained in the previous step degraded underflow is filtered, obtains thalline degraded clear liquid and filtering residue.Detected using aminoacid
Instrument detects the species of aminoacid and the concentration that thalline is degraded in clear liquid, is specifically listed in Table 8 below.
The solid containing organic acid potassium salt and inorganic salt that above-mentioned steps are obtained is mixed with filtering residue heating, obtains mixing dense
Slurry, is mixed with other raw materials as raw and auxiliary material, according to the factory formula of solid organic fertilizer or acid soil improving agent, uses
Production in solid organic fertilizer or acid soil improving agent.
(2-3) preparation method of Water soluble fertilizer and Water soluble fertilizer
The solid containing organic acid potassium salt and inorganic salt that obtain above-mentioned steps and thalline degraded clear liquid heating mixing, obtain
To mixed solution, mix with other raw materials as raw and auxiliary material, the factory formula according to Water soluble fertilizer is used for the life of Water soluble fertilizer
Produce.
Table 5
| Composition | Concentration (g/L) | Composition | Concentration (g/L) |
| Dry cell weight | 4.0 | Glycerol | 10.2 |
| 1,3- propylene glycol | 75.3 | Lactate | 15.2 |
| 2,3- butanediol | 18.5 | Acetate | 4.7 |
| Ethanol | 1.6 | Succinate | 4.0 |
Table 6
| Composition | Nitrogen | Phosphorus | Potassium | Total amount of organic |
| Concentration (g/g) | 0.0051 | 0.0413 | 0.22 | 0.4290 |
Table 7
| Composition | Concentration (g/L) | Composition | Concentration (g/L) |
| Dry cell weight | 120 | Glycerol | 11.3 |
| 1,3- propylene glycol | 79.1 | Lactate | 15.0 |
| 2,3- butanediol | 18.8 | Acetate | 5.2 |
| Ethanol | 1.7 | Succinate | 4.5 |
Table 8
Embodiment 3
The present embodiment is used for the preparation of the fermentation liquid of 1,3- propylene glycol and processing method and the application that the present invention provides is described
And the preparation method of Water soluble fertilizer and Water soluble fertilizer
Method according to embodiment 1 is carried out, and except for the difference that, the condition that thalline underflow is digested is different, specifically, by bacterium
Body underflow is digested：According to 1kg thalline underflow in thalline underflow：The ratio of 3000000 U adds protease, reaction condition bag
Include：PH is 7.5, and temperature is 40 DEG C, speed of agitator 200rpm, and the time is 48 hours, obtains thalline degraded underflow.
Thalline obtained in the previous step degraded underflow is filtered, obtains thalline degraded clear liquid and filtering residue.Detected using aminoacid
Instrument detects the species of aminoacid and the concentration that thalline is degraded in clear liquid, is specifically listed in Table 9 below.
The solid containing organic acid potassium salt and inorganic salt that above-mentioned steps are obtained is mixed with filtering residue heating, obtains mixing dense
Slurry, is mixed with other raw materials as raw and auxiliary material, according to the factory formula of solid organic fertilizer or acid soil improving agent, uses
Production in solid organic fertilizer or acid soil improving agent.
(3-3) preparation method of Water soluble fertilizer and Water soluble fertilizer
Carry out according to the method in embodiment 1.
Table 9
Embodiment 4
The present embodiment is used for the preparation of the fermentation liquid of 1,3- propylene glycol and processing method and the application that the present invention provides is described
And the preparation method of Water soluble fertilizer and Water soluble fertilizer
(4-1) preparation method of the fermentation liquid of 1,3- propylene glycol
Klebsiella pneumoniae (Klebsiella) is aseptically seeded to the fermentation filling fermentation medium
In tank, fermented, fermentation temperature is 33 DEG C, mixing speed is 200rpm, ventilation is 0.5VVM.Using potassium hydroxide part
(potassium hydroxide accounts for nertralizer 50 weight %) replaces the pH that sodium hydroxide adjusts fermentation liquid is 7, when 1,3-PD in fermentation liquid
Concentration when no longer rising, stop fermentation, obtain 1,3-PD fermentation liquid, its composition is shown in Table 10.
