CA2314356A1 - Anti-coking coatings for refractory alloys used in the petroleum field - Google Patents
Anti-coking coatings for refractory alloys used in the petroleum field Download PDFInfo
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- CA2314356A1 CA2314356A1 CA002314356A CA2314356A CA2314356A1 CA 2314356 A1 CA2314356 A1 CA 2314356A1 CA 002314356 A CA002314356 A CA 002314356A CA 2314356 A CA2314356 A CA 2314356A CA 2314356 A1 CA2314356 A1 CA 2314356A1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/308—Oxynitrides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
- C10G9/18—Apparatus
- C10G9/20—Tube furnaces
- C10G9/203—Tube furnaces chemical composition of the tubes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0209—Pretreatment of the material to be coated by heating
- C23C16/0218—Pretreatment of the material to be coated by heating in a reactive atmosphere
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
- C23C16/0245—Pretreatment of the material to be coated by cleaning or etching by etching with a plasma
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
- C23C16/345—Silicon nitride
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/401—Oxides containing silicon
- C23C16/402—Silicon dioxide
Abstract
The invention concerns anti-coking coats for refractory alloys used in the oil industry. Said coats are obtained by a method comprising the following steps: 1) submitting the refractory alloy surface (5) to the action of an oxygen and/or nitrogen gas plasma at a low frequency; 2) depositing on the treated surface a coating based on silicon oxide, nitride or oxynitride by plasma enhanced chemical vapour deposition at low frequency, from an organosilicon compound and a gas selected among oxygen and nitrogen; the two steps being carried out consecutively and continuously in the same installation (1) without venting between the two steps.
Description
ANTI-COKING COATINGS FOR REFRACTORY ALLOYS USED IN THE
PETROLEUM FIELD
DESCRIPTION
Technical field The object of the present invention is anti-coking coatings for preventing the deposition of coke on refractory alloy parts used in the petroleum field.
In petrol refineries, thermal power stations, polymer production installations and elsewhere, there exist numerous components which are in contact with hot fluids containing hydrocarbons, at temperatures at which degradation products form in the hydrocarbons and may lead to deposits of coke on the components.
The coke has several origins:
- It may be a case of "pyrolitic" coke inherent in the process. Thus, during the steam cracking of hydrocarbons, the chemical reactions result from the cracking of the carbon chains with the consequence of creating the required light gases (ethylene and propylene) and the formation of pyrolitic coke.
- It may be a question of "catalytic" coke due to the presence, in large quantities, of elements reputed to promote coking, such as nickel and iron, in the B 13166.3 MDT
PETROLEUM FIELD
DESCRIPTION
Technical field The object of the present invention is anti-coking coatings for preventing the deposition of coke on refractory alloy parts used in the petroleum field.
In petrol refineries, thermal power stations, polymer production installations and elsewhere, there exist numerous components which are in contact with hot fluids containing hydrocarbons, at temperatures at which degradation products form in the hydrocarbons and may lead to deposits of coke on the components.
The coke has several origins:
- It may be a case of "pyrolitic" coke inherent in the process. Thus, during the steam cracking of hydrocarbons, the chemical reactions result from the cracking of the carbon chains with the consequence of creating the required light gases (ethylene and propylene) and the formation of pyrolitic coke.
- It may be a question of "catalytic" coke due to the presence, in large quantities, of elements reputed to promote coking, such as nickel and iron, in the B 13166.3 MDT
components in contact with the hydrocarbons. These elements (nickel and iron) cause the heterogeneous catalysis of different chemical reactions giving rise to the production of solid carbon deposited on the surfaces in the form of filaments and/or amorphous carbon.
Coke causes corrosion phenomena in the components, for example petrochemical furnace tubes. It becomes established on the walls of the tubes and, preferentially, on the hottest parts. The different problems related to the deposition of coke are as follows:
1) A loss of heat transfer from outside the tube to the inside since the coke acts as a thermal insulant, which requires more energetic heating in order to obtain, for example, the required steam cracking temperature (approximately 850°C). There is then a risk of damaging the refractory alloy in the tube and, at the end of a certain time, the operator must inevitably perform a decoking operation, that is to say eliminate this coke by oxidising it by means of water vapour and/or air.
2) A carbonising of the tubes. This is because, although a protective layer containing chromium generally forms on the surface of the tube, the latter cracks easily because of compression stresses caused by a difference in metal/oxide mesh as well as by the conditions of use of the steam cracking tubes (thermal shacks due to the coking/decoking cycle).
Thus there is a great advantage in finding the means of preventing the deposition of coke on the refractory B 13166.3 MDT
Coke causes corrosion phenomena in the components, for example petrochemical furnace tubes. It becomes established on the walls of the tubes and, preferentially, on the hottest parts. The different problems related to the deposition of coke are as follows:
1) A loss of heat transfer from outside the tube to the inside since the coke acts as a thermal insulant, which requires more energetic heating in order to obtain, for example, the required steam cracking temperature (approximately 850°C). There is then a risk of damaging the refractory alloy in the tube and, at the end of a certain time, the operator must inevitably perform a decoking operation, that is to say eliminate this coke by oxidising it by means of water vapour and/or air.
2) A carbonising of the tubes. This is because, although a protective layer containing chromium generally forms on the surface of the tube, the latter cracks easily because of compression stresses caused by a difference in metal/oxide mesh as well as by the conditions of use of the steam cracking tubes (thermal shacks due to the coking/decoking cycle).
Thus there is a great advantage in finding the means of preventing the deposition of coke on the refractory B 13166.3 MDT
alloy surfaces in contact with hot fluids containing hydrocarbons.
Prior art The most widely used technique for preventing or restricting the deposition of coke on metallic surfaces is to apply an anti-coking coating to the latter.
