CN104418722A - Technique for concentrating diluted formic acid and co-generating monopotassium phosphate - Google Patents
Technique for concentrating diluted formic acid and co-generating monopotassium phosphate Download PDFInfo
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- CN104418722A CN104418722A CN201310409510.XA CN201310409510A CN104418722A CN 104418722 A CN104418722 A CN 104418722A CN 201310409510 A CN201310409510 A CN 201310409510A CN 104418722 A CN104418722 A CN 104418722A
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- formic acid
- potassium
- primary phosphate
- technique
- evaporation
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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
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/30—Alkali metal phosphates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/30—Alkali metal phosphates
- C01B25/308—Methods for converting an alkali metal orthophosphate into another one; Purification; Decolorasing; Dehydrating; Drying
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
Abstract
The invention discloses a technique for concentrating diluted formic acid and co-generating monopotassium phosphate, and aims at solving the problems that the prior art is overlarge in investment, relatively high in energy consumption, inconvenient to operate, difficult to popularize and apply and the like. The technique is characterized by comprising the following steps: firstly, preparing potassium formate solid from diluted formic acid by using potassium hydroxide, dissolving the formate solid and polyphosphoric acid into a high-concentration formic acid solvent; carrying out liquid-phase replacement reaction; and preparing monopotassium phosphate and high-concentration formic acid through operations such as evaporating, cooling, crystallizing, filtering, drying and condensing. The technique has the advantages of simple process, high formic acid yield, high formic acid product concentration and the like; meanwhile, the monopotassium phosphate byproduct is obtained; the environmental pollution caused by direct emission of production wastewater in chemical enterprises is solved; the production benefits of enterprises are improved; and the technique has wide popularization and application value.
Description
One, technical field
The invention belongs to chemical enterprise waste water treatment process, relating in particular to the processing method that a kind of dilute formic acid aqueous solution to producing in the process of producing product such as metronidazole carries out concentrated co-production potassium primary phosphate.
Two, background technology
Metronidazole is the choice drug of anaerobe resistant.The method of the synthesis metronidazole reported at present is: be dissolved in formic acid by 2-5-nitro imidazole, successively add oxyethane at 30-40 DEG C, and adds sulfuric acid in the middle of reinforced.Finish, reaction 1h.Dilute formic acid is reclaimed in evaporation, is cooled to 10 DEG C after being dissolved in water, and filter, filtrate is adjusted to pH=10 with potassium hydroxide solution, places cooling, crystallization, filters, is washed to weakly acidic pH.Use water recrystallization, activated carbon decolorizing, obtain metronidazole.
The dilute formic acid that above-mentioned evaporation is reclaimed is the aqueous formic acid of about 30-80%.In Industrial processes, especially formic acid does in industrial solvent use procedure, can produce a large amount of dilute formic acid solution.The method of purifying formic acid had bibliographical information in the past.Nineteen twenty-nine French Patent report Tetra hydro Phthalic anhydride and water-containing formic acid back flow reaction prepare anhydrous formic acid; English Patent in 1948 is reported in water-containing formic acid and adds new entrainer separating formic; Chinese patent report in 1992, utilizes SOCl
2purification dilute formic acid; Chinese bibliographical information boron trioxide method of purification in 2006.
The investment that aforesaid method has is excessive, and the operation that is higher, that have of some energy consumptions is inconvenient, does not all apply.
Three, summary of the invention
The object of the invention is to reclaim formic acid Problems existing in the production processes such as existing metronidazole, the processing method of the dilute formic acid coproduction potassium primary phosphate produced in a kind of concentrated chemical industry enterprise production process is provided.
The technical solution adopted in the present invention is: first utilize potassium hydroxide that dilute formic acid is made potassium formiate solid; Relief potassium formiate solid and polyphosphoric acid are all dissolved in concentration formic acid and high solvent, carry out liquid phase replacement(metathesis)reaction, by operations such as evaporation, cooling, crystallization, filtration, drying and condensations, and obtained potassium primary phosphate and concentration formic acid and high.First potassium hydroxide is added in the dilute formic acid aqueous solution produced in the process of producing product such as metronidazole, then removed by evaporation moisture content, obtain potassium formiate solid.In the reactor of band cooling and reflux device, the formic acid first adding more than 85% makes solvent, then adds anhydrous formic acid potassium and peroxophosphoric acid or polymer phosphate in phosphorus, the equimolar ratio of potassium, stirs, is heated to 70 to 100 DEG C, makes the formic acid saturated solution of potassium primary phosphate.Then, stop heating, naturally cooling, adds crystal seed, and control speed stirs, and crystallization is filtered, dry potassium primary phosphate granular crystals product.Replace the formic acid of above-mentioned more than 85% to make solvent a part for above-mentioned filter liquor, repeatedly repeat aforesaid operations; By another part filtrate heating evaporation formic acid, until when having potassium primary phosphate solid to separate out at the bottom of still, stop evaporation, naturally cooling, adds crystal seed, and control speed stirs, crystallization, filtration, dry potassium primary phosphate granular crystals product.By the formic acid vapor condensation that above-mentioned drying and evaporation produce, the formic acid product of 85% to 100% can be obtained.