(4-2) processing method of 1,3- propanediol fermentation liquor
1,3-PD fermentation liquid obtained in the previous step is centrifuged using disc centrifuge, separate obtain thalline underflow and
Fermented supernatant fluid.This fermented supernatant fluid is concentrated, is then fed to scrapper thin film evaporator, obtained containing 1,3- from tower top
Propylene glycol and the liquid of 2,3-butanediol, G ＆ W, obtain the solid containing organic acid potassium salt and inorganic salt from bottom of towe.
Carry out component analyses by obtaining the solid containing organic acid potassium salt and inorganic salt, concrete operation step is：Take 1kg
The above-mentioned solid containing organic acid potassium salt and inorganic salt is dissolved in 20kg water, the saline solution obtaining is analyzed measuring, obtains
To in the solid containing organic acid potassium salt and inorganic salt, the content of nitrogen, phosphorus, potassium and total amount of organic, is specifically shown in Table 11.
The thalline obtaining in previous step underflow is carried out component analyses, is specifically shown in Table 12.
Thalline underflow is carried out acidolysis：According to 1kg thalline underflow in thalline underflow：The ratio of 0.04kg acid adds 98 weights
The concentrated sulphuric acid of amount %, reaction condition includes：Temperature is 95 DEG C, speed of agitator 100rpm, and the time is 24 hours, obtains thalline degraded
Underflow.
Thalline obtained in the previous step degraded underflow is filtered, obtains thalline degraded clear liquid and filtering residue.Detected using aminoacid
Instrument detects the species of aminoacid and the concentration that thalline is degraded in clear liquid, is specifically shown in Table 13.
The solid containing organic acid potassium salt and inorganic salt that above-mentioned steps are obtained is mixed with filtering residue heating, obtains mixing dense
Slurry, is mixed with other raw materials as raw and auxiliary material, according to the factory formula of solid organic fertilizer or acid soil improving agent, uses
Production in solid organic fertilizer or acid soil improving agent.
(4-3) preparation method of Water soluble fertilizer and Water soluble fertilizer
The solid containing organic acid potassium salt and inorganic salt that obtain above-mentioned steps and thalline degraded clear liquid heating mixing, obtain
To mixed solution, mix with other raw materials as raw and auxiliary material, the factory formula according to Water soluble fertilizer is used for the life of Water soluble fertilizer
Produce.
Table 10
| Composition | Concentration (g/L) | Composition | Concentration (g/L) |
| Dry cell weight | 3.5 | Glycerol | 13.5 |
| 1,3- propylene glycol | 70.3 | Lactate | 14.1 |
| 2,3- butanediol | 16.6 | Acetate | 3.8 |
| Ethanol | 2.0 | Succinate | 3.3 |
Table 11
| Composition | Nitrogen | Phosphorus | Potassium | Total amount of organic |
| Concentration (g/g) | 0.0055 | 0.0435 | 0.13 | 0.4420 |
Table 12
| Composition | Concentration (g/L) | Composition | Concentration (g/L) |
| Dry cell weight | 115 | Glycerol | 13.5 |
| 1,3- propylene glycol | 71.0 | Lactate | 14.5 |
| 2,3- butanediol | 16.8 | Acetate | 4.1 |
| Ethanol | 1.9 | Succinate | 3.5 |
Table 13
Embodiment 5
The present embodiment is used for the preparation of the fermentation liquid of 1,3- propylene glycol and processing method and the application that the present invention provides is described
And the preparation method of Water soluble fertilizer and Water soluble fertilizer
(5-1) preparation method of the fermentation liquid of 1,3- propylene glycol
Klebsiella pneumoniae (Klebsiella) is aseptically seeded to the fermentation filling fermentation medium
In tank, fermented, fermentation temperature is 30 DEG C, mixing speed is 250rpm, ventilation is 2.0VVM.Whole using potassium hydroxide
(100%) pH that sodium hydroxide adjusts fermentation liquid is replaced to be 6.5, when the concentration of 1,3-PD in fermentation liquid no longer rises,
Stop fermentation, obtain 1,3-PD fermentation liquid, its composition is shown in Table 14.