Thus the document FR-A-2 662 704 [1] makes provision for using, as an anti-coking coating, oxides, carbides, nitrides and/or silicides such as titanium, zirconium and niobium silicides, this coating being able to be applied by conventional methods such as chemical vapour deposition (CVD) or plasma assisted chemical vapour deposition (PACVD). In this document, good results are obtained with a metallic surface of nickel superalloy with a deposit of alumina by impregnation by means of a slurry, or a deposition of titanium carbide by chemical vapour deposition.
The documents EP-A-0 607 651 [2] and EP-A-0 608 081 [3]
illustrate the use of coatings based on metallic oxides, metallic fluorides or mixtures thereof in order to prevent the deposition of coke on stainless steel surfaces.
The document US-A-5,266,360 [4] illustrates the use of coatings based on Si02, alumina or tungsten disulphide, possibly comprising particles of metallic oxides such as alumina, cerium oxide and cupric oxide for inhibiting the formation of coke on gas turbine components.
In documents [2] and [3], deposition is effected by CVD
whilst in document [4] the coatings of Si02 are B 13166.3 MDT
Prior art The most widely used technique for preventing or restricting the deposition of coke on metallic surfaces is to apply an anti-coking coating to the latter.
Thus the document FR-A-2 662 704 [1] makes provision for using, as an anti-coking coating, oxides, carbides, nitrides and/or silicides such as titanium, zirconium and niobium silicides, this coating being able to be applied by conventional methods such as chemical vapour deposition (CVD) or plasma assisted chemical vapour deposition (PACVD). In this document, good results are obtained with a metallic surface of nickel superalloy with a deposit of alumina by impregnation by means of a slurry, or a deposition of titanium carbide by chemical vapour deposition.
The documents EP-A-0 607 651 [2] and EP-A-0 608 081 [3]
illustrate the use of coatings based on metallic oxides, metallic fluorides or mixtures thereof in order to prevent the deposition of coke on stainless steel surfaces.
The document US-A-5,266,360 [4] illustrates the use of coatings based on Si02, alumina or tungsten disulphide, possibly comprising particles of metallic oxides such as alumina, cerium oxide and cupric oxide for inhibiting the formation of coke on gas turbine components.
In documents [2] and [3], deposition is effected by CVD
whilst in document [4] the coatings of Si02 are B 13166.3 MDT
obtained by immersion in an appropriate solution, using the sol-gel technique.
Thus the most widely used coatings for preventing or limiting the deposition of coke on metallic surfaces are based on oxide, in particular Si02.
Disclosure of the invention The object of the present invention is novel coatings and a novel method for preventing the deposition of coke on a refractory alloy surface in contact with fluids containing hydrocarbons.
According to the invention, the method for preventing the deposition of coke on a refractory alloy surface in contact with fluids containing hydrocarbons comprises the following steps:
1) subjecting the refractory alloy surface to the action of a gaseous plasma of oxygen and/or nitrogen at low frequency, and 2) depositing on the surface thus treated a coating based on silicon oxide, nitride or oxynitride by plasma assisted chemical vapour deposition at low frequency, using an organosilicic compound and a gas chosen from amongst oxygen and nitrogen, the two steps being performed consecutively and continuously in the same installation without opening to atmosphere between the two steps.
The first step in this method consists of diffusing oxygen and/or nitrogen in the refractory alloy. This diffusion treatment corresponds either to a nitriding, or to an oxidation, or an oxynitriding. In the case of a metallic refractory alloy surface including nickel B 13166.3 MDT
and iron, this treatment repels the elements facilitating coking such as nickel and iron, and thus prepares the surface for receiving a deposit whilst in addition promoting the adhesion of the deposit which 5 will then be formed in the second step.
According to the invention, the two steps of the method are carried out in the same plasma assisted chemical vapour deposition reactor, which has a system for feeding the different gases used, such as oxygen, nitrogen, the organosilicic compound and possibly argon.
According to the invention, each of the steps is performed using a low frequency, for example a frequency situated in the range from 2 to 450 kHz.
Thus a low plasma density is obtained, along with more homogeneous deposits able to cover parts of large size.
According to a preferred embodiment of the invention, a coating based on silicon oxynitride is deposited in the second step by PACVD.
In this case, it is possible to use, for the PACVD
deposition, an organosilicic compound containing nitrogen, for example hexamethyldisilazane. The mixture used for this deposition of silicon oxynitride is a mixture of the nitrogenous organosilicic compound, for example hexamethyldisilazane, and oxygen.
Preferably, in this case, a gaseous oxygen plasma is used in the first step for oxidising the refractory alloy surface.
The coating obtained under these conditions is a silicon oxynitride coating of formula SiOXNy, in which x and y are such that:
B 13166.3 MDT
Thus the most widely used coatings for preventing or limiting the deposition of coke on metallic surfaces are based on oxide, in particular Si02.
Disclosure of the invention The object of the present invention is novel coatings and a novel method for preventing the deposition of coke on a refractory alloy surface in contact with fluids containing hydrocarbons.
According to the invention, the method for preventing the deposition of coke on a refractory alloy surface in contact with fluids containing hydrocarbons comprises the following steps:
1) subjecting the refractory alloy surface to the action of a gaseous plasma of oxygen and/or nitrogen at low frequency, and 2) depositing on the surface thus treated a coating based on silicon oxide, nitride or oxynitride by plasma assisted chemical vapour deposition at low frequency, using an organosilicic compound and a gas chosen from amongst oxygen and nitrogen, the two steps being performed consecutively and continuously in the same installation without opening to atmosphere between the two steps.
The first step in this method consists of diffusing oxygen and/or nitrogen in the refractory alloy. This diffusion treatment corresponds either to a nitriding, or to an oxidation, or an oxynitriding. In the case of a metallic refractory alloy surface including nickel B 13166.3 MDT
and iron, this treatment repels the elements facilitating coking such as nickel and iron, and thus prepares the surface for receiving a deposit whilst in addition promoting the adhesion of the deposit which 5 will then be formed in the second step.
