CA1140162A - High-temperature treatment of hydrocarbon-containing materials - Google Patents
High-temperature treatment of hydrocarbon-containing materialsInfo
- Publication number
- CA1140162A CA1140162A CA000366750A CA366750A CA1140162A CA 1140162 A CA1140162 A CA 1140162A CA 000366750 A CA000366750 A CA 000366750A CA 366750 A CA366750 A CA 366750A CA 1140162 A CA1140162 A CA 1140162A
- Authority
- CA
- Canada
- Prior art keywords
- hydrocarbon
- member selected
- chromium
- alloys
- nickel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/002—Avoiding undesirable reactions or side-effects, e.g. avoiding explosions, or improving the yield by suppressing side-reactions
- B01J19/0026—Avoiding carbon deposits
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
-
- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/005—Inhibiting corrosion in hydrotreatment processes
-
- 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
- C10G9/16—Preventing or removing incrustation
-
- 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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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
- F28F19/02—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings
- F28F19/06—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings of metal
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4075—Limiting deterioration of equipment
Abstract
Abstract In the treatment of a hydrocarbon-containing material at temperatures of 500°C or above in an apparatus made of a nickel-containing heat-resistant steel, the surfaces of the apparatus that are exposed to the hydrocarbon-containing material are coated with a member selected from nickel-free metals, nickel-free alloys, nickel-free oxides or nitrides, and silicon carbides, whereby the deposition of carbon on those surface is prevented.
Description
¦ SPECIFICATION
Title of the Invention:
I
¦ High-temperature Treatment of Hydrocarbon-¦ containing Materials ¦ Background of the Invention:
I
1. Field of the Invention:
This invention relates to improvements in a process wherein a hydrocarbon, a mixture of a hydrocarbon and steam and/or an oxygen-containing gas, or a mixture of a hydro-carbon and at least one member selected from hydrogen, carbon monoxide and carbon dioxide is subjected to a chemical reaction, such as thermal cracking, steam reforming, partial oxidation, etc., or other high-temperature treatments. Such materials to be treated will hereinafter be referred to simply as hydrocarbon-containing materials.
Title of the Invention:
I
¦ High-temperature Treatment of Hydrocarbon-¦ containing Materials ¦ Background of the Invention:
I
1. Field of the Invention:
This invention relates to improvements in a process wherein a hydrocarbon, a mixture of a hydrocarbon and steam and/or an oxygen-containing gas, or a mixture of a hydro-carbon and at least one member selected from hydrogen, carbon monoxide and carbon dioxide is subjected to a chemical reaction, such as thermal cracking, steam reforming, partial oxidation, etc., or other high-temperature treatments. Such materials to be treated will hereinafter be referred to simply as hydrocarbon-containing materials.
2. Description of the Prior Art:
In these days, ethylene, hydrogen, or a mixture of hydrogen and carbon oxides is produced on a large scale by subjecting a hydrocarbon-containing material to thermal cracking, steam reforming and/or partial oxidation at high temperature and high pressure in the presence or absence of a catalyst. During such chemical reactions and before or after them, the hydrocarbon-containing material being handled is exposed to high temperature. Thus, its hydrocarbon component undergoes thermal decomposition, which results in a deposition of solid carbon. Since this solid carbon tends to accumulate on the surfaces of the reactor and other .. -1- ' ll 114~162 apparatus that are exposed to the hot gas, it is necessary to shut down the production system and remove the deposit-ed solid carbon for the purpose of minimizing its accumula-tion.
As the structural material of apparatus for handling a hydrocarbon-containing material at high tempera-ture, nickel-containing steels which can retain sufficient strength even under such high-temperature conditions are used in most cases. The present inventors have found that the above-described deposition of solid carbon is promoted by the catalytic action of the nickel contained in these steels.
Summary of the Invention It is an object of an aspect of the present invention to provide a method of handling a hydrocarbon-containing material at high te~.perature without causing any substantial degree of carbon deposition.
It is an object of an aspect of the present invention to provide a process for the high-temperature treatment of a hydrocarbon-containing material in which the apparatus made of a nickel-containing metallic material and used for handling the hydrocarbon-containing material at high temperature can be prevented from becoming brittle owing to the occurrence of carburization.