(5-2) processing method of 1,3- propanediol fermentation liquor
1,3-PD fermentation liquid obtained in the previous step is filtered using purpose ceramic-film filter, it is dense that separation obtains thalline
Slurry and fermented supernatant fluid.This fermented supernatant fluid is concentrated, is then fed to scrapper thin film evaporator, is contained from tower top
1,3-PD and the liquid of 2,3-butanediol, G ＆ W, obtain consolidating containing organic acid potassium salt and inorganic salt from bottom of towe
Body.
Carry out component analyses by obtaining the solid containing organic acid potassium salt and inorganic salt, concrete operation step is：Take 1kg
The above-mentioned solid containing organic acid potassium salt and inorganic salt is dissolved in 20kg water, the saline solution obtaining is analyzed measuring, obtains
To in the solid containing organic acid potassium salt and inorganic salt, the content of nitrogen, phosphorus, potassium and total amount of organic, is specifically shown in Table 15.
The thalline obtaining in previous step underflow is carried out component analyses, is specifically shown in Table 16.
Thalline underflow is carried out acidolysis：According to 1kg thalline underflow in thalline underflow：The ratio of 0.05kg acid adds 80 weights
The concentrated sulphuric acid of amount %, reaction condition includes：Temperature is 80 DEG C, speed of agitator 200rpm, and the time is 48 hours, obtains thalline degraded
Underflow.
Thalline obtained in the previous step degraded underflow is filtered, obtains thalline degraded clear liquid and filtering residue.Detected using aminoacid
Instrument detects the species of aminoacid and the concentration that thalline is degraded in clear liquid, is specifically shown in Table 17.
The solid containing organic acid potassium salt and inorganic salt that above-mentioned steps are obtained is mixed with filtering residue heating, obtains mixing dense
Slurry, is mixed with other raw materials as raw and auxiliary material, according to the factory formula of solid organic fertilizer or acid soil improving agent, uses
Production in solid organic fertilizer or acid soil improving agent.
(1-3) preparation method of Water soluble fertilizer and Water soluble fertilizer
The solid containing organic acid potassium salt and inorganic salt that obtain above-mentioned steps and thalline degraded clear liquid heating mixing, obtain
To mixed solution, mix with other raw materials as raw and auxiliary material, the factory formula according to Water soluble fertilizer is used for the life of Water soluble fertilizer
Produce.
Table 14
| Composition | Concentration (g/L) | Composition | Concentration (g/L) |
| Dry cell weight | 3.8 | Glycerol | 6.5 |
| 1,3- propylene glycol | 79.6 | Lactate | 16.2 |
| 2,3- butanediol | 15.6 | Acetate | 4.8 |
| Ethanol | 1.8 | Succinate | 3.5 |
Table 15
| Composition | Nitrogen | Phosphorus | Potassium | Total amount of organic |
| Concentration (g/g) | 0.0051 | 0.0422 | 0.27 | 0.4290 |
Table 16
| Composition | Concentration (g/L) | Composition | Concentration (g/L) |
| Dry cell weight | 112 | Glycerol | 7.1 |
| 1,3- propylene glycol | 81.4 | Lactate | 18.5 |
| 2,3- butanediol | 16.1 | Acetate | 5.1 |
| Ethanol | 1.9 | Succinate | 3.8 |
Table 17
Embodiment 6
The present embodiment is used for the preparation of the fermentation liquid of 1,3- propylene glycol and processing method and the application that the present invention provides is described
And the preparation method of Water soluble fertilizer and Water soluble fertilizer
Method according to embodiment 4 is carried out, and except for the difference that, the condition of thalline underflow acidolysis is different, specifically, thalline is dense
Slurry carries out acidolysis：According to 1kg thalline underflow in thalline underflow：The ratio of 0.03kg acid adds the concentrated sulphuric acid of 90 weight %, instead
Condition is answered to include：Temperature is 100 DEG C, speed of agitator 50rpm, and the time is 36 hours, obtains thalline degraded underflow.
