CN105967995B - The method that embrane method prepares potassium formate - Google Patents
The method that embrane method prepares potassium formate Download PDFInfo
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- CN105967995B CN105967995B CN201610317731.8A CN201610317731A CN105967995B CN 105967995 B CN105967995 B CN 105967995B CN 201610317731 A CN201610317731 A CN 201610317731A CN 105967995 B CN105967995 B CN 105967995B
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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 invention provides a kind of method that embrane method prepares potassium formate, the method that the embrane method prepares potassium formate comprises the following steps：（A1）Sodium formate solution, solution of zinc sulfate are prepared respectively；（A2）The sodium formate solution and solution of zinc sulfate are mixed, filtering reacting liquid, obtains zinc formate；（A3）Potassium sulfate solution is configured, formic acid zinc solution is configured using above-mentioned zinc formate；（A4）Mix potassium sulfate solution and the formic acid zinc solution, mixed liquor is by film, and the monovalent ion in mixed liquor selectively passes through the film, and divalent ion is trapped；（A5）Permeate is concentrated, obtains potassium formate solutions.The present invention has low cost and other advantages.
Description
Technical field
The present invention relates to chemical field, and in particular to the improvement preparation method of potassium formate, more particularly to embrane method prepare formic acid
The method of potassium.
Background technology
At present, potassium formate production technology has following several because of raw material difference.
（1）Formic acid method
Generation potassium formate and water are reacted as raw material using formic acid and potassium hydroxide.
KOH+HCOOH——HCOOK+H2O
Generation potassium formate and water are reacted as raw material using formic acid and potassium carbonate.
K2CO3+2HCOO2——HCOOK+CO2+H2O
With formic acid and potassium hydroxide or potassium carbonate under certain condition directly reaction produce potassium formate, its technical process be by
Methanol and potassium hydroxide or potassium carbonate are added in reactor, are stirred, and controlling reaction temperature, can produce potassium formate, then
The potassium formate produced is sent into evaporator, evaporates in potassium formate and reacts the water of generation, and makes potassium formate be in molten, production is made
Product, can be for users to use.But expect that the potassium formate of higher degree also needs to supporting relative complex purifying technique, cost
Height, quality are relatively low.This method can be found in patent CN02110175.2.
（2）CO and KOH high-pressure synthesis methods
Using CO and potassium hydroxide as raw material, reaction generation potassium formate, without accessory substance.
CO+KOH——HCOOK
It is domestic at present mainly to produce potassium formate using CO methods.
Reach more than 90% CO gases with purity and potassium hydroxide solution that concentration is 3-5M, in pressure 1.0-1.7MPa,
Synthesized at 180 DEG C of temperature, obtain 6.6-7.5M potassium formate Synthesis liquid, product is obtained after last clarified, condensing crystallizing.The party
Method can utilize the waste gas containing CO, reduce environmental pollution, but potassium hydroxide cost is higher, and in order to produce required for reaction
Temperature and pressure condition needs to consume the substantial amounts of energy, belongs to energy intensive process.
Its technical process includes synthesis gas pressure-variable adsorption, synthetic reaction, evaporation and concentration, crystallization, centrifugation, dry packing
Deng processing step, reference can be made to patent CN00112814.0, CN03120711.1.
（3）It is legal in soda acid
The neutralisation includes legal and saleratus and formic acid in legal, potassium carbonate in potassium hydroxide and formic acid and formic acid
Neutralisation, these three methods have the advantages of technique is simple to operation, but the above method is intended to use with volatile corrosion
Formic acid as raw material, cause its high production cost, seriously polluted, high equipment cost and the vulnerable shortcoming of worker.
（4）Anion-cation exchange resin method
This solves the technique that potassium formate is prepared present in prior art generally there are cost high energy consumption
The problem of high.
