CN101607879A - A kind of method of producing concentration formic acid and high and polymer phosphate sodium salt with the mixing acid acidifying sodium formate - Google Patents
A kind of method of producing concentration formic acid and high and polymer phosphate sodium salt with the mixing acid acidifying sodium formate Download PDFInfo
- Publication number
- CN101607879A CN101607879A CNA2009100946830A CN200910094683A CN101607879A CN 101607879 A CN101607879 A CN 101607879A CN A2009100946830 A CNA2009100946830 A CN A2009100946830A CN 200910094683 A CN200910094683 A CN 200910094683A CN 101607879 A CN101607879 A CN 101607879A
- Authority
- CN
- China
- Prior art keywords
- acid
- formic acid
- sodium
- mixing
- sodium salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of method of producing concentration formic acid and high and polymer phosphate sodium salt with the mixing acid acidifying sodium formate relates to the new manufacturing method that concentration formic acid and high and polymer phosphate sodium salt are produced in a kind of mixing acid reaction that utilizes sodium formiate that the carbon monoxide in the source such as yellow phosphoric tail gas makes and polyphosphoric acid and formic acid.Step of the present invention is: (1) drops into formic acid and polyphosphoric acid in the complex acid groove, the ratio of formic acid and polyphosphoric acid quality is 1: 5-1: 1, be stirred into mixing acid, and formic acid concn is more than 90%, and polyphosphoric acid concentration is with P
2O
5Count 72.4%-86.95%; (2) will react in sodium formiate and the mixing acid adding reactor, the mol ratio of sodium formiate and polyphosphoric acid is 1: 1-1: 2; (3) evaporation, separation obtain formic acid and compound phosphoric acid sodium salt; (4) the compound phosphoric acid sodium salt is allocated the various polymer phosphate sodium salts of back preparation with alkali.Method of the present invention can make production operation carry out smoothly, and technical process is simple, produces the formic acid concn height, cost is low.
Description
Technical field
The present invention relates to a kind of mixing acid reaction that utilizes sodium formiate that the carbon monoxide in the source such as yellow phosphoric tail gas makes and polyphosphoric acid and formic acid and produce the new manufacturing method of concentration formic acid and high and polymer phosphate sodium salt.
Background technology
The phosphorus production enterprise in the Yunnan Province and the whole nation is more at present, except some large-scale enterprises, also has a lot of dispersive midget plant, these phosphorus production enterprises are because the difference of its state of the art, yellow phosphoric tail gas utilize degree also different, generally speaking large-lot producer's utilization ratio is higher relatively, small business's utilization ratio is relatively low, but overall utilization ratio is all lower, and a large amount of CO (carbon monoxide converter) gas in the yellow phosphoric tail gas still are drained in the atmosphere by the incendiary mode.The source of pollution of dispersive are not one by one so administered, and the harm that whole atmospheric environment is caused also can not look down upon.At present technical effective, economically feasible method is that preparing sodium formiate with alkali reaction after the purification of yellow phosphoric tail gas process, sodium formiate carries out making formic acid product and sodium salt product after the acidifying.So both can comprehensive regulation yellow phosphoric tail gas, can concentrate acidifying carry out large-scale production sodium formiate again, the yellow phosphoric tail gas that is unfavorable for remote conveying is become be convenient to carry the sodium formiate solid, not only administered environmental pollution but also increase the business economic benefit.
At present sodium formiate carries out that acidifying makes the formic acid product and the sodium salt method for product mainly contains two kinds, a kind of is to prepare formic acid and sodium sulfate with the sulfuric acid acidation sodium formiate, the main drawback of these class methods is: the formic acid concn of production is generally below 85%, produce the by-product sodium sulfate (claiming saltcake again) of low value simultaneously, economic benefit is relatively poor; Another kind is to prepare formic acid and sodium phosphate salt with peroxophosphoric acid (or phosphoric acid) acidifying sodium formate, and the main drawback of this method is: the formic acid concn of being produced is low, and the formic acid rate of recovery is low, produces to be difficult to smooth and easy carrying out, and is difficult to realize serialization production; If adopt the phosphoric acid acidifying, the formic acid concn of being produced does not reach the national standard requirement, if adopt peroxophosphoric acid production, the formic acid yield of recovery is low, long reaction time, and reaction is difficult to carry out smoothly, is difficult to realize serialization production.