The present invention is compared with prior art: neutralized by formic acid dilute solution potassium hydroxide owing to adopting, make potassium formate solutions, evaporation dewaters, and obtains anhydrous formic acid potassium, solves formic acid and water boiling point is close, the problem of the difficulty that dewaters.Again owing to making solvent with product formic acid, utilize the characteristic of potassium primary phosphate solubility with temperature change in formic acid, potassium primary phosphate and concentration formic acid and high is obtained by liquid reactive method, overcome traditional liquid-solid phase reaction production technique, mix uneven, reaction incomplete sum noncrystal potassium primary phosphate parcel formic acid, the problems such as separation difficulty, have that technique is simple, carboxylic acid Yield is high and formic acid product concentration advantages of higher, there is application value widely.
Four, embodiment
Below by embodiment, the present invention is further illustrated.
Embodiment 1:
Added in 3000ml glass reaction still by 50% (quality) potassium hydroxide aqueous solution 1.12kg and 40% (quality) aqueous formic acid 1.15kg, heating evaporation removes moisture content, obtains potassium formiate solid.Then, add the industrial formic acid of appropriate more than 85%, stir, heat, reflux.After being warmed up to 100 DEG C, reflux in limit, limit slowly drips the industrial formic acid of more than 85%, in time only having trace solid at the bottom of still, stops heating.
Add in 5000ml glass reaction still by 85% (quality) industrial phosphoric acid 1.15kg, heating 150-300 DEG C, normal pressure or reduction vaporization remove moisture content, obtain polyphosphoric acid.
Saturated liquid rotating in above-mentioned 3000ml glass reaction still moved on in above-mentioned 5000ml polyphosphoric acid glass reaction still, stir, heat, reflux.After being warmed up to 100 DEG C, reflux in limit, limit slowly drips the industrial formic acid of more than 85%, and in time only having trace solid at the bottom of still, stop heating, naturally cooling, adds crystal seed, and control speed stirs, and crystallization is filtered, dry potassium primary phosphate granular crystals product.
Replace the formic acid of above-mentioned more than 85% to make solvent a part for above-mentioned filter liquor, repeatedly repeat aforesaid operations; By another part filtrate heating evaporation formic acid, until when having potassium primary phosphate to have a small amount of solid to separate out at the bottom of still, stop evaporation, naturally cooling, adds crystal seed, and control speed stirs, crystallization, filtration, dry potassium primary phosphate granular crystals product.By the formic acid vapor condensation that above-mentioned drying and evaporation produce, obtain the formic acid product of 85% to 100%.
Embodiment 2:
Added in 3000ml glass reaction still by 50% (quality) potassium hydroxide aqueous solution 1.12kg and 40% (quality) aqueous formic acid 1.15kg, heating evaporation removes moisture content, obtains potassium formiate solid.
Add in 5000ml glass reaction still by 85% (quality) industrial phosphoric acid 1.15kg, heating 150-300 DEG C, normal pressure or reduction vaporization remove moisture content, obtain polyphosphoric acid.
By potassium formiate solid transfer in above-mentioned 3000ml glass reaction still in the 5000ml glass reaction still having polyphosphoric acid, and add the industrial formic acid of appropriate more than 85%, stir, heat, reflux.After being warmed up to 100 DEG C, reflux in limit, limit slowly drips the industrial formic acid of more than 85%, and in time only having trace solid at the bottom of still, stop heating, naturally cooling, adds crystal seed, and control speed stirs, and crystallization is filtered, dry potassium primary phosphate granular crystals product.