Thalline obtained in the previous step degraded underflow is filtered, obtains thalline degraded clear liquid and filtering residue.Detected using aminoacid
Instrument detects the species of aminoacid and the concentration that thalline is degraded in clear liquid, is specifically shown in Table 18.
Remaining step is carried out according to the method for embodiment 4.
Table 18
Can be seen that the technique of traditional fermentable glycerol production 1,3-PD from the result of embodiment,
It is used potassium hydroxide to replace sodium hydroxide to adjust the pH of fermentation liquid so that generating during producing 1,3-PD as nertralizer
Byproduct organic acids sodium salt become organic acid potassium salt, organic acid potassium salt can be used as solid organic fertilizer and acid soil improving agent
Supplementary material, can fully turn waste into wealth.And another by-product thalline can be by the degraded mode of acidolysis or enzymolysis at
Reason, obtains thalline degraded clear liquid and the filtering residue rich in tropina rich in soluble amino acid, and thalline degraded clear liquid can will have
Machine acid potassium salt and phosphate dissolving, as the supplementary material producing Water soluble fertilizer, reduce fertilizer production cost.Filter rich in tropina
Slag can be used as the supplementary material producing solid organic fertilizer and acid soil improving agent together with organic acid potassium salt.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, multiple simple variant can be carried out to technical scheme, this
A little simple variant belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to various can
The compound mode of energy no longer separately illustrates.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as it is without prejudice to this
The thought of invention, it equally should be considered as content disclosed in this invention.
Claims (11)
1. a kind of preparation method of the fermentation liquid of 1,3-PD, this fermentation liquid is obtained by fermentable glycerol, its feature
It is, during the fermentation, adjust the pH value of fermentation liquid using nertralizer, described nertralizer contains the hydrogen-oxygen of more than 50 weight %
Change potassium.
2. preparation method according to claim 1, wherein, described nertralizer contain 50-100 weight % potassium hydroxide and
The sodium hydroxide of 0-50 weight %.
3. preparation method according to claim 1, wherein, the condition of described fermentable glycerol includes：Temperature is 30-
37 DEG C, fermentation liquid pH is 6-7, and mixing speed is 150-250rpm, and ventilation is 0.5-2.0VVM.
4. a kind of processing method of the fermentation liquid of 1,3-PD is it is characterised in that the method comprises the following steps：
1) fermentation liquid of the 1,3-PD obtaining according to any one in claim 1-3 is carried out the first solid-liquid separation, obtain
Step to thalline underflow and fermented supernatant fluid；
2) from step 1) separate the fermented supernatant fluid that obtains and obtain 1,3- propylene glycol and contain organic acid potassium salt and inorganic salt
Solid step；
3) by step 1) the thalline underflow that obtains degraded, and obtain thalline and degrade the step of underflow；
4) by step 3) the described thalline degraded underflow that obtains carries out the second solid-liquid separation, and obtain thalline and degrade clear liquid and filtering residue
Step；
5) by step 2) solid containing organic acid potassium salt and inorganic salt that obtains and step 4) the described filtering residue that obtains mixes, uses
Step in solid organic fertilizer or the production of soil conditioner.