Its step includes, using cationic ion-exchange resin as reaction carriers, by concentration be 15%-30% KCl solution with sun from
Sub-exchange resin swaps reaction, and the reaction time is 2-12 hours；Then cationic ion-exchange resin is cleaned, then with 20-60%'s
Sodium formate solution continues and cationic ion-exchange resin reacts through row, potassium formate solutions is finally obtained, after concentration and settlement is handled
Crystallization obtains qualified products.Energy consumption substantially reduces, and declines product cost indirectly.There is no harmful substance generation after reaction, do not have
Environmental pollution.Because caused potassium formate solutions almost do not have objectionable impurities, so purity is high after crystallization, it is superior in quality.But institute
The KCl solution for being 15%-30% with raw material, cost of material is higher, causes the cost of product to increase.This method can be found in patent
CN200610012740.2。
（5）Reaction method in formaldehyde, potassium hydroxide and isobutylaldehyde water
This method is 1 using mol ratio:1:1 to 3:2:1 formaldehyde, potassium hydroxide and isobutylaldehyde 0-100 DEG C, preferably
Reacted at a temperature of 30-70 DEG C in water.Reaction solution obtained by neutralizing evaporates for 4-6 and in the first step to pH value,
Thus obtain two-phase, an organic phase and an aqueous phase, the latter include the potassium formate of major part, then by the organic phase and
Aqueous phase separates, and after final evaporation occurs under the pressure of 0-0.1 bars of aqueous phase and at a temperature of 160-250 DEG C, obtains formic acid
The melt of potassium, add water and then filter, obtain the solution that formic acid potassium content is more than 99WT%, the WT% is based on anhydrous basic calculation.
The product purity that this method obtains is high, but due to having used organic solvent formaldehyde and isobutylaldehyde, easily causes environmental pollution.Should
Method can be found in patent CN200780050087.1.
（6）Seawater absorption method
This method is inhaled using seawater, bittern or other bittern containing potassiums as raw material by the use of natural clinoptilolite as inorganic ions
Attached dose is realized that potassium is enriched with, and by the raw material ejection in the adsorbent after adsorption saturation and then absorption is eluted with sodium formate solution with water
Agent, rich potassium liquid is made, then rich potassium liquid is centrifuged through twice evaporation concentration industrial 75% liquid potassium formate finished product is made, or
Liquid potassium formate is centrifugally separating to obtain solid formic acid potassium product through being concentrated by evaporation, cooling down knot again.Natural clinoptilolite is through elution
Reusable edible after regeneration, caused waste water and wet sodium formate can be recycled in course of reaction.Compared with prior art,
This method wide material sources, cost are cheap, environmentally friendly, but suitable for the abundant area of coastal and inland Brine resources.This method can be found in specially
Sharp CN201110234307.4.
The content of the invention
In order to solve the deficiency in above-mentioned prior art, the invention provides a kind of inexpensive embrane method to prepare formic acid
The method of potassium.
The purpose of the present invention is achieved through the following technical solutions：
A kind of method that embrane method prepares potassium formate, the method that the embrane method prepares potassium formate comprise the following steps：
（A1）Sodium formate solution, solution of zinc sulfate are prepared respectively；
（A2）Blend step（A1）Resulting sodium formate solution and solution of zinc sulfate, zinc formate precipitation is obtained, is filtered
To zinc formate；
（A3）Potassium sulfate solution is prepared, utilizes step（A2）Obtained zinc formate prepares formic acid zinc solution；
（A4）Blend step（A3）Resulting potassium sulfate solution and formic acid zinc solution, mixed liquor are concentrated using film,
Monovalent salt potassium formate in mixed liquor selectively passes through the film, and divalent salts zinc sulfate, which is trapped, is recycled back to step（A1）Set
With；
（A5）With film concentration step（A4）Permeate, obtain potassium formate solutions.
The method that potassium formate is prepared according to above-mentioned embrane method, step（A4）Used film is NF membrane.
The method that potassium formate is prepared according to above-mentioned embrane method, step（A5）Used film is reverse osmosis membrane.
The method that potassium formate is prepared according to above-mentioned embrane method, it is preferable that in step（A1）In, the preparation method of solution is：
Sodium formate, zinc sulfate are dissolved in 0-50 DEG C of water respectively.
The method that potassium formate is prepared according to above-mentioned embrane method, it is preferable that in step（A1）In, the sodium formate it is final dense
Spend for 20-60wt%, the ultimate density of zinc sulfate is 10-40wt%.
The method that potassium formate is prepared according to above-mentioned embrane method, it is preferable that in step（A4）In, mixed solution passes through NF membrane
Temperature be 10-80 DEG C, pressure 2-20MPa.
The method that potassium formate is prepared according to above-mentioned embrane method, it is preferable that in step（A5）In, with reverse osmosis membrane concentration step
（A4）Obtained permeate, operating temperature are 0-50 DEG C, pressure 0.5-20MPa.
The method that potassium formate is prepared according to above-mentioned embrane method, it is preferable that in step（A3）In, respectively by zinc formate, sulfuric acid
Potassium is dissolved in 20-80 DEG C of water.