According to the invention, the two steps of the method are carried out in the same plasma assisted chemical vapour deposition reactor, which has a system for feeding the different gases used, such as oxygen, nitrogen, the organosilicic compound and possibly argon.
According to the invention, each of the steps is performed using a low frequency, for example a frequency situated in the range from 2 to 450 kHz.
Thus a low plasma density is obtained, along with more homogeneous deposits able to cover parts of large size.
According to a preferred embodiment of the invention, a coating based on silicon oxynitride is deposited in the second step by PACVD.
In this case, it is possible to use, for the PACVD
deposition, an organosilicic compound containing nitrogen, for example hexamethyldisilazane. The mixture used for this deposition of silicon oxynitride is a mixture of the nitrogenous organosilicic compound, for example hexamethyldisilazane, and oxygen.
Preferably, in this case, a gaseous oxygen plasma is used in the first step for oxidising the refractory alloy surface.
The coating obtained under these conditions is a silicon oxynitride coating of formula SiOXNy, in which x and y are such that:
B 13166.3 MDT
1<x_<3 and 0.02<_y/x<_0.2.
According to a second embodiment of the invention, in the second step a coating based on silicon nitride is deposited. In this case, use is made in this second step of a plasma formed from a mixture of nitrogen and an organosilicic compound containing nitrogen such as hexamethyldisilazane, and preferably the first step is performed with a gaseous nitrogen plasma. In this second embodiment of the invention, it is preferable to first of all carry out an ionic pickling of the refractory alloy surface under argon plasma before performing the two steps of the method of the invention.
In this second embodiment of the invention, it is also possible to carry out a supplementary step of oxidation of the coating obtained in the second step in order to convert it at least partly into silicon oxynitride.
According to a third embodiment of the method of the invention, in the second step a coating based on silicon oxide is deposited, using a plasma formed from a mixture of oxygen and an organosilicic compound containing oxygen, such as hexamethyldisiloxane.
In this case, an oxygen plasma is preferably used in the first step. In this third embodiment, the two steps of the method can be supplemented by a third step of treatment of the coating obtained with a nitrogen plasma, in order to partly convert the SiOX coating into silicon oxynitride.
In order to implement the different steps of the method of the invention, using gaseous plasmas, the operations B 13166.3 MDT
are carried out in the same PACVD installation using very low pressures, for example 10 to 100 Pa.
The durations are chosen as a function of the gaseous flow rates so as to obtain satisfactory coatings.
In the second step, the duration is preferably such that a coating is obtained having a thickness of 0.1 to 100 Vim.
The gaseous flow rates are in the range from 10 to 500 cm3/min .
In particular, the ratios of the oxygen or nitrogen flow rates to the flow rate of organosilicic compound range from 1 to 20.
According to the invention, the refractory alloy subjected to the treatment is a refractory alloy like the ones normally used in petrochemistry. The alloy can in particular be a nickel-chromium-iron alloy containing 0.10 to 0.600 carbon, 0.7 to 2% manganese and 1 to 2°s silicon, and optionally minor additions of niobium, titanium, tungsten and zirconium.
By way of example, this alloy can be of the Manaurite type, in particular a Manaurite such as the ones whose compositions are given in the accompanying Table 1.
Amongst these, preference is given to XM and XTM
Manaurites having the following compositions.
Manaurite XM comprising:
- 33 to 38% nickel, - 23 to 28% chromium, - 0.35 to 0.600 carbon, - 1 to 1.5o manganese, - 1 to 2% silicon, B 13166.3 MDT
the remainder being iron with possibly minor additions of Nb, Ti and Zr.
Manaurite XTM comprising:
- 34 to 37s chromium, - 43 to 48~ nickel, - 0.40 to 0.45% carbon, - 1 to 2% manganese, - 1 to 2o silicon, the remainder being iron with possibly minor additions of Nb and Ti.
Another object of the invention is a part made of refractory alloy having a silicon oxynitride coating of formula SiOxNy in which x and y are such that:
1<x<_3 and 0.02<_y/x<_0.2.
,The refractory alloy is in particular a nickel-chromium-iron alloy, for example a Manaurite such as the ones described above, and the coating can have a thickness of 0.1 to 100 Vim.
Other characteristics and advantages of the invention will emerge more clearly from a reading of the following description given of course for purposes of illustration and non-limitatively, with reference to the accompanying drawing.
Brief description of the drawing Figure 1 depicts schematically in vertical section a reactor suitable for implementing the method of the invention.
B 13166.3 MDT
Detailed disclosure of embodiments In Figure 1, it can be seen that the deposition reactor comprises an earthed enclosure (1), inside which there is disposed a support (3) for the parts to be treated (5), this support being connected to a low-frequency generator (7). The support (3) can be a plate or rod for suspending the parts to be treated.
The generator (7) comprising a system for adjusting the power and frequency and a device for displaying the self-bias voltage.
The gases necessary for the depositions are introduced into the enclosure through a conduit 9 connected to a gas diffuser 11 situated in the enclosure, which can be cylindrical. The conduit 9 is connected to a gas supply system 13 which comprises several lines through which oxygen, nitrogen, argon and the organic silicon compound can be brought to the gas diffuser 11. The enclosure is also connected to a pumping unit 15 at its lower part in order to produce and maintain the required pressure in the enclosure.
A control console, not shown in the figure, has devices for controlling pumping, gas flow rate and total pressure, the pressure measurement being made by a capacitive gauge. Each gas feed line is equipped with an electronically regulated mass flow meter and stop valve which are connected to the control cabinet provided with devices for displaying the flow rate and simultaneous adjustment.
All the steps of the method of the invention can be implemented in this reactor.
B 13166.3 MDT
Thus, after having introduced the parts to be treated into the chamber, it is possible to carry out first of all if necessary an ionic pickling treatment by means of an inert gas plasma, for example argon, using a sufficiently low pressure to allow a powerful ion bombardment, for example a biasing of -700 V.