Be entitled as in the elaboration of " method of producing the various sodium phosphate salts of formic acid coproduction with the peroxophosphoric acid acidifying sodium formate " total P of its used acid in prior art patent 97103209.2
2O
5Scope be 69.6%-86.9%, corresponding H
3PO
4Content range be about 96%-120%, under such concentration, do not return formic acid or only throw and return a spot of formic acid if do not throw at normal temperature or below 45 ℃, or when below the boiling temperature of formic acid, carrying out, realize that the stirring reaction described in the literary composition is unpractical, with not mentioning the amount of returning formic acid of throwing in the eight-legged essay.In addition, in this patent, only mentioned the concentration of obtainable formic acid product, do not mention the quality index of the yield and the product of formic acid product, can't clear and definite its reaction, isolating thoroughness, in addition, do not mention the distillation temperature of formic acid and by product in the patent yet.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of discharging that reduces the carbon monoxide pollution thing is provided, acidification reaction yield height, formic acid product formic acid concn height and technical process are simple, production formic acid concn height, a kind of method of producing concentration formic acid and high and polymer phosphate sodium salt with the mixing acid acidifying sodium formate that cost is low.
Of the present inventionly produce the method for concentration formic acid and high and polymer phosphate sodium salt, the steps include: with the mixing acid acidifying sodium formate
(1) drop into formic acid and polyphosphoric acid in the complex acid groove, the ratio of formic acid and polyphosphoric acid quality is 1: 5-1: 1, be stirred into mixing acid, and formic acid concn is more than 90%, and polyphosphoric acid concentration is with P
2O
5Count 72.4%-86.95%;
(2) will react in sodium formiate and the mixing acid adding reactor, the mol ratio of sodium formiate and polyphosphoric acid is 1: 1-1: 2;
(3) evaporation, separation obtain formic acid and compound phosphoric acid sodium salt;
(4) the compound phosphoric acid sodium salt is allocated the various polymer phosphate sodium salts of back preparation with alkali.
The used polyphosphoric acid concentration of step (1) also can be with H
3PO
4Meter is 100%-120%.
Reaction times in the step (2) is 2-5 hour.
Adopt in the step (2) mixing acid of polyphosphoric acid and formic acid can make to be reflected at liquid phase state under and fully react, sodium formiate be with the yellow phosphoric tail gas be feedstock production or with the sodium formiate of other method production, prepared formic acid concn is 90%-99.5%.
The reaction of polyphosphoric acid and sodium formiate in the step (2), sodium formiate is that branch joins for 2-10 time in the mixing acid, reacts in the reactor discontinuous.
The reaction of polyphosphoric acid and sodium formiate in the step (2) is to join in the reactor continuously in proportion mixing acid and the sodium formiate while to react, and reactor adopts in tubular reactor, twin screw or the three screw rod machines a kind of.
The described reaction of step (2) is to carry out under 100.8 ℃-150 ℃ the temperature that is higher than the formic acid boiling point.
The described process separation temperature of step (3) is 110 ℃-180 ℃, and the formic acid that steams is collected through condensing reflux.
The present invention utilizes the carbon monoxide in the source such as yellow phosphoric tail gas, by mixing acid and sodium formiate reaction, obtains the method for concentration formic acid and high and compound phosphoric acid sodium salt.The compound phosphoric acid sodium that adopts this method to make can not only have been reduced the discharging of carbon monoxide pollution thing, and can increase economic benefit of enterprises by the chemical enterprise recycle.The formic acid product formic acid concn that obtains can reach national top grade product standard, and other indexs all can reach the above standard of country-level product.Acidification reaction yield height reaches more than 90%, and solid by-product is fired the tripoly phosphate sodium STPP quality product that obtains and met national top grade product standard through being in harmonious proportion.Method of the present invention compared with prior art has following advantage: the mixing acid of employing polyphosphoric acid and formic acid can make and be reflected at fully reaction under the liquid phase state, and the acidization system is even, good fluidity, can realize industrialization; The used time of whole process is shorter, and process is simple, economical, and acidifying and solid-liquid separation can realize semicontinuous or operate continuously, and the formic acid yield is more than 90%, and formic acid concn can reach 99.5%.Can make formic acid and tripoly phosphate sodium STPP product that index meets national standard.Method of the present invention can make production operation carry out smoothly, and technical process is simple, produces the formic acid concn height, cost is low.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Fig. 2 is a process flow diagram of the present invention.
