SIloxane Kesan Pada Minyak
SIloxane Kesan Pada Minyak
SIloxane Kesan Pada Minyak
Many types of organic material can be used to produce combustible gas, including
organic waste, agricultural biomass, livestock manure, sewage cleaning residue and
landfill. In an oxygen-free environment, bacteria digest the organic material to produce
what is known as biogas, consisting of methane, carbon dioxide and various trace
constituents.
Biogas is converted into electricity by gas engines that typically operate at efficiencies
of greater than 40 percent and produce relatively low levels of harmful exhaust
emissions. Gas engines can run reliably on different qualities of biogas, although
engines running on certain gases require more maintenance than those running on
natural gas.
Engines have been running successfully on biogas in a large number of installations for
many years. For example in 2007, a leading supplier of biogas engines, General Electric
installed more than 1,450 systems in agricultural settings and 1,300 in landfill
applications, totaling more than 2,200 megawatts of electrical capacity. In addition,
several industry sources predict large growth in the coming decade.
The lubricant in engines burning biogas is often more stressed than the same oil in an
engine running on natural gas. The additional stress is caused by trace contaminants in
the gas. Depending on the source, the biogas may contain acidic compounds that can
corrode engine components if not neutralized by alkaline additives. As these additives
are consumed, the oil needs to be changed more frequently.
Other contaminants such as siloxanes have a direct impact on deposit formation in the
combustion chamber. To control deposits, the lubricants contribution to deposit
formation should be minimized. Therefore, the lubricant should prevent the formation of
ash deposits as much as possible.
Biogas Challenges
Biogas from anaerobic bacterial digestion consists of methane, carbon dioxide and a
number of trace compounds. Three challenges related to the combustion of biogas are
acidic compounds, siloxanes and trace compounds.
After combustion and in combination with water, these compounds can form sulfuric
acid, hydrofluoric acid or hydrochloric acid that are highly corrosive to engine
components such as liners, piston rings, piston ring grooves and bearings. They must
be neutralized by the oil to prevent damage.
For this reason, the oil contains alkaline additives that react with acids before they can
reach metal surfaces. Neutralization consumes the additives, and the oil needs to be
changed when they have been depleted.
The alkalinity reserve of oil is represented by its base number. Every engine burns a
small amount of oil, and many types of alkaline additives produce ash when burned that
can contribute to deposits forming in the combustion chamber. For this reason, engine
manufacturers limit the amount of ash producing additives in the oil.
Most OEMs limit ash to 0.6 percent, and such oils are called low-ash oils. Other OEMs
allow oils with up to 1.0 percent ash, and these oils are called medium-ash oils. Because
the oil contains a limited amount of alkaline additives, oil life is highly dependent on the
amount of acidic compounds in the fuel gas.
These deposits cause a number of problems. Piston crown and valve disc deposits
reduce the clearance between these components, potentially causing interference.
Deposits also can increase compression ratio, which can promote detonation (also
called knocking).
Deposits are hard and abrasive, and they have a different coefficient of thermal
expansion than metal. Temperature changes can cause parts of the deposit layer to
break off from the piston and cylinder head, and they can get trapped between the ring
and liner where they are ground up and contribute to high wear.
Other contaminants include ammonia and arsenic. Ammonia can potentially attack the
nonferrous bearing metals.
While technologies have been introduced to remove contaminants from biogas, they are
still relatively new and are quite expensive to install and operate. Therefore, the vast
majority of installations run without such systems.
Although most acids formed by oxidation and nitration are neutralized by the oils
alkaline additives, some acids are so weak that they do not react with the additives. As
long as their concentration is low, these acids are too weak to harm engine bearing
metals.
Total acid number can be used as an indicator of the amount of acid in the oil. Because
even fresh oil will yield a TAN value when tested, the concentration of acids is best
represented by the difference between the TAN of the used oil and that of the fresh oil.
An additional measure is pH number, which describes the strength of the acids
accumulated in the oil. Finally, polymerization products formed during oxidation and
nitration can increase oil viscosity.
It is good practice to take regular oil samples to determine oil condition and rate of
deterioration and, thereby, to determine safe oil drain intervals. This is even more
important in biogas applications because fuel quality can vary significantly over time.
