CN105566093B - A kind of method of continuous manufacture potassium diformate - Google Patents
A kind of method of continuous manufacture potassium diformate Download PDFInfo
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- CN105566093B CN105566093B CN201610084063.9A CN201610084063A CN105566093B CN 105566093 B CN105566093 B CN 105566093B CN 201610084063 A CN201610084063 A CN 201610084063A CN 105566093 B CN105566093 B CN 105566093B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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Abstract
The present invention relates to a kind of method of continuous manufacture potassium diformate.It is characterized in that using carbon dioxide as conditioning agent, formic acid and the method that potassium hydroxide is raw material one-step synthesis potassium diformate, discharged without gas in whole course of reaction.In production process of the present invention, by solid potassium hydroxide wiring solution-forming, quantitative potassium hydroxide solution is taken, carbon dioxide is passed through to it and is prepared into potassium hydroxide and potassium carbonate mixed solution；By the potassium ion amount in mixed solution and formic acid in molar ratio 1:2.0~3.0 add, stirring reaction；Reaction temperature is maintained at 55~75 DEG C in course of reaction；Formic acid in carbon dioxide recovery and the potassium hydroxide solution with being newly passed through caused by mixed solution reaction with reacting；The product of initial reaction is taken out and continues secondary response, reaction temperature is maintained at 55~75 DEG C, and the secondary response time is maintained at 1~2.5h.Whole gentle controllable, the no discharge of reaction, can continuous production；It is adapted to large-scale industrial production.
Description
Technical field
The present invention relates to a kind of method for manufacturing potassium diformate, especially using carbon dioxide as conditioning agent, make whole
A kind of individual gentle controllable synthetic method of reaction.
Background technology
Potassium diformate is a kind of new feed addictive, as the substitute of antibiotic growth accelerator, early in 2001
Potassium diformate just is ratified to use by European Union, is that the first non-antibiotic for being used for substitute antibiotics growth accelerator of European Union's approval is raised
Feed additives.In order to ensure food safety, since 2006, European Union will completely forbid used auxins antibiosis in feed
Element is used as feed addictive.Potassium diformate is a kind of acidulant, compared to the acidulants such as formic acid, potassium diformate convenient transportation, corrosion
Property low irritant is small.Research finds that potassium diformate can improve livestock and poultry feed intake as feed addictive；Adjust soda acid inside enteron aisle
Environment, intestines and stomach pH value is reduced, there is the somatotrophic effect of antibacterial；Suppress enteric microorganism, strengthen animal immune performance；Improve stomach
The activity of middle digestive ferment, improve the digestibility and absorptivity of nutrient；And its good palatability is that antibiotic promotees with security
What growth stimulator can not compare.It should further be appreciated that potassium diformate will not have remnants again as feed addictive in animal body, also not
The drug resistance of bacterium can be caused, is reasonable product of the substitute antibiotics as feed addictive.
Potassium diformate is a kind of acylate, and it is the dimer for passing through hydrogen bond association by formic acid and potassium formate.Close at present
Method into potassium diformate mainly has：Formic acid-potassium oxide method, formic acid-potassium formate method, formic acid-potassium carbonate method, formic acid-hydrogen
Potassium oxide method, methyl formate-potassium carbonate or potassium hydroxide method.
Chinese invention patent CN1844074 describes the method that potassium diformate is prepared using formic acid and potassium oxide as raw material, but
Because raw materials used potassium oxide source is less in this method, price is high, and potassium oxide can not be placed directly within air and preserve, and cause
This method cost remains high, and has been limited in terms of commercial Application.U.S. patent Nos US6137005 is described by formic acid and first
The method that sour nak response prepares potassium diformate, although this method reaction yield is higher, due to reaction raw materials potassium formate price
It is higher, cause the method to be difficult to industrial applications always.Chinese patent CN1428325 describes solid carbonic acid potassium and formic acid
The method of synthesizing potassium diformate is reacted, but products obtained therefrom yield is relatively low, only 50% or so.Chinese invention patent CNl704394 is public
A kind of technique by formic acid solution and solution of potassium carbonate reaction production potassium diformate has been opened, has greatly reduced the violent journey of reaction
Degree, but the process problem of reaction generation great amount of carbon dioxide gas is not considered, industrial production is limited to a certain extent
The application of aspect.Formic acid prepares potassium diformate with potassium hydroxide solid or potassium hydroxide solution reaction, although potassium hydroxide price
It is not high, source is wide, but the reaction is exothermic reaction, and reaction is violent, and reaction temperature is difficult to control.U.S. patent Nos
US20050010067 discloses a kind of technique that potassium diformate is prepared by methyl formate, water and potassium carbonate/potassium hydroxide reaction,
Secondary method combines formic acid industrial manufacturing process so that this method can produce fairly largely.But the course of reaction time
Long, complex process considerably increases equipment investment and loss, it is necessary to increase the separating step of process product methanol.
