Académique Documents
Professionnel Documents
Culture Documents
I
n petroleum refineries, distillation and Types of cleaning chemicals which requires the draining of the
storage equipment frequently needs The most common types of chemicals hydrocarbon phase first. The cleaning
to be inspected during turnarounds. used for the cleaning of equipment are and degassing programmes are
Necessary cleaning procedures can inorganic and organic acids, chelating commonly designed for injection into
require several weeks of downtime if and complexing agents, alkaline the wash water phase at temperatures
storage tanks, distillation columns, cleaners, surfactants, organic solvents between 60°C and 100°C with circulation
product lines and heat exchangers have and speciality additives. times of 2–16 hours. Some cleaning
to be drained. The presence of volatile For the removal of oxides and scales, programmes create a temporary emulsion
hydrocarbons and hydrogen sulphide common acid cleaning agents such as for scavenging the hydrogen sulphide
gas, as well as deposits of pyrophoric inhibited sulphuric acid and and volatile hydrocarbons. The emulsion
iron sulphide and other fouling material, hydrochloric acid, phosphoric acid, will later break down on its own in the
can be particularly problematic, which citric acid or other weaker acids are used. API separator or in a separate holding
is why they have to be removed before By varying the chemical concentration, tank. The addition of an emulsion
inspection. temperature and agitation, the metal breaker after the cleaning procedure is
For many years, traditional mechanical surface can be cleaned slowly or more completed can accelerate the separation
cleaning methods such as high-pressure rapidly. Concentrated solutions and process. In many cases, the intermittent
and ultra-high-pressure water jetting, higher temperatures will accelerate the storage of cleaning solutions for emulsion
steaming procedures and cold or hot cleaning procedure, but leads to the breaking is limited, because the necessary
water washing methods have been used generation of dangerous and corrosive holding tanks are occupied for other
to remove volatile hydrocarbon and fumes as well as increased corrosion purposes during planned turnarounds,
hydrogen sulphide gases. However, large potential. and some refiners refuse to apply
volumes of water are required and the Caustic cleaning agents are less chemical cleaning programmes that
resulting wash water can be high in TOC. efficient and less economical compared create emulsions. Kurita is asked to
Based on regulatory, safety and with acid cleaning agents, but they can deliver cleaning and degassing
environmental requirements, more remove organic soils, including oils and programmes that create a temporary
powerful chemical cleaning and grease, better than acids. emulsion, as well as programmes without
degassing products have been developed Chelating and complexing additives any emulsification tendency.
to shorten downtime by reducing the containing EDTA, NTA and sodium
need for mechanical cleaning. diethanolglycine or ethylenediamine Removal of pyrophoric iron
The applied technology and cleaning play a less important role in refinery sulphide deposits
procedure will depend on the equipment cleaning procedures because of their Due to the pyrophoric nature of iron
to be cleaned. For example, the chemical negative environmental impacts. sulphide and the potential for
cleaning of a crude oil tank or sludge Surfactants can contain anionic, spontaneous ignition, refiners are very
oil system using external mobile heat nonionic or amphoteric compounds interested in removing or neutralising
exchangers will take longer than the and sometimes they are formulated iron sulphide deposits. Although some
chemical cleaning of a distillation together with organic solvents to chemical programmes are fairly effective
column or heat exchanger, where improve their cleaning performance. and can eliminate small, localised iron
high-pressure cleaning equipment sulphide deposits, they have limitations
can be used. The chemical cleaning Cleaning and degassing and are often less effective when the
itself is defined as the removal of organic chemicals iron sulphide deposits are spread
and inorganic fouling material from In general, cleaning agents are designed throughout the packing material of the
process lines, distillation equipment and for scale and fouling removal (ie, viscous distillation equipment.
metal surfaces by a combination of fouling, pyrophoric iron sulphides) with If higher amounts of iron sulphide
solvency, fluid velocity and, in most metal surface cleaning. In addition to deposits are expected (ie, in packing
cases, heat. While the fluid velocity these requirements, the cleaning and areas), the cleaning and degassing
comes from spraying, stirring, degassing agents for refinery and chemicals may reach their limits, as they
circulation, steam or air addition and petrochemical applications are designed are designed mainly for volatile
the heat will be supplied through for the reduction of benzene and other hydrocarbons and hydrogen sulphide
steaming, hot water injection or heating volatile hydrocarbons, as well as removal. For this reason, a formulation
up the metal surfaces, the solvency hydrogen sulphide in the vapour phase. for providing fast and efficient removal
depends on the chemistry of the These chemical programmes are of iron sulphide deposits has been
cleaning agent and its concentration. typically injected into an aqueous phase, developed. This formulation does not
Chemical cleaning of
distillation equipment
While tank-cleaning procedures may
require dosing pumps for the chemicals,
mobile heat exchangers, high-pressure
or ultra-high water jetting, steam, hot
water, gas oil or diesel diluents, the
Figure 2 Cleaning methods application of a chemical for a tower-
cleaning and degassing procedure is
generate hydrogen sulphide or produce tank. When such storage tanks are more simple. During the turnaround
solid reaction products, which is why it emptied to be cleaned, conventional procedure, the refinery heat exchangers
is ideally suited to iron sulphide cleaning methods may require some and pumps can be used to provide
dissolution applications. As a further days or even weeks. For this reason, new the heat and fluid velocity. The way
advantage, it can be injected into both chemical cleaning programmes have in which the chemical is applied to
hydrocarbon and aqueous product been developed to reduce the time the system depends on the process
streams and combined with Kurita’s required to remove the sludge from conditions.