Oil analysis can also detect premature wear in the engine, notably bearing wear and
cooling water leakage. Therefore, it can provide additional safety and peace of mind for
the operator. General criteria for oil rejection are:
Total acid number – maximum 3 milligrams potassium hydroxide/ gram increase over
fresh oil
Minimum pH of 4
A discussion about allowable levels of contaminants is beyond the scope of this article
with the exception of silicon. Silicon accumulation in the oil is normal at plants where
siloxanes are present in the fuel gas. Sometimes, customers use silicon content as a
criterion for oil drain because they see a correlation between silicon level and engine
wear rate. However, while the correlation exists, it is not a cause and effect correlation.
Both conditions are a consequence of high siloxanes in the fuel.
If the oil filtering system removes particles effectively, any silicon in the oil is harmless.
Some OEMs limit silicon in used oil to 300 parts per million; others state that silicon
content has no limit.
Lubricant Formulation
Lubricants formulated for gas engines burning biogas must first be suitable for use with
gas from any source, including biomass, manure, sewage and landfill. And they must be
able to handle the contaminants that these different types of biogas may contain. Also,
ash content must comply with the latest OEM requirements, and the oil must provide
significantly longer life than conventional oils. Finally, it must provide a high level of
engine protection and be suitable for use in engines equipped with exhaust gas catalyst.
The following approach has been used to develop candidate formulations. First,
formulate the oil to retard oxidation and nitration. Slower oxidation contributes directly
to longer oil life. Second, make base number as high as possible to maximize the oils
alkalinity reserve and extend oil life for engines operating on gases containing acidic
compounds. Third, minimize the oil contribution to deposit formation by limiting ash
producing additives to 0.6 percent and by formulating the base oil and additive
combination to be highly resistant to oxidation and carbonization.
To meet all these criteria, modern lubricants are typically formulated with severely
processed API Group II base oils. This approach has been endorsed by a leading OEM
that explicitly prefers Group II based lubricants for its engines running on biogas.
The table compares the characteristics of three candidate formulations, based on a
different additive technology, with a reference oil. Following laboratory bench tests and
in-house engine tests, the candidate oils were tested in GEs Jenbacher J312 GSC21
installed on a landfill site. The installation was not equipped with fuel gas cleaning, but
fuel acidity was relatively mild. An exhaust gas cleaning catalyst was installed.
The rate of oil oxidation was similar for the three candidates. Even after 2,000 hours,
oxidation was below 10, which is considered excellent. However, the oils exhibited very
different base number depletion rates. In fact, rapid base number depletion of Oils C
and D produced shorter oil life than Shell Mysella S5 S, despite their higher initial base
numbers.
With Oil C, oil drain interval would have to be set at 1,200 running hours, and for Oil D
drain interval would have to be set at 1,500 hours. Mysella S5 S, however, can safely
reach 2,680 hours, and extrapolation of the oil condition trends predicts that it could
safely reach 3,000 running hours.
Comparisons of oil life with the benchmark oil at this site show that only Mysella S5 S,
despite its low initial base number, provides significantly longer oil life than the bench-
mark. This is due to its high oxidation resistance, combined with the relatively mild
acidity of the fuel gas. If the fuel gas had a high content of aggressive acidic
compounds, a slow rate of oxidation would not contribute to the oil life extension.
Instead, the oils alkalinity reserve would neutralize the acid compounds to extend oil
life.
Many OEMs, however, do not support the use of medium-ash oils and recommend the
use of low-ash oil even for aggressive landfill gases. In such cases, the new oil would be
expected to provide longer oil life than conventional low-ash oils because its slow rate
of oxidation leaves more base number available for acid neutralization.
For engines running on landfill gas, component condition is a function not only of
running hours, but it is also strongly dependent on fuel characteristics. Besides
neutralizing acid compounds, another important effect is the formation of hard deposits
because of siloxanes in the fuel. The oil has limited influence on deposits because they
are formed during fuel combustion with minimal interaction of the oil. One area where
the oil can contribute is in minimizing the formation of oil-related deposits such as ash
and oil coke.
To check the deposit performance, the combustion chamber was inspected by
boroscope after 3,670 running hours. The inspection showed that liners were in
excellent condition with hardly any wear of the honing pattern. A few liners were
scratched by hard silicon dioxide particles. The good condition was also confirmed by
the engines low and stable oil consumption. Deposits in the combustion chamber were
well controlled, ash layers were relatively thin and no large pieces of solid material
broke out of the deposit layer.