The content of the invention
It is an object of the invention to using potassium hydroxide and formic acid as raw material, carbon dioxide is conditioning agent, continuous production diformazan
The method of sour potassium.A kind of method of continuous manufacture potassium diformate, it is characterised in that：
First reactor deposit potassium hydroxide solution, by carbon dioxide be passed through first reactor be prepared into mixing it is molten
Liquid；Mixed solution and formic acid are delivered to second reactor by delivery pump, and the control of its mol ratio is mixed solution potassium ion：Formic acid=
1:2.0~3.0；
Second reactor reaction temperature is maintained at 60~65 DEG C in course of reaction；
Primary product in second reactor is pumped to piston flow reactor and is carried out secondary response, secondary counter by conveying
Temperature is answered to be maintained at 55~75 DEG C, the secondary response time is maintained at 1~2.5h, and reaction is evaporated under reduced pressure after terminating to reaction mixture,
Normal temperature is stood, and is filtered, and is dried, is obtained potassium diformate product；
Continue to provide potassium hydroxide solution, the carbon dioxide produced in second reactor to first reactor in course of reaction
Gas is passed through first reactor by pipeline and recycled, and carbon dioxide is as the conditioning agent entirely reacted.
Further, the molar ratio of mixed solution potassium hydroxide and potassium carbonate is 0.4/0.6~0.6/ in first reactor
0.4。
Further, the molar ratio of mixed solution potassium hydroxide and potassium carbonate is 0.667~1.5 in first reactor.
Further, mol ratio potassium ion in second reactor mixed solution：Formic acid is 1:2.4~2.6.
Further, for temperature at 60~65 DEG C, the secondary response time is 1.5~2h during secondary response.
A) first reactor is prepared for mixed solution, and second reactor is that formic acid reacts with mixed solution；
B) first reactor connects second reactor by pipeline, and the carbon dioxide of generation is reacted in second reactor
First reactor is back to by pipeline, second reactor connects piston flow reactor by pipeline；
C) solution is continuously added to each reactor by delivery pump, and second reactor is controlled by controlling the flow of delivery pump
The mol ratio of middle formic acid and the potassium ion in mixed solution；
D part potassium hydroxide solution and the carbon dioxide gas precursor reactant with being passed through first) are put into first reactor, it is remaining
Solution is continuously added to first reactor with returning to the carbon dioxide gas precursor reactant of the reactor by delivery pump.Whole production process
Middle carbon dioxide recycles as growth regulation.
E by the primary product in second reactor by delivery pump to piston flow reactor while) reaction, to last production
Thing solution is evaporated under reduced pressure, normal temperature is stood, filter, drying and grinding obtains potassium diformate product.
Technical scheme is as follows：
1) a certain amount of carbon dioxide is passed through in the potassium hydroxide solution of first reactor and is prepared into mixed solution, made just
The ratio of potassium hydroxide and potassium carbonate is 0.4/0.6~0.6/0.4 (0.667~1.5) in beginning mixed solution.
2) carbon dioxide as conditioning agent, is recycled, discharged in whole course of reaction without gas in course of reaction；
3) control conveying pump discharge, it is 1 to make in second reactor the mol ratio of potassium ion and formic acid in mixed solution:2.4
~2.6；
4) at 60~65 DEG C, the control of second reactor reaction time exists the control of the reaction temperature of reactor second in course of reaction
2-3min；
5) initial product in second reactor being continued into secondary response, secondary response temperature is maintained at 60~65 DEG C,
The secondary response time is maintained at 1.5~2h.
Compared with existing synthetic technology, the present invention is using potassium hydroxide and potassium carbonate mixed solution and formic acid solution
Directly react, conditioning agent of the carbon dioxide as the reaction in course of reaction.Potassium diformate is prepared using mixed solution, by
Formic acid-potassium hydroxide method is compared to, the technique as reaction control agent using carbon dioxide in the course of reaction
The severe degree entirely reacted is significantly reduced, reaction is gentle controllable；Formic acid and the carbon dioxide gas of mixed solution reaction generation
Body circulation utilizes, and is compared to formic acid-potassium carbonate method, and caused gas is less in the course of reaction, and gas circulation utilizes
Make the discharge without greenhouse gases in whole production process.The continuity of course of reaction shows as delivery pump offer power and persistently adds original
Material, and initial reaction product is taken out, carbon dioxide caused by first set reaction and the potassium hydroxide solution being newly passed through react again
Secondary formation mixed solution, while secondary response is carried out to primary product, and so on, whole production process links up free of discontinuities.Should
Reaction unit is simple, and safety is easy to operate, with short production cycle, manpower financial capacity is saved, suitable for large-scale industrial production.