Next the first step of the method of the invention can be carried out in this enclosure by means of an oxygen or nitrogen plasma, for example at a frequency of 50 kHz. The deposition of the silicon-based coating is then carried out, still in the same enclosure, by modifying the gases introduced and the gaseous flow rates and by adapting and changing the frequency of the plasma, if necessary.
Thus the operating frequency can be chosen for each operation in order to provide the treatment or growth of the coating under the best possible conditions in order to obtain the expected properties and good adhesion of the coating.
The following examples, given as an indication and no way limitatively, illustrate the method of the invention.
In the following examples, a Manaurite XM substrate is used, which has the composition given in Table 1.
Example 1 On the Manaurite XM substrate, an ionic oxidation treatment is carried out using a pure oxygen plasma, at a working pressure of around 16 Pa (0.16 mbar) with an oxygen flow rate of 50 cm3/min and a frequency of 50 kHz. This treatment is carried out for 30 minutes.
B 13166.3 MDT
Next a coating based on silicon oxide is formed on the substrate by means of an oxygen and hexamethyldisiloxane plasma with respective flow rates of 250 cm3/min for oxygen and 25 cm3/min for hexamethyldisiloxane. The operation is carried out at a pressure of 50 Pa (0.5 mbar) and at a frequency of 50 kHz, for 40 minutes.
In this way a coating based on silicon oxide is obtained with a thickness of 1 ~tm.
The behaviour under coking of the Manaurite substrate thus coated is tested by putting it in contact with a flow of hydrocarbon (naphtha) at a temperature of 810°C
for 20 minutes. For comparison, the same test is carried out on an untreated Manaurite XM substrate.
The improvement of the coking behaviour of the coated substrate compared with the non-coated substrate is 6 to 10 0 .
Example 2 In this example, a Manaurite substrate is used identical to the one of Example 1 and first of all an ionic pickling treatment is carried out on it under argon plasma for one hour using an argon flow rate of 50 cm3/min, a pressure of 10 Pa (0.1 mbar) and a frequency of 50 kHz.
After this treatment, the substrate is subjected to the action of a nitrogen plasma for 30 minutes at a total pressure of 30 Pa (0.3 mbar) , operating at a frequency of 50 kHz with a nitrogen flow rate of 50 cm3/min.
Next a coating based on silicon nitride is deposited using a plasma formed from a gaseous mixture of nitrogen and hexamethyldisilazane, with respective flow B 13166.3 MDT
rates of 100 cm3/min for the nitrogen and 10 cm3/min for the hexamethyldisilazane at a pressure of 30 Pa and a frequency of 50 kHz, for 45 minutes.
After this coating formation step, the substrate is subjected to oxidation in air for one hour at 1000°C.
In this way a 2 ~m thick coating based on silicon oxynitride is obtained.
The substrate thus treated is subjected to the same behaviour under coking test as in the Example 1. It is thus found that it exhibits an improvement in behaviour under coking of 9 to 10% compared with the uncoated Manaurite substrate.
Example 3 In this example, a coating based on silicon oxynitride is formed on a Manaurite substrate identical to the one in Example 1.
For this purpose, the substrate is first of all subjected to an ionic oxidation treatment by means of a pure oxygen plasma at a working pressure of around 16 Pa (0.16 mbar) and at a frequency of 50 kHz with an oxygen flow rate of 50 cm3/min for 30 minutes.
Next the deposition by PACVD is carried out, using a mixture of oxygen and hexamethyldisiloxane with respective flow rates of 100 cm3/min for oxygen and 10 cm3/min for hexamethyldisiloxane, at a pressure of 50 Pa (0.5 mbar) and at a frequency of 50 kHz, for 40 minutes.
After the formation of this coating, a post-treatment is carried out in the same enclosure by means of a nitrogen plasma using a nitrogen flow rate of 100 B 13166.3 MDT
cm3/min, a working pressure of around 30 Pa and a frequency of 50 kHz, for 30 minutes.
The substrate thus treated is subjected to the same behaviour under coking test as in Example 1. It is thus found that it exhibits an improvement in behaviour under coking of 16 to 21% compared with the uncoated Manaurite XM substrate.
Example 4 In this example, a Manaurite substrate identical to the 10~ one in Example 1 is subjected to an ionic oxidation treatment by means of a pure oxygen plasma, using an oxygen flow rate of 50 cm3/min, a working pressure of around 16 Pa (0.16 mbar) and a frequency of 50 kHz, for 30 minutes.
After this treatment, a coating of silicon oxynitride is deposited by PACVD using a oxygen-hexamethyldisilazane mixture with respective flow rates of 24 cm3/min for the oxygen and 12 cm3/min for the hexamethyldisilazane, at a pressure of 50 Pa (0.5 mbar) and a frequency of 50 kHz, for 40 minutes.
The product obtained is subjected to the same behaviour under coking test as in Example 1. The improvement obtained is 39 to 54o compared with the uncoated Manaurite XM substrate.
Example 5 Under conditions similar to those of Example 4, the coating of Manaurite XM tubes with a length of 70 cm and a diameter of 4 cm is carried out.
These tubes are then subjected to a behaviour under coking test at 810°C, and a very significant improvement in the behaviour under coking of the coated B 13166.3 MDT
tube is observed compared with the uncoated tube, this improvement being around 40~.
Extreme conditions of the coking oven are then tested, that is to say a temperature of 980°C, and an improvement of around 20°s is also obtained under these conditions.
A third test is finally carried out on the same tubes at a temperature of 810°C and it is found that the coating still behaves effectively since the improvement obtained is again 50 to 530.