Embodiment
Further the invention will be further described below in conjunction with accompanying drawing, but be not limited to embodiment.
Embodiment 1
In reactor, add 500kg concentration and be 100% polyphosphoric acid, add 100kg concentration and be 90.0% formic acid and stir, divide 2 times then and add the 400kg sodium formiate.After waiting to add sodium formiate, improve temperature to 101 ℃, under stirring action, reacted 5 hours, obtain formic acid and compound phosphoric acid sodium salt.Be heated to 180 ℃ of distillation condensations and go out product formic acid.Making formic acid concn is 90.50%, and the acidification reaction yield is 96.54%.Evaporate to dryness for based on the compound phosphoric acid sodium salt of monosodium phosphate, disodium.Migrate out compound phosphoric acid sodium salt and alkali and allocate preparation tripoly phosphate sodium STPP product salt in the ratio of tripolyphosphate sodium salt.
Embodiment 2
Adding 500kg concentration is 105% polyphosphoric acid in reactor, and adding 150kg concentration is that 93.8% formic acid stirs, and divides 5 times then and adds the 250kg sodium formiate.After waiting to add sodium formiate, improve temperature to 110 ℃, under stirring action, reacted 3.5 hours, obtain formic acid and compound phosphoric acid sodium salt.Be heated to 150 ℃ of distillation condensations and go out product formic acid.Making formic acid concn is 92.2%.The acidification reaction yield is 94.87%.Evaporate to dryness be the compound phosphoric acid sodium salt.Migrate out the production that the compound phosphoric acid sodium salt carries out required sodium phosphate salt.
Embodiment 3
Adding 500kg concentration is 120% polyphosphoric acid in reactor, and adding 500kg concentration is that 95.6% formic acid stirs.Divide 10 times then and add the 450kg sodium formiate.After waiting to add sodium formiate, improve temperature to 150 ℃, under stirring action, reacted 2 hours, obtain formic acid and compound phosphoric acid sodium salt.To react feed liquid and put into a vaporizer, go out product formic acid at 155 ℃ of following evaporative condensers.Making formic acid concn is 94.5%, and the acidifying yield is 97.24%.Obtain the compound phosphoric acid sodium salt at evaporator outlet, carry out the production of required sodium phosphate salt.
Embodiment 4
In 500kg concentration is that to add 250kg concentration in 110% the polyphosphoric acid be 96.7% formic acid, mixes.400kg sodium formiate and mixing acid are added in the double-screw reactor together continuously.Temperature of reaction is 125 ℃, and distillation temperature is 140 ℃, obtains formic acid and the compound phosphoric acid sodium salt that condensation goes out respectively at reactor outlet.The compound phosphoric acid sodium salt carries out the production of required sodium phosphate salt.Formic acid concn is 96.3%, and the acidifying yield is 95.65%.
Embodiment 5
In 500kg concentration is that to add 200kg concentration in 115% the polyphosphoric acid be 94.5% formic acid, mixes.500kg sodium formiate and mixing acid are added in the tubular reactor together continuously.Temperature of reaction is 115 ℃, and distillation temperature is 130 ℃, obtains formic acid and the compound phosphoric acid sodium salt that condensation goes out respectively at reactor outlet.The compound phosphoric acid sodium salt carries out the production of required sodium phosphate salt.Formic acid concn is 95.9%, and the acidifying yield is 94.85%.