According to one aspect of this invention there is provided in a process for treating a hydrocarbon-containing material at temperaturesof 500C or above in an apparatus made of a nickel-containing heat-resistant steel, said hydrocarbon-containing material being select-ed from the group consisting of a hydrocarbon, a mixture of a hydrocarbon and at least one member selected from steam and an oxygen-containing gas, and a mixture of a hydrocarbon and at least one member selected from hydrogen, carbon monoxide, carbon dioxide and olefins, the improve-ment which comprises coating the surfaces of said apparatusthat are exposed to said hydrocarbon-containing material, with la) a member selected from titanium, cobalt, chromium, iron and alloys thereof;
(b) a member selected from titanium, cobalt, chromium, iron and alloys thereof containing aluminum or aluminum and silicon;
(c) a steel not containing nickel;
(d) an alloy steel containing aluminum or aluminum and silicon and not containing nickel;
(e) a member selected from alloys of titanium and niobium and alloys of copper and chromium; or (f) a member selected from alumina, titania, silica, sili-con carbide, silicon nitride, boron nitride and chromia.
According to another aspect of this invention there is provided in a process for reacting a hydrocarbon with steam and/or an oxygen~containing gas at high pressure in a reactor made of a nickel-containing heat-resistant steel to produce a gaseous mixture containing hydrogen and carbon monoxide, the improvement which comprises coating the surfaces of said reactor that are exposed to said hydrocarbon, with (a) a member selected from titanium, cobalt, chromium, iron and alloys thereof;
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b) a member selected from titanium, cobalt, chromium, iron and alloys thereof containing aluminum or aluminum and silicon;
Ic) a steel not containing nicXel;
Id) an alloy steel containing aluminum or aluminum and silicon and not containing nickel;
(e) a member selected from alloys and titanium and niobium and alloys of copper and chromium; or (f) a member selected from alumina, titania, silica, silicon carbide, silicon nitride, boron nitride and chromia.
Detailed Description of the Invention In the practice of the present invention, any of the coating materials belonging to the aforesaid categories (a) to (f) may be used to coat the surfaces of the apparatus that are exposed to the hydrocarbon-containing material to be treated. These coating materials are more specifically explained in the following.
Among the metallic materials belonging to the category (a), typical examples of the alloys of iron and -3a-il4U16Z
chromium are an iron-chromium alloy containing 17 to 19% by weight of chromium and 0 3% by weight of carbon, and an iron-chromium alloy containing 26 to 28% by weight of chromium and 0.1% by weight of carbon.
Typical examples of the alloys belonging to the category ~b) are a titanium-aluminum alloy containing 6% by weight of aluminum and a Ti-Al-Zr-V alloy containing 6% by weight of aluminum, 4% by weight of zirconium, and 1% by weight of vanadium.
A typical example of the alloys belonging to the category ~d) is an Fe-Cr-Al-Si alloy containing 23% by weight of chromium, 1.5% by weight of aluminum, and 1.5% by weight of silicon.
The alloys of titanium and niobium belonging to the category ~e) may consist of 91 to 99% by weight of titanium, 1 to 3% by weight of niobium, and O to 2% by weight each of other components such as zirconium, aluminum and tantalum.
The alloys of copper and chromium belonging to the category (e) may consist of 95 to 99% by weight of copper, 1 to 3% by weight of chromium, and O to 2% by weight of other components such as beryllium.
No particular limitation is placed on the method by which the surfaces of the apparatus that are exposed to the hydrocarbon-containing material is coated with a met~llic material belonging to any of the aforesaid categories (a) to (e). However, this coating is usually accomplished by the so-called casting method in which a melt of the metallic material is poured over the surfaces to be covered of the structural material previously formed into tubes, plates or other members; the method in which a means for producing high '' , temperatures, such as acetylene burner, electric arc, etc., is ¦ used to cause a melt of the metallic material to adhere to the surfaces to be covered of the structural material; the method in which a melt of the metallic material is sprayed and deposited on the surfaces to be covered of the structural material as in the flame spraying or the plasma jet process;
the chemical vapor deposition method in which a vapor of a i metallic compound is contacted with the surfaces to be coated of the structural material and subjected to a chemical reaction to deposit the metal thereon; the physical vapor deposition method in which a vapor of a metal or its compound is lj ionized in a high vacuum, and the resulting ions are supplied ¦1, with kinetic energy in an electric field and then led into a plasma or other space where they are directly deposited on i the surfaces to be coated of the structural material or Il subjected to a chemical reaction to deposit ~ the metal !l thereon; or the so-called cladding method in which tubes, plates or other members are separately fabricated of the metallic material and bonded to the surfaces to be coated of the previously shaped structural material by the application l of pressure.