References cited [1] FR-A-2 662 704 [2] EP-A-0 607 651 [3] EP-A-0 608 081 [4] US-A-5,266,360 B 13166.3 MDT
Table 1 RefractoryThermalloyComposition Any $
alloy (T) C Mn Si Ni Cr Fe additions designation ManauriteT-04 0.35/0.601.00/ 1.00/33/38 23/28remainderNb 36X 1.50 2.00 TX-63 0.35/0.501.00/ 1.00/33/38 23/28remainderTi, W
1.50 2.00 ManauriteMA-6300 0.35/0.601.00/ 1.00/33/38 23/28remainderNb, Ti, XM 1.50 2.00 Zr Manaurite 0.35/0.600.70/ 1.00/33/38 21/28remainderW + Nb 36X5 1.25 2.00 ManauriteT-63W 0.35/0.600.70/ 1.00/33/38 21/28remainderW
35-25W 1.25 2.00 Manaurite 0.35/0.501.00/ 1.00/39/90 20/27remainderNb XA 2.00 2.00 T-58 0.40/0.600.70/ 1.00/37/90 18/21remainderNb 1.25 2.00 Manaurite 0.35/0.951.00/ 1.00/92/96 32/37remainderNb XT 1.50 2.00 Manaurite 0.40/0.951.00/ 1.00/93/98 34/37remainderNb, Ti XTM 2.00 2.00 ManauriteT-45 0.35/0.501.00/ 1.00/23.5/ 19/ remainderNb 29/29 1.50 2.00 26.5 26.5 Nb ManauriteT-53 0.06/0.151.00/ 0.75/29/37 16/22remainderNb 900 1.50 1.50 ManauriteTX-53 0.10/0.181.00/ 1.00/33/37 24/27remainderNb 900B 1.50 1.50 ManauriteT-50 0.25/0.601.00/ 1.00/30/38 14/23remainderNb, Ti 35 1.50 2.00 and W
B 13166.3 MDT
According to a second embodiment of the invention, in the second step a coating based on silicon nitride is deposited. In this case, use is made in this second step of a plasma formed from a mixture of nitrogen and an organosilicic compound containing nitrogen such as hexamethyldisilazane, and preferably the first step is performed with a gaseous nitrogen plasma. In this second embodiment of the invention, it is preferable to first of all carry out an ionic pickling of the refractory alloy surface under argon plasma before performing the two steps of the method of the invention.
In this second embodiment of the invention, it is also possible to carry out a supplementary step of oxidation of the coating obtained in the second step in order to convert it at least partly into silicon oxynitride.
According to a third embodiment of the method of the invention, in the second step a coating based on silicon oxide is deposited, using a plasma formed from a mixture of oxygen and an organosilicic compound containing oxygen, such as hexamethyldisiloxane.
In this case, an oxygen plasma is preferably used in the first step. In this third embodiment, the two steps of the method can be supplemented by a third step of treatment of the coating obtained with a nitrogen plasma, in order to partly convert the SiOX coating into silicon oxynitride.
In order to implement the different steps of the method of the invention, using gaseous plasmas, the operations B 13166.3 MDT
are carried out in the same PACVD installation using very low pressures, for example 10 to 100 Pa.
The durations are chosen as a function of the gaseous flow rates so as to obtain satisfactory coatings.
In the second step, the duration is preferably such that a coating is obtained having a thickness of 0.1 to 100 Vim.
The gaseous flow rates are in the range from 10 to 500 cm3/min .
In particular, the ratios of the oxygen or nitrogen flow rates to the flow rate of organosilicic compound range from 1 to 20.
According to the invention, the refractory alloy subjected to the treatment is a refractory alloy like the ones normally used in petrochemistry. The alloy can in particular be a nickel-chromium-iron alloy containing 0.10 to 0.600 carbon, 0.7 to 2% manganese and 1 to 2°s silicon, and optionally minor additions of niobium, titanium, tungsten and zirconium.
By way of example, this alloy can be of the Manaurite type, in particular a Manaurite such as the ones whose compositions are given in the accompanying Table 1.
Amongst these, preference is given to XM and XTM
Manaurites having the following compositions.
Manaurite XM comprising:
- 33 to 38% nickel, - 23 to 28% chromium, - 0.35 to 0.600 carbon, - 1 to 1.5o manganese, - 1 to 2% silicon, B 13166.3 MDT
the remainder being iron with possibly minor additions of Nb, Ti and Zr.
Manaurite XTM comprising:
- 34 to 37s chromium, - 43 to 48~ nickel, - 0.40 to 0.45% carbon, - 1 to 2% manganese, - 1 to 2o silicon, the remainder being iron with possibly minor additions of Nb and Ti.
Another object of the invention is a part made of refractory alloy having a silicon oxynitride coating of formula SiOxNy in which x and y are such that:
1<x<_3 and 0.02<_y/x<_0.2.
,The refractory alloy is in particular a nickel-chromium-iron alloy, for example a Manaurite such as the ones described above, and the coating can have a thickness of 0.1 to 100 Vim.
Other characteristics and advantages of the invention will emerge more clearly from a reading of the following description given of course for purposes of illustration and non-limitatively, with reference to the accompanying drawing.
Brief description of the drawing Figure 1 depicts schematically in vertical section a reactor suitable for implementing the method of the invention.
B 13166.3 MDT
Detailed disclosure of embodiments In Figure 1, it can be seen that the deposition reactor comprises an earthed enclosure (1), inside which there is disposed a support (3) for the parts to be treated (5), this support being connected to a low-frequency generator (7). The support (3) can be a plate or rod for suspending the parts to be treated.
The generator (7) comprising a system for adjusting the power and frequency and a device for displaying the self-bias voltage.
The gases necessary for the depositions are introduced into the enclosure through a conduit 9 connected to a gas diffuser 11 situated in the enclosure, which can be cylindrical. The conduit 9 is connected to a gas supply system 13 which comprises several lines through which oxygen, nitrogen, argon and the organic silicon compound can be brought to the gas diffuser 11. The enclosure is also connected to a pumping unit 15 at its lower part in order to produce and maintain the required pressure in the enclosure.