Claims (8)
1, a kind ofly produce the method for concentration formic acid and high and polymer phosphate sodium salt, it is characterized in that step is with the mixing acid acidifying sodium formate:
(1) drop into formic acid and polyphosphoric acid in the complex acid groove, the ratio of formic acid and polyphosphoric acid quality is 1: 5-1: 1, be stirred into mixing acid, and formic acid concn is more than 90%, and polyphosphoric acid concentration is with P
2O
5Count 72.4%-86.95%;
(2) will react in sodium formiate and the mixing acid adding reactor, the mol ratio of sodium formiate and polyphosphoric acid is 1: 1-1: 2;
(3) evaporation, separation obtain formic acid and compound phosphoric acid sodium salt;
(4) the compound phosphoric acid sodium salt is allocated the various polymer phosphate sodium salts of back preparation with alkali.
2, a kind ofly produce the method for concentration formic acid and high and polymer phosphate sodium salt with the mixing acid acidifying sodium formate by claim 1 is described, it is characterized in that, the used polyphosphoric acid concentration of step (1) is with H
3PO
4Count 100%-120%.
3, a kind ofly produce the method for concentration formic acid and high and polymer phosphate sodium salt by claim 1 is described, it is characterized in that the reaction times in the step (2) is 2-5 hour with the mixing acid acidifying sodium formate.
4, by the described a kind of method of producing concentration formic acid and high and the above sodium phosphate salt of polymerization with the mixing acid acidifying sodium formate of claim 1, it is characterized in that, the mixing acid of employing polyphosphoric acid and formic acid can make and be reflected at fully reaction under the liquid phase state in the step (2), sodium formiate is to be sodium formiate feedstock production or that produce with other method with the yellow phosphoric tail gas, and prepared formic acid concn is 90%-99.5%.
5, by the described a kind of method of producing concentration formic acid and high and polymer phosphate sodium salt with the mixing acid acidifying sodium formate of claim 1, it is characterized in that, the reaction of polyphosphoric acid and sodium formiate in the step (2), sodium formiate is that branch joins for 2-10 time in the mixing acid, reacts in the reactor discontinuous.
6, by the described a kind of method of producing concentration formic acid and high and polymer phosphate sodium salt with the mixing acid acidifying sodium formate of claim 1, it is characterized in that, the reaction of polyphosphoric acid and sodium formiate in the step (2), be to join in the reactor continuously in proportion mixing acid and the sodium formiate while to react, reactor adopts in tubular reactor, twin screw or the three screw rod machines a kind of.
7, a kind ofly produce the method for concentration formic acid and high and polymer phosphate sodium salt by claim 1 is described, it is characterized in that the described reaction of step (2) is to carry out under 100.8 ℃-150 ℃ the temperature that is higher than the formic acid boiling point with the mixing acid acidifying sodium formate.
8, a kind ofly produce the method for concentration formic acid and high and polymer phosphate sodium salt with the mixing acid acidifying sodium formate by claim 1 is described, it is characterized in that the described process separation temperature of step (3) is 110 ℃-180 ℃, the formic acid that steams is collected through condensing reflux.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100946830A CN101607879A (en) | 2009-07-01 | 2009-07-01 | A kind of method of producing concentration formic acid and high and polymer phosphate sodium salt with the mixing acid acidifying sodium formate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100946830A CN101607879A (en) | 2009-07-01 | 2009-07-01 | A kind of method of producing concentration formic acid and high and polymer phosphate sodium salt with the mixing acid acidifying sodium formate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101607879A true CN101607879A (en) | 2009-12-23 |
Family
ID=41481805
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2009100946830A Pending CN101607879A (en) | 2009-07-01 | 2009-07-01 | A kind of method of producing concentration formic acid and high and polymer phosphate sodium salt with the mixing acid acidifying sodium formate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101607879A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102001928A (en) * | 2010-10-18 | 2011-04-06 | 云南省化工研究院 | Method for efficiently separating product formic acid from by-product sodium salt by using sodium formiate method |