When the members coated with a metallic material belonging to any of the aforesaid categories ~a) to ~e) are I used at high temperature, a slight degree of interdiffusion or mixing of components occurs between the nickel-containing structural material and the coating material. It is desirable, therefore, that the coating material has a thickness of not less than 100 microns so as to w~thstand a long-term service.
I
The resulting shaped and coated structural material may further be subjected to bending, tube-expanding, welding and other working operations to fabricate an apparatus or its parts having any desired shapes. However, if the structural material is in the form of castings it is desireble not to subject the covered structural material to bending, tube-expanding, or other working operations.
The method of coating the structural material with a non-metallic material belonging to the aforesaid category (f) depends on the type of the non-metallic material.
~ A) If the non-metallic material is an oxide, the coating can be accomplished by the so-called spraying method in which the oxide is melted and sprayed on the surfaces to be coated of the structural material as in the flame spraying or the plasma jet process; or the so-called baking method in which a suspension of the oxide is applied to the surfaces to be coated of the structural material and then baked at high temperature. In the latter case, however, it is desirable to bake the oxide in combination with a mixture consisting of varying proportions of oxides selected from silica, alumina, boron oxide, calcium oxide, zinc oxide, barium oxide, l zirconium oxide and the like, for the purpose of reducing the ¦ melting temperature of the oxide to lower than that of the structural material and thereby preventing melting or alteration of the structural material. Nevertheless, the temperature at which the coated structural material obtained by this baking method can be used is limited to the melting temperautre of the covering layer.
I
l - 6 -.
114~)162 (B) If the non-metallic material is silicon carbide, silicon nitride or boron nitride, the coating can be accomplished by the method in which a melt or solution of a compound containing silicon-to-carbon, nitrogen-to-boron or nitrogen-to-silicon bonds is applied to the surfaces to be coated of the structural material and then subjected to a chemical reaction in air or an inert gas at high temperature to deposit the desired compound thereon; the above-described spraying method in which a powder or rod of silicon carbide, boron nitride or silicon nitride is melted and sprayed on the surfaces to be coated of the structural material according to the plasma jet process; the above-described chemical vapor deposition method; or the above-described physical vapor deposition method.
~ here the surfaces to be coated of the structural material aforesaid category ~f), the structural material may be in the form of tubes, plates or any other members, as is the case with the metallic materials belonging to the aforesaid categories (a) to (e). When such a non-metallic material is used, a coating layer having a thickness of not less than 10 microns is required. However, the thickness of the coating layer is desirably not greater than 1 millimeter.
This is because, when an apparatus having a unduly thick coating layer is subjected to a heating step or the like, the coating layer not only reduces the overall coefficient of heat transfer to interfere with the flow of heat therethrough but also is liable to spall off owing to the difference in thermal expan on coefficient between he structural material and the I
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coating material.
Among various members made of the above-described structural material and coated with the above-described coating material, tubes are particularly important because they are often used as reactors, heat exchangers and the li~e and, therefore, have abundant opportunities of being exposed to a hot hydrocarbon-containing material. Accordingly, depending on the pathway by which a hydrocarbon-containing material flows through a reactor or heat exchanger, it may often be necessary to coat not only one surface of the tube but both surfaces thereof.
No particular limitation is placed on the hydrocarbon which is treated in the practice of the present invention.
Specific examples of the hydrocarbon can range from hydrocarbons having a small number of carbon atoms, such as methane, ethane, etc., to hydrocarbons having a large number of carbon atoms, such as heavy oil obtained as a distillate by subjecting reduced crude to vacuum distillation Generally speaking, the hydrocarbon which is treated in the practice of the present invention has an H/C atomic ratio of 2.0 to 4Ø The present invention is significantly effective when it is applied to the treatment of the aforesaid heavy oil.
The above-described hydrocarbon may be used alone in the form of a gas or liquid. Alternatively, it may be used in admixture with steam and/or an oxygen-containing gas, or in admixture with hydrogen, carbon monoxide, carbon dioxide and/or olefins (they may represent a product gas obtained by treating a hydrocarbon or a mixture of a hydrocarbon and steam 114V~62 I
and/or an oxygen-containing gas). The content of the hydrocarbon in such mixtures are usually in the range of 10 to 60% by weight.
The term "treat" as used herein means not only to subject a hydrocarbon-containing material to a chemical reaction such as thermal cracking, steam reforming, partial oxidation, etc., but also to handle a feed stream and a product stream before and after this chemical reaction.