A control console, not shown in the figure, has devices for controlling pumping, gas flow rate and total pressure, the pressure measurement being made by a capacitive gauge. Each gas feed line is equipped with an electronically regulated mass flow meter and stop valve which are connected to the control cabinet provided with devices for displaying the flow rate and simultaneous adjustment.
All the steps of the method of the invention can be implemented in this reactor.
B 13166.3 MDT
Thus, after having introduced the parts to be treated into the chamber, it is possible to carry out first of all if necessary an ionic pickling treatment by means of an inert gas plasma, for example argon, using a sufficiently low pressure to allow a powerful ion bombardment, for example a biasing of -700 V.
Next the first step of the method of the invention can be carried out in this enclosure by means of an oxygen or nitrogen plasma, for example at a frequency of 50 kHz. The deposition of the silicon-based coating is then carried out, still in the same enclosure, by modifying the gases introduced and the gaseous flow rates and by adapting and changing the frequency of the plasma, if necessary.
Thus the operating frequency can be chosen for each operation in order to provide the treatment or growth of the coating under the best possible conditions in order to obtain the expected properties and good adhesion of the coating.
The following examples, given as an indication and no way limitatively, illustrate the method of the invention.
In the following examples, a Manaurite XM substrate is used, which has the composition given in Table 1.
Example 1 On the Manaurite XM substrate, an ionic oxidation treatment is carried out using a pure oxygen plasma, at a working pressure of around 16 Pa (0.16 mbar) with an oxygen flow rate of 50 cm3/min and a frequency of 50 kHz. This treatment is carried out for 30 minutes.
B 13166.3 MDT
Next a coating based on silicon oxide is formed on the substrate by means of an oxygen and hexamethyldisiloxane plasma with respective flow rates of 250 cm3/min for oxygen and 25 cm3/min for hexamethyldisiloxane. The operation is carried out at a pressure of 50 Pa (0.5 mbar) and at a frequency of 50 kHz, for 40 minutes.
In this way a coating based on silicon oxide is obtained with a thickness of 1 ~tm.
The behaviour under coking of the Manaurite substrate thus coated is tested by putting it in contact with a flow of hydrocarbon (naphtha) at a temperature of 810°C
for 20 minutes. For comparison, the same test is carried out on an untreated Manaurite XM substrate.
The improvement of the coking behaviour of the coated substrate compared with the non-coated substrate is 6 to 10 0 .
Example 2 In this example, a Manaurite substrate is used identical to the one of Example 1 and first of all an ionic pickling treatment is carried out on it under argon plasma for one hour using an argon flow rate of 50 cm3/min, a pressure of 10 Pa (0.1 mbar) and a frequency of 50 kHz.
After this treatment, the substrate is subjected to the action of a nitrogen plasma for 30 minutes at a total pressure of 30 Pa (0.3 mbar) , operating at a frequency of 50 kHz with a nitrogen flow rate of 50 cm3/min.
Next a coating based on silicon nitride is deposited using a plasma formed from a gaseous mixture of nitrogen and hexamethyldisilazane, with respective flow B 13166.3 MDT
rates of 100 cm3/min for the nitrogen and 10 cm3/min for the hexamethyldisilazane at a pressure of 30 Pa and a frequency of 50 kHz, for 45 minutes.
After this coating formation step, the substrate is subjected to oxidation in air for one hour at 1000°C.
In this way a 2 ~m thick coating based on silicon oxynitride is obtained.
The substrate thus treated is subjected to the same behaviour under coking test as in the Example 1. It is thus found that it exhibits an improvement in behaviour under coking of 9 to 10% compared with the uncoated Manaurite substrate.
Example 3 In this example, a coating based on silicon oxynitride is formed on a Manaurite substrate identical to the one in Example 1.
For this purpose, the substrate is first of all subjected to an ionic oxidation treatment by means of a pure oxygen plasma at a working pressure of around 16 Pa (0.16 mbar) and at a frequency of 50 kHz with an oxygen flow rate of 50 cm3/min for 30 minutes.
Next the deposition by PACVD is carried out, using a mixture of oxygen and hexamethyldisiloxane with respective flow rates of 100 cm3/min for oxygen and 10 cm3/min for hexamethyldisiloxane, at a pressure of 50 Pa (0.5 mbar) and at a frequency of 50 kHz, for 40 minutes.
After the formation of this coating, a post-treatment is carried out in the same enclosure by means of a nitrogen plasma using a nitrogen flow rate of 100 B 13166.3 MDT
cm3/min, a working pressure of around 30 Pa and a frequency of 50 kHz, for 30 minutes.
The substrate thus treated is subjected to the same behaviour under coking test as in Example 1. It is thus found that it exhibits an improvement in behaviour under coking of 16 to 21% compared with the uncoated Manaurite XM substrate.
Example 4 In this example, a Manaurite substrate identical to the 10~ one in Example 1 is subjected to an ionic oxidation treatment by means of a pure oxygen plasma, using an oxygen flow rate of 50 cm3/min, a working pressure of around 16 Pa (0.16 mbar) and a frequency of 50 kHz, for 30 minutes.
After this treatment, a coating of silicon oxynitride is deposited by PACVD using a oxygen-hexamethyldisilazane mixture with respective flow rates of 24 cm3/min for the oxygen and 12 cm3/min for the hexamethyldisilazane, at a pressure of 50 Pa (0.5 mbar) and a frequency of 50 kHz, for 40 minutes.
The product obtained is subjected to the same behaviour under coking test as in Example 1. The improvement obtained is 39 to 54o compared with the uncoated Manaurite XM substrate.
Example 5 Under conditions similar to those of Example 4, the coating of Manaurite XM tubes with a length of 70 cm and a diameter of 4 cm is carried out.