The method that potassium formate is prepared according to above-mentioned embrane method, it is preferable that in step（A4）In, zinc formate and sulphur in mixed liquor
Sour potassium mol ratio is 1:1.
Compared with prior art, the device have the advantages that being：
Technique is simple, and course of reaction is easily controlled, and product purity is high, and cost of material is cheap, low cost.
Brief description of the drawings
Referring to the drawings, the disclosure will be easier to understand.Skilled addressee readily understands that be：This
A little accompanying drawings are used only for illustrating technical scheme, and are not intended to and protection scope of the present invention is construed as limiting.
Fig. 1 is the flow chart for the method that embrane method according to embodiments of the present invention prepares potassium formate.
Embodiment
Fig. 1 and following description describe the present invention optional embodiment with instruct those skilled in the art how to implement and
Reproduce the present invention.In order to instruct technical solution of the present invention, simplify or eliminate some conventional aspects.Those skilled in the art should
The understanding is derived from the modification of these embodiments or replacement will within the scope of the invention.Under those skilled in the art should understand that
Stating feature can combine to form multiple modifications of the present invention in a variety of ways.Thus, the invention is not limited in following optional
Embodiment, and only limited by claim and their equivalent.
Embodiment 1
Fig. 1 schematically illustrate the embodiment of the present invention 1 embrane method prepare potassium formate method flow chart, such as Fig. 1 institutes
Show, the method that the embrane method prepares potassium formate comprises the following steps：
（A1）Sodium formate, zinc sulfate are dissolved in 0-50 DEG C of water respectively, prepare sodium formate solution, solution of zinc sulfate,
The concentration of the sodium formate is 20-60wt%, and sulfuric acid zinc concentration is 10-40wt%；
（A2）Blend step（A1）The sodium formate solution and solution of zinc sulfate of gained, filtering reacting liquid, obtain zinc formate and sink
Form sediment；
（A3）Above-mentioned zinc formate, potassium sulfate are dissolved in 20-80 DEG C of water respectively, it is molten to prepare potassium sulfate solution, zinc formate
Liquid；
（A4）The potassium sulfate solution and formic acid zinc solution that blend step (A3) obtains, zinc formate and potassium sulfate mol ratio are 1:
1, mixed liquor is concentrated by NF membrane, and the monovalent ion in mixed liquor selectively passes through the film, and divalent ion is trapped；It is mixed
It is 10-80 DEG C to close the temperature that solution passes through film, pressure 2-20MPa；The zinc sulfate being rejected by is used for step（A1）In；
（A5）The nanofiltration permeate liquid that concentration step (A4) obtains, potassium formate solutions are obtained, concentration uses reverse osmosis membrane, works
Temperature is 0-50 DEG C, pressure 0.5-20MPa.
The method technique of the present embodiment is simple, and course of reaction is easily controlled, and cost of material is cheap, greatly reduces cost,
Final products purity is high, and after testing, whole purity reaches 97.6wt%；On cost, and conventional CO methods and ion-exchange-resin process
Compare, cost reduces by 70% or so and 40% or so respectively.
Embodiment 2
The application examples of according to embodiments of the present invention 1 preparation method, in the application examples, preparation method is specially：
（A1）Sodium formate, zinc sulfate are dissolved in 50 DEG C of water respectively, prepare sodium formate solution, solution of zinc sulfate, institute
The concentration for stating sodium formate is 60wt%, and sulfuric acid zinc concentration is 10wt%；
（A2）Blend step（A1）The sodium formate solution and solution of zinc sulfate of gained, filtering reacting liquid, obtain zinc formate and sink
Form sediment；
（A3）Above-mentioned zinc formate, potassium sulfate are dissolved in 80 DEG C of water respectively, prepare potassium sulfate solution, formic acid zinc solution；
（A4）Blend step（A3）The potassium sulfate solution and formic acid zinc solution of gained, zinc formate and potassium sulfate mol ratio are 1:
1, mixed liquor is concentrated by NF membrane, and the monovalent ion in mixed liquor selectively passes through the film, and divalent ion is cut
Stay；The temperature that mixed solution passes through film is 80 DEG C, pressure 12MPa；The zinc sulfate being rejected by is used for step（A1）In；
（A5）Concentration step（A4）The permeate of gained, obtains potassium formate solutions, and concentration uses reverse osmosis membrane, operating temperature
For 50 DEG C, pressure 10MPa.
