CN1172028C - Method for preparing hypophosphorous acid by using electrolytic method - Google Patents
Method for preparing hypophosphorous acid by using electrolytic method Download PDFInfo
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- CN1172028C CN1172028C CNB011420243A CN01142024A CN1172028C CN 1172028 C CN1172028 C CN 1172028C CN B011420243 A CNB011420243 A CN B011420243A CN 01142024 A CN01142024 A CN 01142024A CN 1172028 C CN1172028 C CN 1172028C
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Abstract
The present invention relates to a preparation method of phosphorous acid, particularly to a method for preparing phosphorous acid by an electrolysis method. Alkali metal phosphite as raw material is electrolyzed by a method of electrolyzing water in an electrodialysis cell with graphite used as an anode and stainless steel used as a cathode, wherein the concentration of sodium phosphate solution in a raw material chamber is 300 to 500 g/L, the initial solution in an anode chamber is 5 to 15 g/L sulfuric acid solution, the initial solution in a cathode chamber and the initial solution in a surge chamber adjacent to the cathode chamber are 5 to 15 g/L alkali solution, and the initial solution in a product chamber and the initial solution in the surge chamber adjacent to the product chamber are 5 to 15 g/L phosphorous acid solution. The present invention has the advantages of no waste slag and no waste liquid, and belongs to clean production.
Description
Technical field
The present invention relates to the preparation of Hypophosporous Acid, 50, it is a kind of method of method for preparing hypophosphorous acid by using electrolytic.
Background technology
Hypophosporous Acid, 50 is one of widely used phosphorus chemical product.Traditional preparation method is yellow phosphorus and hydrated barta reaction, adds sulfuric acid again and makes except that barium.But because barium hypophosphite solubleness is less, the Hypophosporous Acid, 50 concentration that makes is not high, and industrial goods also will carry out repeatedly recrystallization purifies, thereby the application of this technology is restricted.Other has the ion-exchange-resin process of employing to prepare Hypophosporous Acid, 50, just is raw material with the sodium hypophosphite, and the employing strongly acidic cation-exchange removes sodium and makes dilute acid soln [Arzoumanidis et al, U S Patent, 4265866,1981].This kind method is more loaded down with trivial details, and production cost is higher, only is fit to small serial production.Recent years, the existing abroad patent that adopts electroosmose process to produce Hypophosporous Acid, 50 was reported.With precious metal, make anode as platinum, iridium and ruthenium etc., with stainless steel, graphite and platinum etc. as anode, adopt Room 3, the method that Room 4 or 5 Room electrodialysis cells carry out dc electrolysis prepares Hypophosporous Acid, 50 [Nobel, Fred I et al, U S Patent 5480517,5578182].
Above-mentioned patent thinks that hypophosphite ion at anode oxidizing reaction does not take place, experiment showed, that through us this is impossible---the nascent oxygen that anode electrolysis produces must be oxidized to the part hypophosphite ion orthophosphite or phosphate anion.In addition, noble metal electrode costs an arm and a leg, and large-scale commercial production is restricted.
Summary of the invention
The present invention is a kind of improvement of method for preparing hypophosphorous acid by using electrolytic, it is to be raw material with the alkalt metal hypophophite, the graphite that adopts sufficient raw and cheapness is as anode, and as negative electrode, the method for using six Room electrodialysis cell brine electrolysis prepares Hypophosporous Acid, 50 with stainless steel.Used anion and cation exchange membrane is available from Shanghai Chemical Plant.The structure of six Room electrodialysis cells is formed as shown in Figure 1.
Feed chamber placement concentration is the sodium hypophosphite aqueous solution of 300-500g/L before the electrolysis, initial soln in the anolyte compartment is that concentration is the dilution heat of sulfuric acid of 5-15g/L, initial soln in the cathode compartment surge chamber adjacent with it is that concentration is the rare alkaline metal hydroxide solution of 5-15g/L, optimal selection is sodium hydroxide or potassium hydroxide, and the initial soln in the product chambers surge chamber adjacent with it is that concentration is rare Hypophosporous Acid, 50 solution of 5-15g/L.Working current is 1-5A, and electrolysis time is 6-30H.