Based on this testing, Shell has commercialized Mysella S5 S and expects it to provide
good engine protection because it has low ash content, reducing the contribution of
lube oil to combustion chamber deposits, and it is formulated with Group II base oil,
which helps to minimize ash and carbon deposits.
Richard Holdsworth is Global Product Marketing Manager – Power and Industry, Shell
International Petroleum Co. Ltd, U.K., he can be contacted at R.Holdsworth@shell.com.
Joerg Reher is Project Leader Marine & Power Engine Lubricants Development, Shell
Global Solutions (Deutschland) GmbH, Germany.
Banyak jenis bahan organik dapat digunakan untuk menghasilkan gas yang mudah
terbakar, termasuk sisa organik, biomas pertanian, baja ternakan, sisa pembersihan
kumbahan dan tempat pembuangan sampah. Dalam persekitaran bebas oksigen,
bakteria mencerna bahan organik untuk menghasilkan apa yang dikenali sebagai
biogas, yang terdiri daripada metana, karbon dioksida dan pelbagai unsur jejak.
Biogas diubah menjadi elektrik oleh enjin gas yang biasanya beroperasi pada
kecekapan melebihi 40 persen dan menghasilkan tahap pelepasan ekzos berbahaya
yang rendah. Enjin gas dapat diandalkan dengan menggunakan kualiti biogas yang
berbeza, walaupun enjin yang menggunakan gas tertentu memerlukan penyelenggaraan
lebih banyak daripada yang menggunakan gas asli.
Laporan Lube Percuma
Ikuti perkembangan industri pelincir global setiap minggu.
Daftar secara PERCUMA
Mesin telah berjaya dijalankan pada biogas dalam sebilangan besar pemasangan
selama bertahun-tahun. Sebagai contoh pada tahun 2007, pembekal enjin biogas
terkemuka, General Electric memasang lebih daripada 1.450 sistem di kawasan
pertanian dan 1.300 dalam aplikasi pelupusan sampah, dengan jumlah kapasiti elektrik
lebih dari 2.200 megawatt. Di samping itu, beberapa sumber industri meramalkan
pertumbuhan yang besar dalam dekad yang akan datang.
Pelincir dalam enjin yang membakar biogas sering lebih tertekan daripada minyak yang
sama pada mesin yang menggunakan gas asli. Tekanan tambahan disebabkan oleh
pencemaran surih di dalam gas. Bergantung pada sumbernya, biogas mungkin
mengandungi sebatian berasid yang dapat menghakis komponen enjin jika tidak
dinetralkan oleh bahan tambahan alkali. Oleh kerana bahan tambahan ini dimakan,
minyak perlu ditukar lebih kerap.
Bahan cemar lain seperti siloksana mempunyai kesan langsung terhadap pembentukan
deposit di ruang pembakaran. Untuk mengawal deposit, sumbangan pelincir untuk
pembentukan deposit harus diminimumkan. Oleh itu, pelincir harus mengelakkan
pembentukan timbunan abu sebanyak mungkin.
Cabaran Biogas
Biogas dari pencernaan bakteria anaerob terdiri daripada metana, karbon dioksida dan
sebilangan sebatian surih. Tiga cabaran yang berkaitan dengan pembakaran biogas
adalah sebatian berasid, siloksana dan sebatian surih.
Selepas pembakaran dan dalam kombinasi dengan air, sebatian ini dapat membentuk
asid sulfurik, asid hidrofluorik atau asid hidroklorik yang sangat menghakis komponen
mesin seperti pelapik, cincin omboh, alur cincin dan galas omboh. Mereka mesti
dinetralkan oleh minyak untuk mengelakkan kerosakan.
Atas sebab ini, minyak mengandungi bahan tambahan alkali yang bertindak balas
dengan asid sebelum boleh sampai ke permukaan logam. Neutralisasi memakan bahan
tambahan, dan minyak perlu diganti apabila habis.
Sebilangan besar OEM mengehadkan abu hingga 0.6 peratus, dan minyak seperti itu
disebut minyak abu rendah. OEM lain membenarkan minyak dengan abu hingga 1.0
peratus, dan minyak ini disebut minyak abu sederhana. Kerana minyak mengandungi
jumlah bahan tambahan alkali yang terhad, jangka hayat minyak sangat bergantung
pada jumlah sebatian berasid dalam gas bahan bakar.
