Method and system for the integral chlorine dioxide production with relatively independent sodium chlorate electrolytic production and chlorine dioxide production

Patent metadata

Field	Value
Publication number	US-9776163-B1
Application number	US-201715589094-A
Country	US
Kind code	B1
Filing date	May 8, 2017
Priority date	Jun 7, 2016
Publication date	Oct 3, 2017
Grant date	Oct 3, 2017

Abstract

A system for the integral chlorine dioxide production with relatively independent sodium chlorate electrolytic production and chlorine dioxide production is provided. The system may feed electrolyte solution into a solid-liquid filter, filtering out the crystal and eliminating sodium chloride and sodium dichromate. The sodium chlorate crystal may be fed into a chlorine dioxide generator after dissolving, while sodium chloride and sodium dichromate solution separately return to electrolyzer for electrolysis process. Sodium chloride may be constantly formed as a by-product in the chlorine dioxide production unit, and solution containing the sodium chloride is withdrawn from the generator and, after filtration, washing and dissolution, recycled back to sodium chlorate production unit. This way, there is no need of sodium chloride make-up.

First claim

The invention claimed is:

1. A system for integral chlorine dioxide production with independent sodium chlorate electrolytic production and chlorine dioxide production, the system comprising:
an electrolytic production unit for sodium chlorate (NaClO3) and a crystallization unit;
a chlorine dioxide (ClO2) production unit; and
a hydrochloric acid (HCl) synthesis unit,
wherein
the NaClO3 electrolytic production unit and crystallization unit comprise
an electrolysis loop formed by connecting in series an electrolyzer, a degasifier, an electrolyte feed header, an electrolyte cooler, and a chlorine dioxide reactor,
a NaClO3 crystallization unit formed by linking with pipelines an electrolyte storage tank, an electrolyte transit pump, an electrolyte buffer tank, an electrolyte transfer pump, an evaporator crystallizer, a sodium chlorate slurry pump, and a solid-liquid filter, and
a sodium chlorate feeding system formed by linking with pipelines a sodium chlorate dissolve tank, a sodium chlorate transit pump, a sodium chlorate buffer tank, a sodium chlorate feed pump, and a sodium chlorate filter, wherein
one end of the solid-liquid filter is connected with the chlorine dioxide reactor through pipelines and other end is connected with the sodium chlorate dissolve tank; and

the ClO 2 production unit comprise
a generation system formed by a circulation loop with a heat generator, a lower circulation pipe, a chlorine dioxide generator, and an upper circulation pipe, pumping liquor with a circulation pump;
a chlorine dioxide solution production unit formed by connecting in sequence via pipelines a generator exhaust pipe, an indirect cooler, a chlorine dioxide absorber, a tail gas fan, a liquid-gas separator, and a dilute chlorine dioxide solution cooler;
a sodium chloride recycle system formed by linking in sequence a sodium chloride extraction pipe, a sodium chloride filter, a sodium chloride dissolve tank, a sodium chloride transit pump, and a sodium chloride buffer tank, the sodium chloride buffer tank is connected with the chlorine dioxide reactor through pipelines; and

a HCl synthesis unit comprising
a unit formed by connecting in sequence a hydrogen cooler, a hydrogen demister, a hydrochloric acid synthesis burner, a hydrochloric acid storage tank, and a hydrochloric feed pump, the hydrochloric acid feed pump is connected with the heat generator heater via pipelines, and the hydrogen cooler is connected with the chlorine dioxide reactor via one or more hydrogen exhaust pipes.

2. The system of claim 1 , further comprising:
a sodium chlorate electrolyzer fed with refined brine solution, and generated electrolyte enters the degasifier through pipelines to separate gases that come along, wherein the gases are introduced into hydrogen cooler, passing hydrogen demister, and arriving at hydrochloric acid synthesis burner, while liquor enters sodium chlorate chlorine dioxide reactor to generate concentrated sodium chlorate solution;
evaporator crystallizer receives sodium chlorate solution to form sodium chlorate crystals in the solution, the solution is introduced into solid-liquid filter, removing sodium chloride and sodium dichromate, sodium chlorate crystals enter chlorine dioxide generator lower circulation pipe after dissolving, while sodium chloride and sodium dichromate are separated out by filter, returning back to the electrolysis system for further processing with the electrolyzer;
hydrogen gas from the electrolysis unit enters the cooler and demister to remove vapors, the hydrogen gas enters hydrochloric acid synthesis burner to burn with chlorine gas, forming hydrogen chloride gas in the burner, the gas being cooled and absorbed to form the hydrochloric acid solution for the chlorine dioxide production unit; and
strong sodium chlorate solution from electrolysis unit reacts with hydrochloric acid within chlorine dioxide generator, wherein flash evaporation occurs to form a production stream of chlorine dioxide, chlorine gas, sodium chloride and vapor, mixed gases are withdrawn from top of generator, flowing through exhaust pipes, cooling down by indirect cooler prior to the absorber where the mixed gases are absorbed and form chlorine dioxide solution.

3. The system of claim 2 , wherein the generated electrolyte generated comprises concentrated sodium chlorate solution at a concentration of 600-700 g/l and sodium chloride solution at a concentration of 100-110 g/l.

4. The system of claim 2 , wherein reaction temperature range within the generator is in range of 68 and 72 degree Celsius, vacuity is between −77 and −78 kpa, concentration of sodium chlorate added into the generator is between 640 and 660 g/l, and weight concentration of hydrochloric acid added into the generator is between 29 and 32%.

5. The system of claim 2 , wherein the electrolyte is introduced into the electrolyte buffer tank through an electrolyte transit pump, and
the electrolyte from the buffer tank enters the evaporator crystallizer via transfer pump to form crystals.

6. The system of claim 2 , wherein the generated sodium chlorate crystals are fed into a dissolve tank to be processed prior to pumping to the buffer tank by way of the transit pump, and
the sodium chlorate is withdrawn from the buffer tank via the feed pump, passing through the sodium chlorate filter and arriving at chlorine dioxide generator lower circulation pipe afterwards.

7. The system of claim 2 , wherein a byproduct of chlorine gas formed during the reaction is fed into the hydrochloric acid burner to react with hydrogen gas from the electrolyzer and outsourced chlorine gas to form hydrochloric acid,
within the chlorine dioxide generator, reaction liquor comprising sodium chloride crystal is introduced into the sodium chloride filter to filter out crystals, dissolving the crystals in the dissolve tank for recycling back to the electrolysis system, while the filtered liquor is recycled back to the chlorine dioxide generator.

8. The system of claim 2 , wherein tail gas from the absorber enters the gas-liquid separator to separate chlorine dioxide, which returns back to the absorber after cooler, and separated chlorine gas is introduced into the burner and mixed with outsourced chlorine gas to react with the hydrogen gas from the electrolysis system to form hydrochloric acid in the burner.

Assignees

• Univ Guangxi

Inventors

• Wang Shuangfei
• Qin Chengrong
• Song Xueping
• Li Xusheng
• Nie Shuangxi
• Liang Chen

Classifications

• B01J19/2465 Primary

  externally, i.e. the mixture leaving the vessel and subsequently re-entering it · CPC title

• C25B1/265

  Chlorates · CPC title

• C25B15/08

  Supplying or removing reactants or electrolytes; Regeneration of electrolytes · CPC title

• C01B11/025 Primary

  from chlorates without any other reaction reducing agent than chloride ions · CPC title

• B01J19/087

  employing electric or magnetic energy · CPC title