| CN102260158A (en) * | 2011-06-15 | 2011-11-30 | 浙江大学 | Continuous production system for preparing high-quality formic acid by acidifying sodium formate with polyphosphoric acid |
| CN103130636A (en) * | 2013-02-04 | 2013-06-05 | 贵州省惠水川东化工有限公司 | Method enabling polyphosphoric acid to react with sodium formate to cooperatively generate high-purity formate acid and sodium dihydrogen phosphate |
-
2009
- 2009-07-01 CN CNA2009100946830A patent/CN101607879A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102001928A (en) * | 2010-10-18 | 2011-04-06 | 云南省化工研究院 | Method for efficiently separating product formic acid from by-product sodium salt by using sodium formiate method |
| CN102260158A (en) * | 2011-06-15 | 2011-11-30 | 浙江大学 | Continuous production system for preparing high-quality formic acid by acidifying sodium formate with polyphosphoric acid |
| CN102260158B (en) * | 2011-06-15 | 2013-06-05 | 浙江大学 | Continuous production system for preparing high-quality formic acid by acidifying sodium formate with polyphosphoric acid |
| CN103130636A (en) * | 2013-02-04 | 2013-06-05 | 贵州省惠水川东化工有限公司 | Method enabling polyphosphoric acid to react with sodium formate to cooperatively generate high-purity formate acid and sodium dihydrogen phosphate |
| CN103130636B (en) * | 2013-02-04 | 2015-08-12 | 贵州省惠水川东化工有限公司 | A kind of method of polyphosphoric acid and sodium formiate reaction dense, the high-purity formic acid of coproduction height and SODIUM PHOSPHATE, MONOBASIC |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103113208B (en) | The continuous production processes of calcium formiate is prepared by calcium hydroxide carbonylation | |
| CN102775441B (en) | Continuous production method of glyphosate synthetic liquid | |
| CN103382092B (en) | A kind of preparation method of naphthalene water reducer | |
| CN101607888B (en) | Alpha-keto-leucine-calcium preparation method | |
| CN102875594B (en) | Continuous synthesis technique of hydroxyethylidenediphosphonic acid | |
| CN101265160A (en) | Method for purifying biological diesel oil byproduct glycerin | |
| CN104445124A (en) | Method for producing monopotassium phosphate by using supergravity technology | |
| CN101607879A (en) | A kind of method of producing concentration formic acid and high and polymer phosphate sodium salt with the mixing acid acidifying sodium formate | |
| CN1915954A (en) | Method for producing formic acid through phosphoric acid and sodium formate | |
| CN102753512B (en) | By improving one's methods of glycerine synthesis of acrolein | |
| CN1994999A (en) | 95% high concentration formic acid production method | |
| CN103342642A (en) | Process for continuously producing dimethyl adipate through reaction-rectification method | |
| CN104190104A (en) | Process equipment and method for refining dimethoxymethane in byproducts produced in production of glyphosate by glycine method | |
| CN101531580A (en) | Crystallization method of stearoylbenzoylmethane | |
| CN101357755B (en) | Production process of potassium dihydrogen phosphate | |
| CN105669926A (en) | Preparation method of high-content naphthalene water reducer | |
| CN102513132B (en) | Dedicated DYD catalyst for one-step bio-diesel production and production method thereof | |
| CN115536620B (en) | System and method for continuously producing furfural and 5-hydroxymethylfurfural from cellulosic biomass | |
| CN103497323B (en) | The synthetic method of methoxy polyoxyethylene ether (methyl) acrylate | |
| CN102675363B (en) | 2-phosphonobutane-1,2,4-tricarboxylic acid production process | |
| WO2009072106A3 (en) | Preparation of a potassium phosphate based composition | |
| CN102816058A (en) | Method for preparing 2, 2-bis (hydroxymethyl) butyric acid | |
| CN203938664U (en) | A kind of device of energy saving and environment friendly base-catalyzed transesterification method production biofuel | |
| CN101214943B (en) | Technique for preparing high concentration low carbonic acid from low carbonate acidified by polymeric acid | |
| CN104087426B (en) | A kind of device and method of energy saving and environment friendly base-catalyzed transesterification method production biofuel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20091223 |