Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
Sulfuric Acid T O D A Y
E B R A T
20
L
www.H 2S0 4Today.com Fall/Winter 2014 E
I
C
N
G
1994
2014
Y
E A
R S
Spreading
HydrOgen SaFety
wOrldwide page 7
Theoretical background about the possible sources and mechanism of the ignition.
introduction Understand the causes of hydrogen incidents.
The formation of hydrogen in sulfuric acid plants Plant and equipment design
is a known phenomenon resulting from the corrosion Issues and facts to consider when designing/modifying
explosion limits
of metallic materials under specific conditions. Those This section discusses the factors relating to hydrogens
a plant or equipment. explosion limits.
conditions are strongly dependent on acid strength and Operational and maintenance practices Explosion limits of hydrogen in air and air/nitrogen
temperature. As a result, a mixture of hydrogen and oxygen How do you know that there is an issue and do you at room temperature, measured by various standards (in
containing process gas can occur with the potential risk of know how to respond if there is an issue? mole-%)
a hydrogen explosion. The intention of this work is to bring awareness to this
Over the last few years, several incidents related to this important topic and provide high level recommendations DIN 51649 EN 1839(T) EN 1839(B) ASTM E681
have been reported. The majority of the reported hydrogen and support for decision and concept finding, training of LEL (H2 in air) 3.8 3.6 4.2 3.75
events took place in intermediate absorption systems, personnel and/or establishing mitigation measures. Firstly,
UEL (H2 in air) 75.8 76.6 77.0 75.1
converters or heat recovery systems. In general, the an understanding of the chemistry and the root causes for
incidents occurred during maintenance or after stopping such events is fundamental. The measures to be undertaken LEL (40% N2 +air) 3.6 3.6 4.4 3.65
the gas flow through the plant. In all cases, water ingress, to avoid or mitigate such events must cover a multitude UEL (40% N2 + air) 38.2 38.4 38.2 37.3
resulting in low acid concentration, caused the formation of of aspects that cant be covered in one general document.
the hydrogen. In most of the cases, the water ingress was One has to be aware that there are, to each and every plant,
ignored or not noted and mitigation measures were not in details that need to be elaborated individually. The case with 40 percent by volume N2 leaves a residual
place. As a result, plant equipment was severely damaged. oxygen content of about 13 percent by volume, which is
An international group from the sulfuric acid industry about double to triple the content usually experienced at the
theoretical considerations
formed an expert committee dedicated to this topic. The The risk of a hydrogen explosion basically depends on
members of this committee are from plant operation, three factors, which have to happen in sequence: Influence of temperature on explosion limits of hydrogen/air mixtures
consultancy as well as equipment/plant design disciplines. Hydrogen generation (corrosion). Temperature in C LEL (mole-%) UEL (mole-%)
The aim of the group was to analyze well Formation of an explosive mixture of hydrogen and 20 3.9 75.2
documented hydrogen incidents in acid plants and oxygen containing process gas. 100 3.4 77.6
identify high level considerations to assist operators Ignition of the hydrogen/oxygen/process gas mixture.
200 2.9 81.3
and plant designers in avoiding/minimizing risk and While the formation of hydrogen and the explosion
300 2.1 83.9
mitigating potential consequences. This document limits are well known and based on hydrogen release as
400 1.5 87.6
summarizes the findings, considering: an effect of corrosion products, there are no hard facts
area of the highest potential for hydrogen formation. Do operators understand to look out for early warning Bartlett, email: collin.bartlett@outotec.com; Karl Daum,
What are implications of construction materials? signals? email: karl-heinz.daum@outotec.com; and George Wang,
Stainless steel towers are easy to install, however How are new operators trained? email: George.Wang@solvay.com. q
they offer a reduced operation window. Can it be Is the equipment regularly inspected/tested?
ensured that the towers can be drained in case of upset Ensure that bypass and drain valves work.
operation (weak acid)? Ensure the drain line and disposal area is not
references
V.Scroeder and K Holtappels, Explosion Characteristics of
Bricklined towers are significantly more robust and blocked.
Hydrogen-Air and Hydrogen-Oxygen Mixtures at Elevated
less exposed to corrosion and so weak acid could Ensure that drains are cleaned at every shut down. Pressures
remain stored in the tower sump or pump tank for Early warning of a problem is vital.
some time. Has the material decision been triggered Are sufficient instruments installed? Z. M. Shapiro and T. R. Moffette, Hydrogen Flammability
by the draining concept? Analyzers on cooling water return, one per cooler. Data and Application to PWR Loss of Coolant Accident-
Consider a design to minimize vapor and stagnant gas Consider water and acid temperature measurement. WAPD-SC -545 1957
spaces. Redundancy of acid measurement in cooling water HF Coward and GW Jones, Limits of Flammability of Gases
Consider standing vs. hanging candle filters, as in (pH-meter, conductivity, etc.). and Vapors-Bureau of Mines Bulletins 503-1952
Fig. 9. Are instruments maintained regularly, including I.L. Drell and F.E. Belles, Report 1383, Survey of Hydrogen
Consider top vs. lateral gas outlet, as in Fig. 10. cooling water loops? Combustion Properties NACA Lewis Lab-1957
Consider the maintenance concept: in-tower candle Is the available information used in a smart way?
