Method for preparing hypophosphorous acid by using electrolytic method

https://patents.google.com/patent/CN1341779A/en

Abstract

The method for preparing hypophosphorous acid by using electrolysis method is characterized by that it
uses the alkali metal hypophosphite as raw material, uses graphite as anode, uses stainless steel as
cathode and uses the mehtod of electrolyzing water by utilizing electrolysis bath to make electrolysis, in
which the raw material chamber possesses aqueous solution of sodium hypophosphite whose
concentration is 300-500 g/L, the primary solution in anode chamber is sulfuric acid solution whose
concentration is 5-15 g/L, the primary solution in the cathode chamber and its adjacent buffer chamber
is an alkali solution whose concentration is 5-15 g/L, and the primary solution in the product chamber
and its adjacent buffer chamber is the hypophosphorous acid solution whose concentration is 5-15 g/L.
Said invention does not produce waste residue and waste liquid, and it is a clean production method.
Background technique

Hypophosphorous acid is one of phosphorus chemical products widely used.Traditional methods of

preparation are barium hydroxide and phosphorus, plus barium sulfate addition to the system. However,
since the solubility of barium hypophosphite small, resulting hypophosphorous acid concentration is not
high, but also industrial purified by recrystallization several times, so that the application of this process is
limited. Another ion exchange resin prepared by Method hypophosphite, sodium hypophosphite as raw
materials i.e., a strong acid cation exchange resin in addition to a dilute acid solution prepared sodium
[Arzoumanidis et al, US Patent, 4265866,1981]. Such a method is more cumbersome, higher production
costs, only suitable for small batch production. In recent years it has been the use of foreign production
hypophosphorous patent coverage electrodialysis. Noble metal such as platinum, iridium and ruthenium,
as an anode, stainless steel, graphite, platinum or the like as the anode and using the chamber 3, to
prepare hypophosphite [Nobel 4 electrodialysis cell compartment or chamber 5 for the method of direct
current electrolysis, Fred I et al, USPatent 5480517,5578182].

The above patent that hypophosphite ion oxidation reaction occurs at the anode, through our experiments
show, this is impossible - nascent oxygen produced by electrolysis anodes will necessarily portion
hypophosphite ions are oxidized to the phosphite or phosphate ions . In addition, the noble metal is
expensive, so large-scale industrial production is limited.

SUMMARY

The present invention is an improved phosphate prepared times by electrolysis, which is the raw material
for the alkali metal hypophosphites, using abundant and inexpensive source of raw material graphite as
an anode, stainless steel as the cathode, application of six chamber electrodialysis cell electrolytic water
method hypophosphorous acid is prepared. Anion and cation exchange membranes used were
purchased from Shanghai Chemical. Structure composed of six chamber electrodialysis cell as shown in
Figure 1.

A buffer chamber disposed before electrolysis chamber feed concentration of 300-500g / L sodium
hypophosphite aqueous solution, the initial solution in the anode compartment at a concentration of 5-15g
/ L dilute sulfuric acid solution, and the adjacent cathode compartment in the initial solution a
concentration of 5-15g / L of a dilute alkali metal hydroxide solution, the best choice is sodium hydroxide
or potassium hydroxide, the initial solution and the product chambers adjacent buffer chamber is at a
concentration of 5-15g / L a dilute solution of hypophosphorous acid.

The electrodialysis cell after the DC 10-15V on to the anionic and cationic feed chamber is moved to the
poles, respectively, the cation, and the anion moves to the anode move to the cathode. However, mainly
the anion exchange membrane allows anions, the main chamber into the secondary product chamber
phosphate ion (H2PO2-); mainly the same cation exchange membrane allows cations to pass, so that the
cathode compartment and sodium ions are mainly (Na +).

The main reaction in the graphite anode during the electrolysis is electrolysis of water occurs to oxygen
and hydrogen ions, the reaction is:

E0 = + 0.401V electrolytically produced hydrogen ions from the anode compartment into the anode
through the membrane to the product compartment, and into the secondary chamber of the phosphate
anion binding generating hypophosphorous acid product. When the cathode electrolysis chamber is
mainly water electrolysis reaction to produce hydrogen and hydroxide anions, the reaction is:
2H ++ 2e = H2E0 = 0.0004V hydroxide ions generated by electrolysis into the chamber to generate
binding Sodium hydroxide.

Since the hypophosphite ion is a strong reductant latter, anode electrolytic water discharged oxygen, this
nascent oxygen will be oxidized to phosphite ions in an aqueous solution. In order to prevent oxidation of
the root of a hypophosphite ion, plus a male membrane to separate the anode chamber and the product
chamber adjacent to the anode. This is the crux of this law using phosphoric acid production times.

To avoid loss of current efficiency and increase the purity of the product, between the feed compartment
and a cathode compartment plus two male film constituting the buffer chamber, plus two female film may
constitute a buffer chamber between the feed chamber and the product chamber. A first buffer chamber
for preventing the hydroxide ions into the feed compartment is extremely advantageous; Likewise, the
second buffer chamber for preventing the hydrogen ions into the feed chamber and prevents sodium ions
into the product chamber is very advantageous.