proprietary hydrogen sulphide and the tank. It is sometimes not possible to provide
benzene scavengers to provide a highly There are a number of different a system where the chemical can be
effective all-round chemical-treatment standard cleaning procedures pumped back. More chemical and wash
programme (Figure 1). introduced to the oil refining industry, water is therefore required. In this case,
and each cleaning technique can be the chemical has to be applied to the
Tank cleaning characterised according to a cleaning wash water at the top section of the
In crude oil and heavy oil storage, sludge procedure. Some cleaning procedures distillation column or reflux line
always accumulates at the bottom of the will require the use of a suitable (cascading method). Steam can be added
Conclusions
Refinery equipment that is commonly
cleaned chemically includes boilers,
tanks, heat exchangers, fin-fan coolers,
hydraulic lines, reactors, condensers
piping systems, refinery towers and
cooling systems. During a refinery
turnaround, much of the work involves
cleaning, and the turnaround is carefully
planned months in advance. Regulatory,
safety and environmental requirements
are increasing the demands on
turnaround operations in refineries and
other petrochemical plants.
Figure 4 Packing area of a distillation column after chemical cleaning Whenever a piece of equipment has
to be cleaned, there are key parameters
distribution system, the potential representative samples are taken. Storage to be considered for a proper cleaning
formation of ammonium salt deposits is tanks are not homogenous, which is method selection:
considered to be a critical factor for the why samples should be taken from as — The surface to be cleaned
continuous and efficient operation of many sampling points as possible. If — Waste removal
the fuel gas system. samples have to be taken from tanks, — Application method
The mechanical cleaning of blocked most refineries use different types of — Present results
burner nozzles requires three to four sample thieves. A cage with a sample — Available contact time
man-hours and an average burner bottle, or a graduated glass cylinder in a — Chemical content restrictions
cleaning cycle is three to four months. sampling container with a trap door — Process conditions
Having 30–50 heaters with many burner that closes on the bottom of the — Final conditions of work.
nozzles installed, mechanical cleaning graduated cylinder are two examples of The type of cleaning chemical has to
may cost some hundred thousand sampling devices. If there are no be chosen carefully. Concentrated
euros per year. Although ammonium sampling points installed, the water solutions of inhibited acid cleaners can
salts are water-soluble, steam-cleaning draw can be used for sampling. After generate dangerous and corrosive fumes
procedures often show a limited success. opening the valve, any sludge-type at higher temperatures, and can cause
An alternative to mechanical cleaning material can be collected. This way stress corrosion cracking at high nickel
and steam cleaning is the ACF of sampling may not be representative, alloys. Alkaline cleaners can remove
technology developed by Kurita, where but it is better than having no sample only limited types of scale, and higher
the ACF product is injected into at all. temperatures are required.
the fuel gas system to remove The chemical cleaning of distillation Suitable chemicals including
ammonium salt deposits. Within a few equipment will require 2–16 hours. proprietary products to remove
minutes, the fouling material can be Before and during the procedure, pyrophoric iron sulphide deposits have
removed, and burner flames will samples can be taken to observe the been developed for degassing and
look good and the burner tips will progress of the cleaning. The decontamination, and can be solvent-
live longer. concentration of “actives”, the or water-based products. Refineries
temperature of the washing solution, generally prefer water-based cleaners
Sampling and monitoring colour, pH, iron concentration, and solvent cleaners that do not
For tank cleaning, the success of the chlorides, ammonia and sulphides are form emulsions. These products will
cleaning technology can be determined typical parameters for refinery cleaning provide faster and safer results on
by a good survey and laboratory testing procedures. During cleaning, the cleaning the metal surface, reducing
before and during cleaning. It is samples appear to look more and more benzene and other volatile
important to obtain information on the dirty, and the increase in analysed hydrocarbons, hydrogen sulphide and
composition of the bottom sludge, iron, chlorides, sulphides and ammonia ammonia levels. This will help reduce
which can contain oil, water, volatile indicates the mobilisation of the fouled the turnaround time, air emissions,
solids, ash and sediments. The material. When the increase in waste, labour costs and pollution-
concentration of water and sediment concentration of these parameters control costs.
content of crude oils is significant, slows down, it is an indication that
because it can cause corrosion of the the end of the cleaning is imminent
distillation equipment. A determination or more or new cleaning chemical is
of water and sediments is required to required.
measure accurately net volumes of The heat-transfer coefficient and the
actual oil in sales. Based on the cleaning pressure drop of heat exchangers, the Berthold Otzisk is a technical engineer at
technology, recovered oil can be directed sampling of fouled materials, ultrasonic Kurita Europe GmbH, Viersen, Germany.
to the refining process again, increasing measuring equipment and former Otzisk has more than 15 years’ experience
refinery profit. turnaround reports on observed fouling in sales, service and research of new
The best results are obtained when are all good tools for estimating the technologies. Email: otzisk@kurita.de