After electrodialysis cell being passed to the direct current of 10-15V, the zwitterion of feed chamber moves to the two poles of the earth respectively, and positively charged ion moves to negative electrode, and the negatively charged ion anode moves.But anion-exchange membrane mainly allows negatively charged ion to pass through, so enter the main chamber hypophosphite ion (H of product chambers
2PO
2 -); Same cationic exchange membrane mainly allows positively charged ion to pass through, so that enter cathode compartment mainly is sodium ion (Na
+).
The principal reaction that takes place at graphite anode in the electrolytic process is that water electrolysis is oxygen and hydrogen ion, and reaction formula is:
The hydrogen ion that electrolysis produces enters into product chambers from the anolyte compartment by anode membrane, combines with the Hypophosporous Acid, 50 root negatively charged ion that enters into this chamber to generate the Hypophosporous Acid, 50 product.What cathode compartment mainly took place during electrolysis is the reaction that water electrolysis produces hydrogen and hydroxide radical anion, and reaction formula is:
The hydroxide ion that electrolysis produces with enter into this chamber sodium ion and combine generation sodium hydroxide.
Because hypophosphite ion is a kind of strong reductive agent in the aqueous solution, after anode electrolysis water was emitted oxygen, this nascent oxygen can be oxidized to orthophosphite ions with it.In order to prevent the oxidation of hypophosphite ion, the place adds an anode membrane at contiguous anode, and anolyte compartment and product chambers are separated.This is to use this law to produce the crucial part of Hypophosporous Acid, 50.
For fear of the loss of current efficiency with improve the purity of product, between feed chamber and cathode compartment, add two anode membranes and constitute surge chamber, between feed chamber and product chambers, add two cavity blocks and also constitute surge chamber.First surge chamber is very favourable for preventing that hydroxide ion from entering into feed chamber; Equally, second surge chamber is for preventing that hydrogen ion from entering into feed chamber and preventing that sodium ion from entering into product chambers also is very favorable.
Be the life-span of protection and prolongation anion and cation exchange membrane, the Hypophosporous Acid, 50 concentration of using this law to produce should be about 100g/L.At this moment, on anode, can produce the sodium hydroxide of equivalent.Solution in feed chamber and the surge chamber can keep motionless substantially.After rising near the Na ion concentration in the surge chamber solution of product chambers, it can be turned back to feed chamber, feed chamber is then constantly replenished sodium hypophosphite, to keep constantly carrying out of reaction.
The present invention is the improvement to method for preparing hypophosphorous acid by using electrolytic, and technology is simple, and low price is easy to large-scale industrial production.The present invention does not have waste residue, waste liquid produces, and belongs to cleaner production.
Description of drawings
The principle of work synoptic diagram of Fig. 1 six Room electrodialysis cells, 1-anolyte compartment, 2-product chambers, 3-surge chamber, 4-feed chamber, 5-surge chamber, 6-cathode compartment.
Embodiment
Embodiment 1
Anode material is a graphite, and electrode area is 40cm
2, negative electrode is a stainless steel electrode.Anion and cation exchange membrane is available from Shanghai Chemical Plant, and the membrane area that uses during electrolysis is 48cm
2The liquor capacity of the every chamber of electrodialysis cell, six Room is 500ml.The preceding anolyte compartment of electrolysis initial soln is a 10g/L sulfuric acid, and feed chamber is the 500g/L sodium hypophosphite, and the surge chamber that cathode compartment is adjacent with it is 10g/L sodium hydroxide, and product chambers and its adjacent buffer chamber are the 10g/L Hypophosporous Acid, 50.
Operating voltage is 10-15V, and holding current is under the 3.0A condition, and behind the lasting electrolysis 6H, the concentration of Hypophosporous Acid, 50 is 69.3g/L in the product chambers, and the current efficiency of calculating this moment is 80.9%.
Behind the electrolysis 6H, the concentration of Hypophosporous Acid, 50 solution is as shown in table 1 in the product chambers under the different current condition.
Product concentration and current efficiency under the table 1 different operating electric current
Electric current (A) Hypophosporous Acid, 50 concentration (g/L) current efficiency (%)
1.0 20.2 70.7
2.0 42.7 73.8
3.0 69.3 80.9
4.0 84.1 73.5
5.0 103.1 71.4
Embodiment 2
Six Room electrodialysis cell initialization conditions are with example 1.
When working current was 3A, electrolysis time was 30H, and Hypophosporous Acid, 50 concentration is 178.6g/L in the product chambers, and this moment, current efficiency was 55.3%.