These tubes are then subjected to a behaviour under coking test at 810°C, and a very significant improvement in the behaviour under coking of the coated B 13166.3 MDT
tube is observed compared with the uncoated tube, this improvement being around 40~.
Extreme conditions of the coking oven are then tested, that is to say a temperature of 980°C, and an improvement of around 20°s is also obtained under these conditions.
A third test is finally carried out on the same tubes at a temperature of 810°C and it is found that the coating still behaves effectively since the improvement obtained is again 50 to 530.
References cited [1] FR-A-2 662 704 [2] EP-A-0 607 651 [3] EP-A-0 608 081 [4] US-A-5,266,360 B 13166.3 MDT
Table 1 RefractoryThermalloyComposition Any $
alloy (T) C Mn Si Ni Cr Fe additions designation ManauriteT-04 0.35/0.601.00/ 1.00/33/38 23/28remainderNb 36X 1.50 2.00 TX-63 0.35/0.501.00/ 1.00/33/38 23/28remainderTi, W
1.50 2.00 ManauriteMA-6300 0.35/0.601.00/ 1.00/33/38 23/28remainderNb, Ti, XM 1.50 2.00 Zr Manaurite 0.35/0.600.70/ 1.00/33/38 21/28remainderW + Nb 36X5 1.25 2.00 ManauriteT-63W 0.35/0.600.70/ 1.00/33/38 21/28remainderW
35-25W 1.25 2.00 Manaurite 0.35/0.501.00/ 1.00/39/90 20/27remainderNb XA 2.00 2.00 T-58 0.40/0.600.70/ 1.00/37/90 18/21remainderNb 1.25 2.00 Manaurite 0.35/0.951.00/ 1.00/92/96 32/37remainderNb XT 1.50 2.00 Manaurite 0.40/0.951.00/ 1.00/93/98 34/37remainderNb, Ti XTM 2.00 2.00 ManauriteT-45 0.35/0.501.00/ 1.00/23.5/ 19/ remainderNb 29/29 1.50 2.00 26.5 26.5 Nb ManauriteT-53 0.06/0.151.00/ 0.75/29/37 16/22remainderNb 900 1.50 1.50 ManauriteTX-53 0.10/0.181.00/ 1.00/33/37 24/27remainderNb 900B 1.50 1.50 ManauriteT-50 0.25/0.601.00/ 1.00/30/38 14/23remainderNb, Ti 35 1.50 2.00 and W
B 13166.3 MDT
Claims (19)
1. A method for preventing the deposition of coke on a refractory alloy surface in contact with fluids containing hydrocarbons, which comprises the following steps:
1) subjecting the refractory alloy surface to the action of a gaseous plasma of oxygen and/or nitrogen at low frequency, and 2) depositing on the surface thus treated a coating based on silicon oxide, nitride or oxynitride by plasma assisted chemical vapour deposition at low frequency, using an organosilicic compound and a gas chosen from amongst oxygen and nitrogen, the two steps being carried out consecutively and continuously in the same installation without opening to atmosphere between the two steps.
1) subjecting the refractory alloy surface to the action of a gaseous plasma of oxygen and/or nitrogen at low frequency, and 2) depositing on the surface thus treated a coating based on silicon oxide, nitride or oxynitride by plasma assisted chemical vapour deposition at low frequency, using an organosilicic compound and a gas chosen from amongst oxygen and nitrogen, the two steps being carried out consecutively and continuously in the same installation without opening to atmosphere between the two steps.
2. A method according to Claim 1, in which each of the steps is performed at a frequency of 2 to 450 kHz.
3. A method according to Claim 1 or 2, in which the organosilicic compound is hexamethyldisilazane.
4. A method according to Claim 3, in which in the first step an oxygen plasma is used and in the second step a plasma formed from oxygen and hexamethyldisilazane.
5. A method according to Claim 3, in which in the first step a nitrogen plasma is used and in the second step a plasma formed from a mixture of nitrogen and hexamethyldisilazane.
6. A method according to Claim 5, in which first of all an ionic pickling treatment of the refractory alloy surface is carried out under argon plasma before performing the two steps of the method.
7. A method according to Claim 5 or 6, in which a supplementary step of oxidation of the coating obtained in the second step is performed.
8. A method according to Claim 1 or 2, in which the organosilicic compound is hexamethyldisiloxane.
9. A method according to Claim 8, in which in the first step an oxygen plasma is used and in the second step a plasma from a mixture of oxygen and hexamethyldisiloxane.
10. A method according to Claim 9, which also comprises a supplementary step of treating the coating obtained in the second step, in a nitrogen plasma.
11. A method according to any one of Claims 1 to 10, in which the duration of the second step is such that a coating is formed with a thickness of 0.1 to 100 µm.
12. A method according to any one of Claims 1 to 11, in which the refractory alloy is a nickel-chromium-iron alloy containing 0.10 to 0.600 carbon, 0.7 to 2%
manganese and 1 to 2% silicon.
manganese and 1 to 2% silicon.
13. A method according to Claim 12, in which the nickel-chromium-iron alloy has the following composition:
- 33 to 38% nickel, - 23 to 28% chromium, - 0.35 to 0.60% carbon, - 1 to 1.5% manganese, - 1 to 2% silicon, the remainder consisting essentially of iron, with possibly minor additions of Nb, Ti and/or Zr.
- 33 to 38% nickel, - 23 to 28% chromium, - 0.35 to 0.60% carbon, - 1 to 1.5% manganese, - 1 to 2% silicon, the remainder consisting essentially of iron, with possibly minor additions of Nb, Ti and/or Zr.
14. A method according to Claim 12, in which the nickel-chromium-iron alloy comprises:
- 34 to 37% chromium, - 43 to 48% nickel, - 0.40 to 0.45% carbon, - 1 to 2% manganese, - 1 to 2% silicon, the remainder consisting of iron and possibly minor additions of niobium and/or titanium.