5. processing method according to claim 4, wherein, the side of described first solid-liquid separation and described second solid-liquid separation
Formula is identical or different, and the mode of described first solid-liquid separation is to filter and/or be centrifuged, and the mode of described second solid-liquid separation was
Filter and/or centrifugation；Preferably, in step 2) in by fermented supernatant fluid carry out detached method be carry out successively concentrating, desalination and
Rectification.
6. processing method according to claim 4, wherein, step 3) in degraded mode be acidolysis and/or enzymolysis；Described
Acidolysis includes being contacted described thalline underflow with acid, and described enzymolysis includes being contacted described thalline underflow with enzyme.
7. processing method according to claim 6, wherein, the acid that acidolysis is used is the concentrated sulphuric acid of 80-98 weight %, excellent
Selection of land, with respect to the thalline underflow of 100 weight portions, with H2SO4The consumption of the concentrated sulphuric acid of meter is 3-5 weight portion；It is highly preferred that institute
The condition stating acidolysis includes：Temperature is 60-120 DEG C, preferably 80-100 DEG C；Time is 10-60 hour, and preferably 26-48 is little
When.
8. processing method according to claim 6, wherein, digest used enzyme be protease it is preferable that with respect to
The thalline underflow of 1kg, the consumption of described protease is 500,000-500 ten thousand U；It is highly preferred that the condition of described enzymolysis includes：PH is
6.5-7.5, temperature is 40-60 DEG C, and the time is 24-48 hour.
9. the solid containing organic acid potassium salt and inorganic salt that the method described in any one in claim 4-8 obtains with
And application in preparation Water soluble fertilizer for the thalline degraded clear liquid.
10. a kind of preparation method of Water soluble fertilizer is it is characterised in that the method is included in any one in usage right requirement 4-8
The described solid containing organic acid potassium salt and inorganic salt and thalline degrade clear liquid as the preparing raw material of Water soluble fertilizer, according to water
Molten fertile factory formula preparation Water soluble fertilizer.
11. Water soluble fertilizer being prepared by the preparation method described in claim 10.
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| CN110981587A (en) * | 2019-11-28 | 2020-04-10 | 张家港美景荣化学工业有限公司 | Organic potassium fertilizer for drip irrigation and preparation method thereof |
| CN111019136A (en) * | 2019-12-25 | 2020-04-17 | 四川晨光博达新材料有限公司 | Environment-friendly method for producing MQ silicon resin |
| CN111116258A (en) * | 2019-11-28 | 2020-05-08 | 张家港美景荣化学工业有限公司 | Organic potassium composition containing polyhydric alcohol and preparation method thereof |
| CN112479868A (en) * | 2020-11-26 | 2021-03-12 | 广州国宏新材料有限公司 | Method and device for extracting organic acid from mixed salt obtained by separating fermentation liquor |
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| CN1460663A (en) * | 2003-05-20 | 2003-12-10 | 何孝金 | Preparation method of amino acid foliage fertilizer |
| CN103074217A (en) * | 2012-09-17 | 2013-05-01 | 贾平 | Composite flora and application of the same in biological bacterial liquid pulping process |
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| CN110981587A (en) * | 2019-11-28 | 2020-04-10 | 张家港美景荣化学工业有限公司 | Organic potassium fertilizer for drip irrigation and preparation method thereof |
| CN111116258A (en) * | 2019-11-28 | 2020-05-08 | 张家港美景荣化学工业有限公司 | Organic potassium composition containing polyhydric alcohol and preparation method thereof |
| CN111019136A (en) * | 2019-12-25 | 2020-04-17 | 四川晨光博达新材料有限公司 | Environment-friendly method for producing MQ silicon resin |
| CN112479868A (en) * | 2020-11-26 | 2021-03-12 | 广州国宏新材料有限公司 | Method and device for extracting organic acid from mixed salt obtained by separating fermentation liquor |
| CN114230380A (en) * | 2021-12-07 | 2022-03-25 | 山东睿智医药科技有限公司 | Utilization method of 7-aminocephalosporanic acid production waste |
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