Deposit keras dan kasar, dan mereka mempunyai pekali pengembangan haba yang
berbeza daripada logam. Perubahan suhu boleh menyebabkan bahagian lapisan
deposit terlepas dari piston dan kepala silinder, dan mereka dapat terperangkap di
antara cincin dan pelapik di mana mereka berada di bawah dan menyumbang kepada
keausan yang tinggi.
Walaupun teknologi telah diperkenalkan untuk membuang bahan cemar dari biogas,
teknologi masih relatif baru dan agak mahal untuk dipasang dan dikendalikan. Oleh itu,
sebahagian besar pemasangan dijalankan tanpa sistem sedemikian.
Walaupun sebilangan besar asid yang terbentuk oleh pengoksidaan dan nitrat
dinetralkan oleh bahan tambahan alkali minyak, sebilangan asid begitu lemah sehingga
tidak bertindak balas dengan bahan tambahan. Selagi kepekatannya rendah, asid ini
terlalu lemah untuk membahayakan logam yang mengandungi enjin.
Jumlah bilangan asid boleh digunakan sebagai petunjuk jumlah asid dalam
minyak. Kerana minyak segar bahkan akan menghasilkan nilai TAN ketika diuji,
kepekatan asid paling baik ditunjukkan oleh perbezaan antara TAN minyak terpakai dan
minyak segar. Ukuran tambahan adalah nombor pH, yang menggambarkan kekuatan
asid yang terkumpul di dalam minyak. Akhirnya, produk polimerisasi yang terbentuk
semasa pengoksidaan dan nitrasi dapat meningkatkan kelikatan minyak.
Adalah praktik yang baik untuk mengambil sampel minyak biasa untuk menentukan
keadaan minyak dan kadar kemerosotan dan, dengan itu, untuk menentukan selang
pembuangan minyak yang selamat. Ini lebih penting lagi dalam aplikasi biogas kerana
kualiti bahan bakar dapat berubah dengan ketara dari masa ke masa.
PH minimum 4
Kelikatan pada 100 darjah C dari 12.0 hingga 17.5 milimeter persegi sesaat
Perbincangan mengenai tahap pencemaran yang dibenarkan adalah di luar ruang
lingkup artikel ini kecuali silikon. Pengumpulan silikon dalam minyak adalah normal
pada tanaman di mana siloksana ada di dalam gas bahan bakar. Kadang kala,
pelanggan menggunakan kandungan silikon sebagai kriteria pengaliran minyak kerana
mereka melihat hubungan antara tahap silikon dan kadar haus enjin. Walau
bagaimanapun, walaupun korelasi itu ada, itu bukan korelasi sebab dan akibat. Kedua-
dua keadaan adalah akibat daripada siloksana tinggi dalam bahan bakar.
Formulasi pelincir
Pelincir yang diformulasikan untuk enjin gas yang membakar biogas terlebih dahulu
sesuai digunakan dengan gas dari mana-mana sumber, termasuk biojisim, baja,
kumbahan dan tempat pembuangan sampah. Dan mereka mesti dapat menangani
bahan cemar yang mungkin terdapat dalam pelbagai jenis biogas ini. Juga, kandungan
abu mesti memenuhi keperluan OEM terkini, dan minyak mesti memberikan jangka
hayat yang lebih lama daripada minyak konvensional. Akhirnya, ia mesti memberikan
tahap perlindungan enjin yang tinggi dan sesuai digunakan dalam mesin yang
dilengkapi dengan pemangkin gas ekzos.
Untuk memenuhi semua kriteria ini, pelincir moden biasanya diformulasikan dengan
minyak asas API II yang diproses dengan teruk. Pendekatan ini telah disokong oleh
OEM terkemuka yang secara eksplisit lebih suka pelumas berasaskan Kumpulan II
untuk enjinnya yang menggunakan biogas.
Jadual membandingkan ciri tiga formula calon, berdasarkan teknologi aditif yang
berbeza, dengan minyak rujukan. Setelah ujian bangku makmal dan ujian mesin
dalaman, minyak calon diuji dalam GEs Jenbacher J312 GSC21 yang dipasang di tapak
pelupusan sampah. Pemasangannya tidak dilengkapi dengan pembersihan gas bahan
bakar, tetapi keasidan bahan bakar relatif ringan. Pemangkin pembersih gas ekzos
dipasang.