In the practice of the present invention, the hydrocarbon-containing material is treated at temperatures of 500C or above. Moreover, this treatment is preferably carried out at a pressure of 6 to 100 kg/cm2G. As the structural material of apparatus for treatment under such severe conditions, nickel-containing materials such as nickel-containing heat-resistant steels are used in ordinary cases.
In accordance with one feature of the present invention, when a hydrocarbon-containing material is treated at temperatures of 500C or above and especially when it is subjected to a chemical reaction, such as thermal cracking, steam reforming, partial oxidation, etc., in the presence or absence of a catalyst, the deposition and accumulation of solid carbon on the surfaces of the reactor that are exposed to the hydrocarbon-containing material can be decreased significantly. If the deposited and accumulated solid carbon is left as it is, it interferes with the passage of a fluid containing the hydrocarbon and causes an increase in pressure loss. Moreover, in cases where it is necessary to remove or supply the heat of reaction for the purpose of effecting the 11~0~L62 aforesaid chemical reaction, the deposited and accumulated solid carbon also causes a marked decrease in overall coefficient of heat transfer and thus makes it difficult to continue the operation. As a countermeasure, therefore, it is necessary to shut down the large-scale system at regular intervals and remove the deposited carbon by any of the well- `
known means. If the present invention is applied, the frequency of this carbon-removing operation can be reduced to 2/3 less of that required in the prior art.
Another feature of the present invention is that the carburization of the nickel-containing structural material can be diminished greatly. It is well known that, when a carbon steel or an alloy steel containing nickel, chromium, iron and the like are exposed to carbon-containing substances, such as hydrocarbons, carbon oxides, etc., at temperatures of 700C or above, the so-called carburi~ation phenomenon occurs. That is, their carbon component infiltrates and diffuses into the microstructure of the steel and thereby reduces its strength to such a degree that the steel is no longer fit for use. It is said that such carburization is not only due to the infiltration and diffusion of the deposited carbon into the microstructure of the steel but also attributable to the presence of a gaseous carbon-containing substance. Thus, the present invention makes it possible to prolong the service lives of members, such as reactor tubes, pipings, etc~, which would otherwise have to be replaced at intervals of 2 or 3 years.
The present invention can produce marked effects when . '~
il40~62 it is applied to parts, members or apparatus made of a nickel-containing heat-resistant steel and used at temperatures of 500C or above and specifically to the surfaces thereof that are exposed to a stream of hydrocarbon-containing material.
Although these parts, members and apparatus may have any desired shapes, tubular members used as reactors are particularly important. This is because, in the reactor, the stream of hydrocarbon-containing material usually reaches a maximum temperature, the deposition of carbon is most likely to occur owing to the necessity of removing or supplying a large amount of reaction heat, and the reduction in overall coefficient of heat transfer caused by the deposited carbon leads to the greatest trouble.
The present invention is further illustrated by the following examples. However, these examples,are not to be construed to limit the scope of the invention.
Example Ethane was subjected to steam cracking in reactor tubes having an inner diameter of 27 mm and a length of 800 mm.
These reactor tubes were made of a nickel-containing steel (Fe-20% Ni-25% alloy) and had their inner surface covered with the respective covering materials shown in Table 1.
The ratio of ethane to steam was 7 : 3 and the reactor tube was maintained at a temperature of 700C or 1,100C by external heating. After the operation was continued for 10 hours at a pressure of 1 kg/cm2G and at a feed rate of 100 cc/min, the conditions of carbon deposition on theinside surface of the reactor tube were examined. The results th`us obtained are il4V162 i~
summarized in Table 1.
Table 1 I Coating Material on Inside Surface of Reactor Tube and Conditions of Carbon Deposition ~ I
Test Coating Material Testing Conditions of Carbon Deposition Tube on Inside Surface Temper- on Inside Surface of Tube No. of Tubeature . _ (C)Amount Deposited _. _ (mgicm /10 hr) Form 1 Chromium1,000 1.0 Filmy 1!2 Fe-28%Cr Alloy1,000 2.i Filmy 1!3 Ti-6%Al Alloy 700 0.3 Sootlike 4 1.5%Si Alloyl,DOO 2.1 Filmy . 5 Ti-2%Nb Alloy 700 0.3 Sootlike 6 Cu-1%Cr Ailoy 700 < 0.1 Sootlike 7 Alumina1,000 2.0 Filmy 8 Titania1,000 1.4 Filmy 9 Silica 1,000 1.6 Filmy Silicon Carbide1,000 1.2 Filmy ~,11 Silicon Nitride1,000 1.4 Filmy !!12 Boron Nitride1,000 1.4 Pilmy 13 Chromia1,000 1.0 Filmy 14 None 1,000 -3.4 .~ilmy ~1 !