Under the different electrolysis times in the resulting product chambers concentration of Hypophosporous Acid, 50 solution as shown in table 2.
Product concentration and current efficiency under the different electrolysis times of table 2
Electrolysis time (H) Hypophosporous Acid, 50 concentration (g/L) current efficiency (%)
6 69.3 80.9
12 101.9 77.4
18 136.1 68.3
24 169.1 60.5
30 178.6 55.3
Embodiment 3
Six Room electrodialysis cell initialization conditions are with example 1.
When working current was 3A, electrolysis time was 30H, and the content of sodium ion and sulfate ion is respectively 50ug/L and 0.80g/L in the product chambers.
Under the different electrolysis times in the resulting product chambers sodium ion and sulfate ion content as shown in table 3.
Sodium ion and sulfate ion content are over time in the table 3 Hypophosporous Acid, 50 product
Electrolysis time (H) sodium ions content (ug/L) sulfate radical content (g/L)
6 5 0.11
12 13 0.36
18 25 0.48
24 40 0.76
30 50 0.80
Claims (3)
1, a kind of method of method for preparing hypophosphorous acid by using electrolytic is characterized in that it is is raw material with the alkalt metal hypophophite, and graphite is as anode, and as negative electrode, the method for electrodialysis groove brine electrolysis is carried out electrolysis with stainless steel; Wherein, it is the sodium hypophosphite aqueous solution of 300-500g/L that feed chamber is placed concentration, initial soln in the anolyte compartment is that concentration is the sulphuric acid soln of 5-15g/L, initial soln in the cathode compartment surge chamber adjacent with it is that concentration is the alkaline solution of 5-15g/L, and the initial soln in the product chambers surge chamber adjacent with it is that concentration is the Hypophosporous Acid, 50 solution of 5-15g/L; Said electrodialysis cell is six Room electrodialysis cells, comprises anolyte compartment, product chambers, surge chamber, feed chamber, surge chamber and cathode compartment successively; Said alkaline solution is sodium hydroxide or potassium hydroxide.
2, according to the method for the said method for preparing hypophosphorous acid by using electrolytic of claim 1, it is characterized in that said electrolysis operating voltage 10-15V, working current is 1-5A, electrolysis time is 6-30H.
3,, it is characterized in that said electrolysis working current is 3A according to the method for claim 1 or 2 said method for preparing hypophosphorous acid by using electrolytic.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011420243A CN1172028C (en) | 2001-09-07 | 2001-09-07 | Method for preparing hypophosphorous acid by using electrolytic method |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB011420243A CN1172028C (en) | 2001-09-07 | 2001-09-07 | Method for preparing hypophosphorous acid by using electrolytic method |
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|---|---|
| CN1341779A CN1341779A (en) | 2002-03-27 |
| CN1172028C true CN1172028C (en) | 2004-10-20 |
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| CNB011420243A Expired - Fee Related CN1172028C (en) | 2001-09-07 | 2001-09-07 | Method for preparing hypophosphorous acid by using electrolytic method |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313641C (en) * | 2003-12-09 | 2007-05-02 | 南开大学 | Method for chemical plating nickel phosphor alloy |
| CN1297691C (en) * | 2003-12-09 | 2007-01-31 | 南开大学 | Method for preparing nickel hypophosphite by electrolytic method |
| CN103318862B (en) * | 2013-06-08 | 2015-08-19 | 武汉工程大学 | Five Room electroosmose processs prepare the technique of Hypophosporous Acid, 50 |
| CN104386659B (en) * | 2014-11-15 | 2019-10-25 | 周骏宏 | A method of hypophosphorous acid is produced with phosphorous chemical industry waste material |
| CN109589793B (en) * | 2018-12-28 | 2024-01-26 | 浙江蓝极膜技术有限公司 | Bipolar membrane device for producing hypophosphorous acid |
| CN110670084A (en) * | 2019-11-07 | 2020-01-10 | 惠州市臻鼎环保科技有限公司 | Method for preparing salt by adopting electrolysis method |
| CN112047315A (en) * | 2020-08-31 | 2020-12-08 | 江苏康祥实业集团有限公司 | Clean production process for co-producing sodium hypophosphite, calcium phosphite and calcium hydroxide |
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2001
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| CN1341779A (en) | 2002-03-27 |
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