Hydrochloric acid regeneration - Wikipedia, the free encyclopedia

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Hydrochloric acid regeneration

From Wikipedia, the free encyclopedia

Hydrochloric acid regeneration or HCl regeneration refers to a chemical process for the reclamation of bound and
unbound HCl from metal chloride solutions such as hydrochloric acid.[1]

Contents
1 Field of application
2 Known processes
2.1 Regeneration
2.2 Recovery of free HCl
2.3 Transformation of FeCl2 to FeCl3
3 Hydrothermal regeneration
3.1 Step1: Oxidation
3.2 Step2: Hydrolysis
3.3 Advantages
3.4 Known implementations
4 Pyrohydrolysis of spent pickle liquor
4.1 Main differences between different implementations of pyrohydrolytic acid regeneration
4.2 Basic process flow diagram of spray roaster hydrochloric acid regeneration plant
4.3 Process description of spray roaster hydrochloric acid regeneration plant
4.3.1 Preconcentration
4.3.2 Roasting
4.3.3 Absorption
4.3.4 Exhaust gas treatment
4.4 Environmental impact
5 Notes
6 External links

Field of application
The commercially most relevant field of application for HCl regeneration processes is the recovery of HCl from waste pickle
liquors from carbon steel pickling lines. Other applications include the production of metal oxides such as, but not limited, to
Al2O3 and MgO as well as rare earth oxides by pyrohydrolysis of aqueous metal chloride or rare earth chloride solutions.
A number of different process routes are available. The most widely used is based on pyrohydrolysis and adiabatic absorption
of hydrogen chloride in water, a process invented in the 1960s. However tightening environmental standards and stringent air
permit policies render it increasingly difficult to establish new pyrohydrolysis based acid regeneration plants.

Known processes
The following processes for the regeneration of HCl from spent pickle liquors have been adopted by the ferrous metals
processing industry:

Regeneration
Pyrohydrolysis

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Spray Roaster Pyrohydrolysis

Fluidised Bed Pyrohydrolysis
Hydrothermal Regeneration
Electrolytic Fe-precipitation

Recovery of free HCl

Retardation
Dialysis
Ion Exchange

Transformation of FeCl2 to FeCl3

Electrolytic Oxidation
Chemical Oxidation

Hydrothermal regeneration
Hydrothermal Hydrolysis of hydrochloric SPL from carbon steel pickling lines is a hydrometallurgical reaction which takes
place according to the following chemical formulae:

Step1: Oxidation
12 FeCl2 + 3 O2 -> 8 FeCl3 + 2 Fe2O3

Step2: Hydrolysis
2 FeCl3 + 3 H2O -> 6 HCl + Fe2O3
Today hydrothermal hydrolysis, which operates at very low temperatures, consumes only a fraction of the energy other
processes demand and produces virtually no emissions, is considered the most effective way to regenerate any given quantity
of spent pickle liquor.

Advantages
low energy consumption (approx. 1300 kJ per litre waste acid)
no gaseous emissions
wide operating range (10 to 100% of nominal capacity)
high value by product (>20m3/g BET specific surface;>2 kg/l specific weight;<0.05% water soluble Chlorides)
theoretically unlimited operating capacity

Known implementations
Known implementations of the hydrothermal HCl regeneration processes include the PORI process (1974 for J&L Steel,
dismantled) and the optimized SMS Demag wet process (2008 for ThyssenKrupp Steel, under construction).

Pyrohydrolysis of spent pickle liquor

Pyrohydrolysis of hydrochloric spent pickle liquor from carbon steel pickling lines is a hydrometallurgical reaction which
takes place according to the following chemical formulae:
4 FeCl2 + 4 H2O + O2 = 8 HCl + 2 Fe2O3
2 FeCl3 + 3 H2O = 6 HCl + Fe2O3

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The process is an inversion of the chemical descaling (pickling) process.