- 34 to 37% chromium, - 43 to 48% nickel, - 0.40 to 0.45% carbon, - 1 to 2% manganese, - 1 to 2% silicon, the remainder consisting of iron and possibly minor additions of niobium and/or titanium.
15. A refractory alloy part having a coating of silicon oxynitride of formula SiO X N y in which x and y are such that:
1 ~ x ~ 3 and 0.02 ~ y/x ~ 0.2.
1 ~ x ~ 3 and 0.02 ~ y/x ~ 0.2.
16. A part according to Claim 15, in which the refractory alloy is a nickel-chromium-iron alloy.
17. A part according to Claim 16, in which the nickel-chromium-iron alloy comprises:
- 33 to 38% nickel, - 23 to 28% chromium, - 0.35 to 0.60% carbon, - 1 to 1.5% manganese, - 1 to 2% silicon, the remainder consisting essentially of iron, with possibly minor additions of Nb, Ti and/or Zr.
- 33 to 38% nickel, - 23 to 28% chromium, - 0.35 to 0.60% carbon, - 1 to 1.5% manganese, - 1 to 2% silicon, the remainder consisting essentially of iron, with possibly minor additions of Nb, Ti and/or Zr.
18. A part according to Claim 16, in which the nickel-chromium-iron alloy comprises:
- 34 to 37% chromium, - 43 to 48% nickel, - 0.40 to 0.45% carbon, - 1 to 2% manganese, - 1 to 2% silicon, the remainder consisting of iron and possibly minor additions of niobium and/or titanium.
- 34 to 37% chromium, - 43 to 48% nickel, - 0.40 to 0.45% carbon, - 1 to 2% manganese, - 1 to 2% silicon, the remainder consisting of iron and possibly minor additions of niobium and/or titanium.
19. A part according to any one of Claims 15 to 18, in which the cladding has a thickness of 0.1 to 100 µm.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9812687A FR2784396B1 (en) | 1998-10-09 | 1998-10-09 | ANTI-COCK COATINGS OF REFRACTORY ALLOYS USED IN THE OIL FIELD |
| FR9812687 | 1998-10-09 | ||
| PCT/FR1999/002403 WO2000022068A1 (en) | 1998-10-09 | 1999-10-07 | Anti-coking coatings |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2314356A1 true CA2314356A1 (en) | 2000-04-20 |
Family
ID=9531388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002314356A Abandoned CA2314356A1 (en) | 1998-10-09 | 1999-10-07 | Anti-coking coatings for refractory alloys used in the petroleum field |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1040175B1 (en) |
| JP (1) | JP2002527572A (en) |
| AT (1) | ATE265513T1 (en) |
| CA (1) | CA2314356A1 (en) |
| DE (1) | DE69916789D1 (en) |
| FR (1) | FR2784396B1 (en) |
| WO (1) | WO2000022068A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9862892B2 (en) | 2012-02-21 | 2018-01-09 | Battelle Memorial Institute | Heavy fossil hydrocarbon conversion and upgrading using radio-frequency or microwave energy |
| US11021661B2 (en) | 2012-02-21 | 2021-06-01 | Battelle Memorial Institute | Heavy fossil hydrocarbon conversion and upgrading using radio-frequency or microwave energy |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10109312B4 (en) * | 2001-02-27 | 2005-08-04 | Thyssenkrupp Vdm Gmbh | Use of the gas oxynitriding process for austenitic nickel alloy components |
| DE102015101312A1 (en) * | 2015-01-29 | 2016-08-04 | Thyssenkrupp Steel Europe Ag | A method of applying a metallic protective coating to a surface of a steel product |
| CN112759374B (en) * | 2020-12-31 | 2023-03-24 | 上海化学工业区升达废料处理有限公司 | Anti-coking agent for hazardous waste incineration line and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2104054B (en) * | 1981-08-11 | 1984-11-14 | British Petroleum Co Plc | Protective silica coatings |
| US5208069A (en) * | 1991-10-28 | 1993-05-04 | Istituto Guido Donegani S.P.A. | Method for passivating the inner surface by deposition of a ceramic coating of an apparatus subject to coking, apparatus prepared thereby, and method of utilizing apparatus prepared thereby |
-
1998
- 1998-10-09 FR FR9812687A patent/FR2784396B1/en not_active Expired - Lifetime
-
1999
- 1999-10-07 JP JP2000575964A patent/JP2002527572A/en not_active Withdrawn
- 1999-10-07 WO PCT/FR1999/002403 patent/WO2000022068A1/en active IP Right Grant
- 1999-10-07 DE DE69916789T patent/DE69916789D1/en not_active Expired - Lifetime
- 1999-10-07 AT AT99970412T patent/ATE265513T1/en not_active IP Right Cessation
- 1999-10-07 CA CA002314356A patent/CA2314356A1/en not_active Abandoned
- 1999-10-07 EP EP99970412A patent/EP1040175B1/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9862892B2 (en) | 2012-02-21 | 2018-01-09 | Battelle Memorial Institute | Heavy fossil hydrocarbon conversion and upgrading using radio-frequency or microwave energy |
| US11021661B2 (en) | 2012-02-21 | 2021-06-01 | Battelle Memorial Institute | Heavy fossil hydrocarbon conversion and upgrading using radio-frequency or microwave energy |
| US11268036B2 (en) | 2012-02-21 | 2022-03-08 | Battelle Memorial Institute | Heavy fossil hydrocarbon conversion and upgrading using radio-frequency or microwave energy |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2784396B1 (en) | 2000-11-10 |
| EP1040175A1 (en) | 2000-10-04 |
| WO2000022068A1 (en) | 2000-04-20 |
| ATE265513T1 (en) | 2004-05-15 |
| JP2002527572A (en) | 2002-08-27 |
| EP1040175B1 (en) | 2004-04-28 |
| FR2784396A1 (en) | 2000-04-14 |
| DE69916789D1 (en) | 2004-06-03 |
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