Dengan Oil C, selang pengaliran minyak harus ditetapkan pada 1.200 jam berjalan, dan
selang pengaliran Minyak D harus ditetapkan pada 1.500 jam. Namun, Mysella S5 S
dapat mencapai 2,680 jam dengan selamat, dan ekstrapolasi tren keadaan minyak
meramalkan bahawa ia dapat mencapai 3,000 jam berjalan dengan selamat.
Perbandingan jangka hayat minyak dengan minyak penanda aras di laman web ini
menunjukkan bahawa hanya Mysella S5 S, walaupun bilangan asas awalnya rendah,
memberikan hayat minyak yang jauh lebih lama daripada penanda aras. Ini disebabkan
oleh ketahanan pengoksidaan yang tinggi, digabungkan dengan keasidan gas bahan api
yang agak ringan. Sekiranya gas bahan bakar mempunyai kandungan sebatian asid
agresif yang tinggi, kadar pengoksidaan yang perlahan tidak akan menyumbang kepada
pelanjutan hayat minyak. Sebaliknya, simpanan alkaliniti minyak akan meneutralkan
sebatian asid untuk memanjangkan jangka hayat minyak.
Melindungi Enjin
Untuk enjin yang menggunakan gas pelupusan, keadaan komponen adalah fungsi
bukan hanya jam berjalan, tetapi juga sangat bergantung pada ciri bahan bakar. Selain
meneutralkan sebatian asid, kesan penting lain adalah pembentukan deposit keras
kerana siloksana dalam bahan bakar. Minyak mempunyai pengaruh terhad terhadap
deposit kerana terbentuk semasa pembakaran bahan bakar dengan interaksi minyak
yang minimum. Salah satu kawasan di mana minyak dapat menyumbang adalah
dengan meminimumkan pembentukan deposit yang berkaitan dengan minyak seperti
abu dan minyak kok.
Untuk memeriksa prestasi deposit, ruang pembakaran diperiksa oleh boroskop setelah
3,670 jam berjalan. Pemeriksaan menunjukkan bahawa pelapik berada dalam keadaan
yang sangat baik dengan hampir tidak memakai corak pengasah. Beberapa pelapik
digores oleh partikel silikon dioksida keras. Keadaan yang baik juga disahkan oleh
penggunaan minyak yang rendah dan stabil. Deposit di ruang pembakaran dikawal
dengan baik, lapisan abu agak tipis dan tidak ada kepingan besar dari bahan pepejal
yang keluar dari lapisan deposit.
Richard Holdsworth adalah Pengurus Pemasaran Produk Global - Tenaga dan Industri,
Shell International Petroleum Co. Ltd, UK, dia dapat dihubungi di
R.Holdsworth@shell.com.
Joerg Reher adalah Pemimpin Projek Pengembangan Pelincir Laut & Enjin Tenaga, Shell
Global Solutions (Deutschland) GmbH, Jerman.
Thijs Schasfoort adalah Pakar Aplikasi Produk - Pelincir untuk Mesin Stasioner, Shell
Global Solutions International BV, Belanda.
Silicon Doesn't Always Mean Dirt
Noria Corporation
One of the most fundamental truths that many oil analysis users learn is that elevated silicon
levels from elemental spectroscopic data equate to dirt ingression. The logic is simple: common
dirt from road dust and other sources contain high levels of silica.
Therefore, elevated silicon from spectrometric analysis means dirt ingression. But is this true in
every situation? What other possible sources of silicon exist in a lubricating oil environment that
may cause silicon levels to rise?
Depending on the environment in which the equipment is operating, silicon may appear in the
lubricant for various reasons.
Salah satu kebenaran paling mendasar yang dipelajari oleh banyak pengguna analisis minyak
adalah bahawa peningkatan tahap silikon dari data spektroskopi elemen sama dengan penyerapan
kotoran. Logikanya mudah: kotoran biasa dari debu jalan dan sumber lain mengandungi silika
yang tinggi.
Oleh itu, silikon tinggi dari analisis spektrometrik bermaksud kemasukan kotoran. Tetapi adakah
ini benar dalam setiap keadaan? Apakah sumber silikon lain yang mungkin terdapat di
persekitaran minyak pelincir yang boleh menyebabkan tahap silikon meningkat?
Bergantung pada persekitaran di mana peralatan beroperasi, silikon mungkin muncul di pelincir
kerana pelbagai sebab.