Brief description of the drawings
Fig. 1 is production technology figure
1- potassium hydroxide solution imports；2- potassium hydroxide solutions export；3- mixed solution imports；4- mixed solutions export；
The circulation of 5- carbon dioxides；6- formic acid imports；7- formic acid exports；8- first batch of newly-designed products imports；9- firsts batch of newly-designed products export；10-
Final products
REACT：Reactor (stirring) RPLUG：Piston flow reactor
Embodiment
Embodiment 1：Potassium hydroxide solid 15.73g (82%) is weighed, distilled water is added and is prepared into potassium hydroxide solution, take
The half of protohydrogen potassium oxide solution is put into first reactor, and 0.04mol carbon dioxides are passed through into potassium hydroxide solution
Mixed solution is formed, it is 1.5 to control the mol ratio of potassium hydroxide and potassium carbonate in mixed solution.With delivery pump respectively by 30ml first
(formic acid mole is 2.6 with potassium ion mol ratio to acid:1) and mixed solution adds stirring reaction in second reactor, reaction temperature
For 60 DEG C, while reaction, remaining potassium hydroxide solution is continually fed into first reactor, two minutes or so rear continuously will
Product is extracted out in second reactor, reacts 1h in the environment of being 60 DEG C in temperature, reaction mixture is evaporated under reduced pressure after stopping reaction,
Stand under normal temperature, cool down, filtered after crystallization, dried in 60 DEG C of air dry oven, it is levigate after product drying, obtain dioctyl phthalate
Potassium 26.75g, product yield 89.52%.
Embodiment 2：Using the charge ratio of example 1, it is 0.05mol to be passed through the carbon dioxide gas scale of construction, is controlled in mixed solution
The mol ratio of potassium hydroxide and potassium carbonate is 0.80, and reaction temperature is 55 DEG C, reaction time 2.5h.Remaining condition and step are same
Example 1, product obtain potassium diformate 25.75g, product yield 86.17% after drying.
Embodiment 3：Potassium hydroxide solid 17.04g is weighed, (formic acid mole is 2.4 with potassium ion mol ratio to formic acid 30ml:
1) add distilled water and be prepared into potassium hydroxide solution, it is 0.05mol to be passed through the carbon dioxide gas scale of construction, potassium hydroxide in mixed solution
Mol ratio with potassium carbonate is 1, and reaction temperature is 65 DEG C, reaction time 2h, and with example 1, product is done for remaining condition and step
27.56g, yield 86.09% are obtained after dry.
Embodiment 4：Using the charge ratio of example 3, it is 0.045mol to be passed through the carbon dioxide gas scale of construction, hydrogen-oxygen in mixed solution
The mol ratio for changing potassium and potassium carbonate is 1.33.Reaction temperature is 60 DEG C, reaction time 2.5h, remaining condition and the same example of step
1, product obtains 26.92g, product yield 84.09% after drying.
Claims (2)
- A kind of 1. method of continuous manufacture potassium diformate, it is characterised in that：First reactor deposits potassium hydroxide solution, and carbon dioxide is passed through into first reactor and is prepared into mixed solution；It is mixed Close solution and formic acid is delivered to second reactor by delivery pump, the control of its mol ratio is mixed solution potassium ion：Formic acid=1:2.0 ~3.0；Second reactor reaction temperature is maintained at 60~65 DEG C in course of reaction；Primary product in second reactor is pumped to piston flow reactor and is carried out secondary response, secondary response temperature by conveying Degree is maintained at 55~75 DEG C, and the secondary response time is maintained at 1~2.5h, and reaction is evaporated under reduced pressure after terminating to reaction mixture, normal temperature Stand, filter, dry, obtain potassium diformate product；Continue to provide potassium hydroxide solution, the carbon dioxide produced in second reactor to first reactor in course of reaction First reactor is passed through by pipeline to recycle, carbon dioxide is as the conditioning agent entirely reacted；Wherein, the molar ratio of mixed solution potassium hydroxide and potassium carbonate is 0.4/0.6~0.6/0.4 in first reactor；The The molar ratio of mixed solution potassium hydroxide and potassium carbonate is 0.667~1.5 in one reactor；Product is in piston flow reactor Secondary response is carried out, for temperature at 60~65 DEG C, the secondary response time is 1.5~2h during secondary response.
- 2. the method as described in claim 1, it is characterised in that：Mol ratio potassium ion in second reactor mixed solution：Formic acid For 1:2.4~2.6.
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| CN201610084063.9A CN105566093B (en) | 2016-02-06 | 2016-02-06 | A kind of method of continuous manufacture potassium diformate |
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| CN201610084063.9A CN105566093B (en) | 2016-02-06 | 2016-02-06 | A kind of method of continuous manufacture potassium diformate |
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| NO300038B1 (en) * | 1995-05-12 | 1997-03-24 | Norsk Hydro As | Process for the preparation of products containing double salts of formic acid |
| CN1428325A (en) * | 2001-12-27 | 2003-07-09 | 徐林坤 | Production method of potassium diformate |
| CN101125809B (en) * | 2007-07-31 | 2010-05-19 | 厦门大学 | Solvent-free heating-free method for synthesizing potassium diformate |
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