The method technique of the present embodiment is simple, and course of reaction is easily controlled, and cost of material is cheap, greatly reduces cost,
Final products purity is high, and after testing, whole purity reaches 96.8wt%.
Embodiment 3
The application examples of according to embodiments of the present invention 1 preparation method, in the application examples, preparation method is specially：
（A1）Sodium formate, zinc sulfate are dissolved in 40 DEG C of water respectively, prepare sodium formate solution, solution of zinc sulfate, institute
The concentration for stating sodium formate is 40wt%, and sulfuric acid zinc concentration is 30wt%；
（A2）Blend step（A1）The sodium formate solution and solution of zinc sulfate of gained, filtering reacting liquid, obtain zinc formate and sink
Form sediment；
（A3）Above-mentioned zinc formate, potassium sulfate are dissolved in 50 DEG C of water respectively, prepare potassium sulfate solution, formic acid zinc solution；
（A4）Blend step（A3）The potassium sulfate solution and formic acid zinc solution of gained, zinc formate and potassium sulfate mol ratio are 1:
1, mixed liquor is concentrated by NF membrane, and the monovalent ion in mixed liquor selectively passes through the film, and divalent ion is cut
Stay；The temperature that mixed solution passes through film is 30 DEG C, pressure 2MPa；The zinc sulfate being rejected by is used for step（A1）In；
（A5）Concentration step（A4）The permeate of gained, obtains potassium formate solutions, and concentration uses reverse osmosis membrane, operating temperature
For 30 DEG C, pressure 2MPa.
After testing, whole purity reaches 96.9wt% to the method final products of the present embodiment.
Above-described embodiment is only the exemplary concrete numerical value for giving the reaction condition in preparation process, such as concentration, temperature
Degree, pressure etc., other numerical value in above range are can also be certainly, such as other numerical value in temperature, pressure, concentration ranges,
And the technique effect similar with above-described embodiment can be reached.As those skilled in the art, other numbers in above range
The specific embodiment and implementation result of value are it is contemplated that arrive, and are also that by the object of the invention.
Claims (7)
1. a kind of method that embrane method prepares potassium formate, the method that the embrane method prepares potassium formate comprises the following steps successively：
（A1）Sodium formate solution, solution of zinc sulfate are prepared respectively；
（A2）Blend step（A1）Resulting sodium formate solution and solution of zinc sulfate, zinc formate precipitation is obtained, is filtrated to get first
Sour zinc；
（A3）Potassium sulfate solution is prepared, utilizes step（A2）Obtained zinc formate prepares formic acid zinc solution；
（A4）Blend step（A3）Resulting potassium sulfate solution and formic acid zinc solution, mixed liquor are concentrated using film, mixing
Monovalent salt potassium formate in liquid selectively passes through the film, and divalent salts zinc sulfate, which is trapped, is recycled back to step（A1）Apply mechanically, walk
Suddenly（A4）Used film is NF membrane；
（A5）With film concentration step（A4）Permeate, obtain potassium formate solutions, step（A5）Used film is reverse osmosis membrane.
2. the method that embrane method according to claim 1 prepares potassium formate, it is characterised in that：In step（A1）In, solution
Preparation method is：Sodium formate, zinc sulfate are dissolved in 0-50 DEG C of water respectively.
3. the method that embrane method according to claim 1 prepares potassium formate, it is characterised in that：In step（A1）In, the first
The ultimate density of sour sodium is 20-60wt%, and the ultimate density of zinc sulfate is 10-40wt%.
4. the method that embrane method according to claim 1 prepares potassium formate, it is characterised in that：In step（A4）In, mixing is molten
The temperature that liquid passes through NF membrane is 10-80 DEG C, pressure 2-20MPa.
5. the method that embrane method according to claim 1 prepares potassium formate, it is characterised in that：In step（A5）In, use reverse osmosis
Permeable membrane concentration step（A4）Obtained permeate, operating temperature are 0-50 DEG C, pressure 0.5-20MPa.
6. the method that embrane method according to claim 1 prepares potassium formate, it is characterised in that：In step（A3）In, respectively will
Zinc formate, potassium sulfate are dissolved in 20-80 DEG C of water.
7. the method that embrane method according to claim 1 prepares potassium formate, it is characterised in that：In step（A4）In, mixed liquor
Middle zinc formate and potassium sulfate mol ratio is 1:1.
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