To protect and extend the life of the anion and cation exchange membrane, this concentration should
Preparation of hypophosphorous acid in about 100g / L. In this case, the anode produces an equivalent
amount of sodium hydroxide. Feed chamber and the buffer solution chamber may be substantially remain
stationary.When the sodium ion concentration of the buffer solution chamber closer to the product
chamber is increased, it can be returned to the feed chamber and feed chamber is continuously added
sodium hypophosphite, to maintain the ongoing reaction.

The present invention is an improvement on the preparation of sub-acid electrolysis process, the process
is simple, inexpensive, easy to large-scale industrial production. The present invention is not waste, waste
liquid, it is a clean production.

BRIEF DESCRIPTION

1 works six schematic chamber electrodialysis cell, the anode chamber 1-, 2- product chamber,
the buffer chamber 3-, 4- feed chamber, the buffer chamber 5-, 6- cathode compartment.

detailed description

Embodiment 1 Example graphite anode material, the electrode area is 40cm2, a stainless steel
electrode as the cathode. Anion and cation exchange membranes were purchased from Shanghai
Chemical, membrane area used for electrolysis is 48cm2. Six chamber electrodialysis cell
solution volume per chamber of 500ml.The initial solution before electrolysis anode chamber
was 10g / L sulfuric acid, the raw material chamber of 500g / L of sodium hypophosphite, and
the cathode compartment are adjacent buffer chamber 10g / L of sodium hydroxide, the product
chamber and the buffer chamber are adjacent 10g / L hypophosphite.

Operating voltage of 10-15V, maintained at 3.0A current conditions, the electrolysis continued
6H, secondary product chamber concentration of phosphoric acid was 69.3g / L, to calculate the
current efficiency at this time was 80.9%.

After the electrolysis 6H different current conditions, the concentration of secondary product
chamber phosphoric acid solution as shown in Table 1.
TABLE product concentration and current efficiency of current (A) at a different operating current
hypophosphorous acid concentration (g / L) Current efficiency (%) 20.2 1.0 73.83.0 70.72.0 42.7 69.3
80.94.0 73.55.0 84.1 71.4 103.1

Example 2 initial operating conditions of six chamber electrodialysis cell of Example 1 embodiment.

3A when the operating current, electrolysis time is 30H, the product chamber views phosphoric acid
concentration 178.6g / L, when the current efficiency was 55.3%.

Chamber electrolysis products at different times of the obtained acid concentration Ci of the solution as
shown in Table 2.

TABLE product concentration and current efficiency electrolysis time (H) at 2 different concentrations of
hypophosphorous acid electrolysis time (g / L) Current efficiency (%) 6 69.3 80.912 101.9 77.418 136.1
68.324 169.1 60.530 55.3 178.6 Example 3 Initial electrodialysis cell compartment embodiment six
working conditions as in example 1.

3A when the operating current, electrolysis time of 30H, a sodium ion content in the product compartment
and sulfate ion were 50ug / L and 0.80g / L.

Chamber electrolysis products at different times of the obtained sodium ion and sulfate ion content shown
in Table 3.

Table 3 Sodium hypophosphite products and sulfate ion content changes with time of electrolysis time (H)
of the sodium ion content (ug / L) Sulfate Content (g / L) 6 5 0.1112 13 0.3618 25 0.4824 40 0.7630 50
0.80

Claims (6)

A method for preparation of hypophosphorous acid by electrolysis, characterized in that it is an alkali

metal hypophosphite as a raw material, graphite as an anode, stainless steel as the cathode for
electrolysis, electrodialysis cell application electrolytic water; a method wherein the feed compartment
placing a concentration of 300-500g / L sodium hypophosphite aqueous solution, the initial solution in the
anode compartment at a concentration of 5-15g / L sulfuric acid solution, a cathode chamber and buffer
chamber adjacent the initial solution is in a concentration of 5- 15g / L of the alkali solution, the product
chamber and the buffer chamber adjacent the initial solution is a concentration of 5-15g / L hypophosphite
solution.

2. The method of preparation of said hypophosphorous acid electrolytic method according to claim 1,
wherein said electrodialysis cell is a six-chamber electrodialysis cell.
3. A method for preparing hypophosphorous said electrolytic method according to claim 1, characterized
in that the operating voltage of said electrolytic 10-15V, operating current. 1-5A, electrolysis time 6-30H.
The method of preparation of said hypophosphorous acid electrolytic method according to claim 1 or 3,
wherein said electrolytic operating current 3A.
The method of preparation of said hypophosphorous acid electrolytic method according to claim 1,
wherein said alkaline solution is sodium hydroxide or potassium hydroxide.
6. The method of preparation of said hypophosphorous acid electrolytic method according to claim 1,
wherein said hypophosphite is sodium hypophosphite.
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