MG Fontana IEC Vol 43, Aug 1951 P65A
replacement vs. cutting of roof. Is a data management system used, e.g., acid plant General Chemical Data
Consider options to remove hydrogen from the water balance system?
potential areas in the tower: Are historical trends used? N.D. Tomashov, Theory of Corrosion and Protection of
Purging using main blower after acid pumps are out Is the anodic protection understood? Changes in Metals
of operation. current/voltage indicate a problem at a very early Inco CEB-1-1983, The Corrosion Resistant of Nickel
Purging using nitrogen (if available). stage. Containing Alloys in Sulfuric Acid and Related Compounds
Purging using high point purging vents. Do maintenance procedures consider adequate purging
and flammable gas testing?
2015 Sulfuric acid roundtable
Conclusion set for florida
Generation of hydrogen in a sulfuric acid plant is a
Fig. 9: Standing well-known phenomenon, but for some unknown reason, COVINGTON, La.Sulfuric Acid Today is pleased
candle filters (left) the incidence of hydrogen explosions has recently been on to announce that the 2015 Sulfuric Acid Roundtable
versus hanging
the rise. Fortunately, there have been no serious injuries to is scheduled for March 23-26, 2015. This years
candle filters. roundtable will take place at the newly constructed
date. But, unless hydrogen safety is brought to the forefront
of our thinking, the consequences could become more dire. Streamsong Resort in central Florida.
Attracting an international audience of
There are many potential causes for the increased incidence
professionals in the phosphate, metallurgical/smelting
of hydrogen explosions, including the age of operating
and acid regeneration industries, this biennial
sulfuric acid plants, the increased use of stainless steel
conference provides a venue for participants to learn
equipment in lieu of traditional brick and cast iron materials, the latest sulfuric acid technologies and exchange best
new maintenance practices, new safety and environmental practices. The schedule will closely follow the model
regulations that limit the ability of operators to perform of previous meetings. It will consist of two and a half
traditional operational checks (such as draining drip acid days of informative presentations from the conferences
Fig. 10: Top gas from equipment) and a loss of operating experience, due to co-sponsoring firms along with insightful producing
outlet (left) versus
demographics. plant presentations, maintenance panel discussions, a
lateral outlet.
Moving forward, all parties involved must recognize keynote address on the global sulfuric acid market for
that equipment failures are inevitable and when water is 2015 and an update on hydrogen safety. There will be
involved, a weak acid excursion can occur. This article has ample networking opportunities to meet co-sponsor
shown that the conditions leading to the formation of an representatives and peruse their exhibits of acid plant
explosive mixture can occur rapidly and immediate action supplies and services.
This years location will also allow roundtable
is required that can only be achieved via thorough planning
operation and maintenance and procedures. By disseminating this information, the
attendees to take advantage of many recreational
Irrespective of implementing previous suggestions, the activities, including golf, fishing, hiking and clay
hope is that operators and designers alike become more
key to avoiding such events is operator and maintenance shooting. An exciting new feature of this years
aware of the hazards, making new plants better equipped roundtable will be a tour of Mosaics New Wales
personnel awareness of the theory behind hydrogen for hydrogen safety and helping existing plants stay out of Phosphate Fertilizer Complex in Mulberry, Fla. The New
formation and the potential consequences. Operators have potentially dangerous situations. Wales site, which has been in operation since 1975, sports
to plan and be prepared for such events, ensuring early Any questions pertaining to hydrogen-related incidents, five sulfuric acid plants producing 14,000 TPD and three
detection, mitigation and prevention.
redesigns or operations can be brought to the attention of turbine generators capable of producing over 100 MW
Do the following operational/maintenance procedures
the Hydrogen Safety Committee by contacting any member of electricity. The site manufactures over 4 million TPY
cover such events? of phosphate fertilizers and is also one of the largest
of the group via email. Len Friedman, email: acideng@
Regular and emergency shutdown procedures. producers of animal feed supplements in the world.
icloud.com; Rick Davis, email: rick@consultdac.com;
Equipment evacuation procedures. For more information on the roundtable or
Steven Puricelli, email: steven.m.puricelli@mecsglobal.
Do operators have the chance to practice for such events? to register, please visit www.acidroundtable.com.
com; Michael Fenton, email: Michael.Fenton@jacobs.com;
How is it is ensured that the procedures will work? Rene Dijkstra, email: Rene.Dijkstra@jacobs.com; James For sponsorship opportunities, please contact
Transfer experience (legacy planning). Kathy Hayward, (985) 807-3868 or email kathy@
W. Dougherty, email: James.Dougherty@mosaicco.com;
Test operator skills. h2so4today.com. q
Hannes Storch, email: hannes.storch@outotec.com; Collin