! l As is evident from the data shown in Table 1, a considerable degree of carbon deposition was noted on the uncovered inside surface of a tube made of a nickel-containing steel, even in the case of steam cracking of ethane which is a i light hydrocarbon. This carbon deposition was decreased to a ;¦ substantial degree by coating that surface with a nickel-free Il metallic or non-metalllc material. Among others, chromium, ¦l a titanium-niobium alloy and a copper-chromium alloy were found to be particularly excellent coating materials.
In these days, ethylene, hydrogen, or a mixture of hydrogen and carbon oxides is produced on a large scale by subjecting a hydrocarbon-containing material to thermal cracking, steam reforming and/or partial oxidation at high temperature and high pressure in the presence or absence of a catalyst. During such chemical reactions and before or after them, the hydrocarbon-containing material being handled is exposed to high temperature. Thus, its hydrocarbon component undergoes thermal decomposition, which results in a deposition of solid carbon. Since this solid carbon tends to accumulate on the surfaces of the reactor and other .. -1- ' ll 114~162 apparatus that are exposed to the hot gas, it is necessary to shut down the production system and remove the deposit-ed solid carbon for the purpose of minimizing its accumula-tion.
As the structural material of apparatus for handling a hydrocarbon-containing material at high tempera-ture, nickel-containing steels which can retain sufficient strength even under such high-temperature conditions are used in most cases. The present inventors have found that the above-described deposition of solid carbon is promoted by the catalytic action of the nickel contained in these steels.
Summary of the Invention It is an object of an aspect of the present invention to provide a method of handling a hydrocarbon-containing material at high te~.perature without causing any substantial degree of carbon deposition.
It is an object of an aspect of the present invention to provide a process for the high-temperature treatment of a hydrocarbon-containing material in which the apparatus made of a nickel-containing metallic material and used for handling the hydrocarbon-containing material at high temperature can be prevented from becoming brittle owing to the occurrence of carburization.
According to one aspect of this invention there is provided in a process for treating a hydrocarbon-containing material at temperaturesof 500C or above in an apparatus made of a nickel-containing heat-resistant steel, said hydrocarbon-containing material being select-ed from the group consisting of a hydrocarbon, a mixture of a hydrocarbon and at least one member selected from steam and an oxygen-containing gas, and a mixture of a hydrocarbon and at least one member selected from hydrogen, carbon monoxide, carbon dioxide and olefins, the improve-ment which comprises coating the surfaces of said apparatusthat are exposed to said hydrocarbon-containing material, with la) a member selected from titanium, cobalt, chromium, iron and alloys thereof;
(b) a member selected from titanium, cobalt, chromium, iron and alloys thereof containing aluminum or aluminum and silicon;
(c) a steel not containing nickel;
(d) an alloy steel containing aluminum or aluminum and silicon and not containing nickel;
(e) a member selected from alloys of titanium and niobium and alloys of copper and chromium; or (f) a member selected from alumina, titania, silica, sili-con carbide, silicon nitride, boron nitride and chromia.
According to another aspect of this invention there is provided in a process for reacting a hydrocarbon with steam and/or an oxygen~containing gas at high pressure in a reactor made of a nickel-containing heat-resistant steel to produce a gaseous mixture containing hydrogen and carbon monoxide, the improvement which comprises coating the surfaces of said reactor that are exposed to said hydrocarbon, with (a) a member selected from titanium, cobalt, chromium, iron and alloys thereof;
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b) a member selected from titanium, cobalt, chromium, iron and alloys thereof containing aluminum or aluminum and silicon;
Ic) a steel not containing nicXel;
Id) an alloy steel containing aluminum or aluminum and silicon and not containing nickel;
(e) a member selected from alloys and titanium and niobium and alloys of copper and chromium; or (f) a member selected from alumina, titania, silica, silicon carbide, silicon nitride, boron nitride and chromia.
Detailed Description of the Invention In the practice of the present invention, any of the coating materials belonging to the aforesaid categories (a) to (f) may be used to coat the surfaces of the apparatus that are exposed to the hydrocarbon-containing material to be treated. These coating materials are more specifically explained in the following.