Replace the formic acid of above-mentioned more than 85% to make solvent a part for above-mentioned filter liquor, repeatedly repeat aforesaid operations; By another part filtrate heating evaporation formic acid, until when having potassium primary phosphate to have a small amount of solid to separate out at the bottom of still, stop evaporation, naturally cooling, adds crystal seed, and control speed stirs,
Crystallization, filtration, dry potassium primary phosphate granular crystals product.By the formic acid vapor condensation that above-mentioned drying and evaporation produce, obtain the formic acid product of 85% to 100%.
Claims (1)
1. the processing method of a concentrated dilute formic acid coproduction potassium primary phosphate, it is characterized in that: first utilize potassium hydroxide that dilute formic acid is made potassium formiate solid, relief potassium formiate solid and polyphosphoric acid are all dissolved in concentration formic acid and high solvent, carry out liquid phase replacement(metathesis)reaction, by operations such as evaporation, cooling, crystallization, filtration, drying and condensations, obtained potassium primary phosphate and concentration formic acid and high, concrete steps are:
(1) added by potassium hydroxide in the dilute formic acid aqueous solution produced in Production in Chemical Plant process, then removed by evaporation moisture content, obtains potassium formiate solid;
(2) in the reactor of band cooling and reflux device, the formic acid first adding more than 85% makes solvent, then adds anhydrous formic acid potassium and peroxophosphoric acid or polymer phosphate in the ratio of phosphorus, potassium mole, stirs, be heated to 70 to 100 DEG C, make the formic acid saturated solution of potassium primary phosphate;
(3) naturally cooling, adds crystal seed, and control speed stirs, crystallization, filtration, dry potassium primary phosphate granular crystals product;
(4) formic acid of above-mentioned more than 85% is replaced to make solvent, repeatedly repeating step 2 and step 3 part for above-mentioned filter liquor;
(5) by another part filtrate heating evaporation formic acid, until when having potassium primary phosphate solid to separate out at the bottom of still, stop evaporation, naturally cooling, adds crystal seed, and control speed stirs, crystallization, filtration, dry potassium primary phosphate granular crystals product;
(6) by the formic acid vapor condensation that above-mentioned drying and evaporation produce, the formic acid product of 85% to 100% can be obtained.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310409510.XA CN104418722A (en) | 2013-09-03 | 2013-09-03 | Technique for concentrating diluted formic acid and co-generating monopotassium phosphate |
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| CN201310409510.XA CN104418722A (en) | 2013-09-03 | 2013-09-03 | Technique for concentrating diluted formic acid and co-generating monopotassium phosphate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108751153A (en) * | 2018-05-25 | 2018-11-06 | 百合花集团股份有限公司 | A method of preparing potassium dihydrogen phosphate using quinacridone by-product waste phosphoric acid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1443746A (en) * | 2002-03-13 | 2003-09-24 | 肥城阿斯德化工有限公司 | Method for producing potassium formate |
| CN101462943A (en) * | 2009-01-08 | 2009-06-24 | 曹勇 | Method for preparing oxalate with co-production products oxalic acid and dihydric phosphate by continuous dehydrogenation of formate |
| CN101475463A (en) * | 2009-01-21 | 2009-07-08 | 曹勇 | Method for coproduction of high purity aminic acid and acid sodium phosphate by reaction of calcium formate and peroxyphosphoric acid |
| US20110319658A1 (en) * | 2010-06-29 | 2011-12-29 | Basf Se | Process for preparing formic acid by reaction of carbon dioxide with hydrogen |
-
2013
- 2013-09-03 CN CN201310409510.XA patent/CN104418722A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1443746A (en) * | 2002-03-13 | 2003-09-24 | 肥城阿斯德化工有限公司 | Method for producing potassium formate |
| CN101462943A (en) * | 2009-01-08 | 2009-06-24 | 曹勇 | Method for preparing oxalate with co-production products oxalic acid and dihydric phosphate by continuous dehydrogenation of formate |
| CN101475463A (en) * | 2009-01-21 | 2009-07-08 | 曹勇 | Method for coproduction of high purity aminic acid and acid sodium phosphate by reaction of calcium formate and peroxyphosphoric acid |
| US20110319658A1 (en) * | 2010-06-29 | 2011-12-29 | Basf Se | Process for preparing formic acid by reaction of carbon dioxide with hydrogen |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108751153A (en) * | 2018-05-25 | 2018-11-06 | 百合花集团股份有限公司 | A method of preparing potassium dihydrogen phosphate using quinacridone by-product waste phosphoric acid |
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Application publication date: 20150318 |