Main differences between different implementations of pyrohydrolytic acid regeneration

Furnace Type (Spray Roaster, Fluidised Bed or Combined Furnace)
Physical Properties of Iron Oxide By-Product (Ferric Oxide Powder or Pellets)
Purity and commercial value of Iron Oxide By-Product
Cl content
SiO2 content (typically 40 to 1000 ppm)
other impurities
specific weight (typically 0.3 to 4 kg per litre)
specific surface (typically 0.01 to 8 m2/g)
Energy Consumption (between 600 and 1200 kcal/l)
Fuel Type
Concentration of regenerated acid (typically approx. 18% wt/wt)
Purity of regenerated acid (remaining Fe content, Cl content)
Recovery Efficiency (typically 99%)
Rinse Water Utilization
Stack Emissions (HCl, Cl2, Dust, CO, NOx)
Liquid Effluents (composition, amount)

Basic process flow diagram of spray roaster hydrochloric acid regeneration plant

Process description of spray roaster hydrochloric acid regeneration plant

Preconcentration
The metal chloride solution (in the most common case waste pickle liquor from a carbon steel pickling line) is fed to the
venturi evaporator (III), where direct mass and heat exchange with the hot roast gas from the roaster (reactor/cyclone) takes
place. The separator (IV) separates the gas and liquid phase of the venturi evaporator product. The liquid phase is
re-circulated back to the venturi evaporator to increase mass and heat exchange performance.
approx. 25 to 30% of the waste acid (H2O, HCl) are evaporated
roast gas is cooled down to approx. 92 to 96 C
dust particles are removed from the roast gas
Roasting

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Preconcentrated waste acid from the preconcentrator (III / IV) is injected into the reactor (I) by means of one or more spray
booms (VIII) bearing one or more injection nozzles each. Injection takes place at reactor top at a pressure between 4 and 10
bar. The reactor is directly fired by tangentially mounted burners that create a hot swirl. Temperatures inside the reactor vary
between 700 C (burner level) and 370 C (roast gas exit duct). In the reactor the conversion of droplets of preconcentrated
waste acid into iron oxide powder and hydrogen chloride gas takes place. Hydrogen Chloride leaves the reactor through the
top, while iron oxide powder is removed from the reactor bottom by means of mechanical extraction devices. A cyclone (II)
in the roast gas duct ensures separation and feed back of larger oxide particles carried by the roast gas.
Absorption
In the absorption column (V) the hydrogen chloride compound of the saturated roast gas leaving the preconcentrator is
adiabatically absorbed in water (which in many cases is acid rinse water from a carbon steel pickling line). Regenerated acid
(typical strength: 18% wt/wt) is collected at absorption column bottom.
Exhaust gas treatment
The roast gas is conveyed through the system by means of an exhaust gas fan (VI). Fans in plants provide pressure increases
of approx. 200 mbar and are feedback-controlled to maintain a relative pressure of -3 mbar between reactor and atmosphere
to avoid any overpressure-related leakinge of acid gas. To rinse the impeller and cool the gas as well as to remove remaining
traces of HCl from the roast gas, the exhaust gas fan is commonly supplied with quenching water, which is separated from the
exhaust gas stream by means of a mist eliminator (VII) at the pressure side of the fan. In a final scrubber, commonly
consisting of a combination of wet scrubbers such as venturi scrubbers (IX) and scrubber columns (X), remaining traces of
HCl and dust are removed. In some plant, absorption chemicals such as NaOH and Na 2S2O3 are used to bind HCl and Cl2
(which is created under certain circumstances in several, but not all spray roasting reactors).

Environmental impact
Pyrohydrolysis based acid regeneration processes produce a considerable amount of stack emissions containing HCl, particles
and chlorine, which has led to numerous violations of the U.S. clean air act in the past.[2]

Notes
1. "Hydrochloric acid regeneration" (http://www.komalgroup.com/waste_water_treatment4.html).
2. U.S. Department of Justice (2006). "Notice of Lodging of Consent Decree Under the Clean Air Act" (http://regulations.justia.com
/view/52449/). Justia Regulation Tracker.

External links
Minimizing Fuel Cost during Regeneration of the HCl Lixiviant (by Hatch) (http://www.hatch.ca/technologies
/fluidization_technologies/articles/minimizing_fuel_costs_thermal_hydrochloric_acid.htm)
3D Animation of Spray Roaster Hydrochloric Acid Regeneration Plant (by SMS Siemag Process Technologies)
(http://www.youtube.com/watch?v=TrmCPkYF4Jg)
3D Animation of Fluidized Bed Hydrochloric Acid Regeneration Plant (by SMS Siemag Process Technologies)
(http://www.youtube.com/watch?v=wfz8N_BdzGs)
3D Animation of Hydrothermal Hydrochloric Acid Regeneration Plant (by SMS Siemag Process Technologies)
(http://www.youtube.com/watch?v=NNR-26Okvco)
Retrieved from "http://en.wikipedia.org/w/index.php?title=Hydrochloric_acid_regeneration&oldid=606344835"
Categories: Inorganic reactions Chemical processes

This page was last modified on 29 April 2014, at 15:52.

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