Among the metallic materials belonging to the category (a), typical examples of the alloys of iron and -3a-il4U16Z
chromium are an iron-chromium alloy containing 17 to 19% by weight of chromium and 0 3% by weight of carbon, and an iron-chromium alloy containing 26 to 28% by weight of chromium and 0.1% by weight of carbon.
Typical examples of the alloys belonging to the category ~b) are a titanium-aluminum alloy containing 6% by weight of aluminum and a Ti-Al-Zr-V alloy containing 6% by weight of aluminum, 4% by weight of zirconium, and 1% by weight of vanadium.
A typical example of the alloys belonging to the category ~d) is an Fe-Cr-Al-Si alloy containing 23% by weight of chromium, 1.5% by weight of aluminum, and 1.5% by weight of silicon.
The alloys of titanium and niobium belonging to the category ~e) may consist of 91 to 99% by weight of titanium, 1 to 3% by weight of niobium, and O to 2% by weight each of other components such as zirconium, aluminum and tantalum.
The alloys of copper and chromium belonging to the category (e) may consist of 95 to 99% by weight of copper, 1 to 3% by weight of chromium, and O to 2% by weight of other components such as beryllium.
No particular limitation is placed on the method by which the surfaces of the apparatus that are exposed to the hydrocarbon-containing material is coated with a met~llic material belonging to any of the aforesaid categories (a) to (e). However, this coating is usually accomplished by the so-called casting method in which a melt of the metallic material is poured over the surfaces to be covered of the structural material previously formed into tubes, plates or other members; the method in which a means for producing high '' , temperatures, such as acetylene burner, electric arc, etc., is ¦ used to cause a melt of the metallic material to adhere to the surfaces to be covered of the structural material; the method in which a melt of the metallic material is sprayed and deposited on the surfaces to be covered of the structural material as in the flame spraying or the plasma jet process;
the chemical vapor deposition method in which a vapor of a i metallic compound is contacted with the surfaces to be coated of the structural material and subjected to a chemical reaction to deposit the metal thereon; the physical vapor deposition method in which a vapor of a metal or its compound is lj ionized in a high vacuum, and the resulting ions are supplied ¦1, with kinetic energy in an electric field and then led into a plasma or other space where they are directly deposited on i the surfaces to be coated of the structural material or Il subjected to a chemical reaction to deposit ~ the metal !l thereon; or the so-called cladding method in which tubes, plates or other members are separately fabricated of the metallic material and bonded to the surfaces to be coated of the previously shaped structural material by the application l of pressure.
When the members coated with a metallic material belonging to any of the aforesaid categories ~a) to ~e) are I used at high temperature, a slight degree of interdiffusion or mixing of components occurs between the nickel-containing structural material and the coating material. It is desirable, therefore, that the coating material has a thickness of not less than 100 microns so as to w~thstand a long-term service.
I
The resulting shaped and coated structural material may further be subjected to bending, tube-expanding, welding and other working operations to fabricate an apparatus or its parts having any desired shapes. However, if the structural material is in the form of castings it is desireble not to subject the covered structural material to bending, tube-expanding, or other working operations.
The method of coating the structural material with a non-metallic material belonging to the aforesaid category (f) depends on the type of the non-metallic material.
~ A) If the non-metallic material is an oxide, the coating can be accomplished by the so-called spraying method in which the oxide is melted and sprayed on the surfaces to be coated of the structural material as in the flame spraying or the plasma jet process; or the so-called baking method in which a suspension of the oxide is applied to the surfaces to be coated of the structural material and then baked at high temperature. In the latter case, however, it is desirable to bake the oxide in combination with a mixture consisting of varying proportions of oxides selected from silica, alumina, boron oxide, calcium oxide, zinc oxide, barium oxide, l zirconium oxide and the like, for the purpose of reducing the ¦ melting temperature of the oxide to lower than that of the structural material and thereby preventing melting or alteration of the structural material. Nevertheless, the temperature at which the coated structural material obtained by this baking method can be used is limited to the melting temperautre of the covering layer.
I
l - 6 -.
114~)162 (B) If the non-metallic material is silicon carbide, silicon nitride or boron nitride, the coating can be accomplished by the method in which a melt or solution of a compound containing silicon-to-carbon, nitrogen-to-boron or nitrogen-to-silicon bonds is applied to the surfaces to be coated of the structural material and then subjected to a chemical reaction in air or an inert gas at high temperature to deposit the desired compound thereon; the above-described spraying method in which a powder or rod of silicon carbide, boron nitride or silicon nitride is melted and sprayed on the surfaces to be coated of the structural material according to the plasma jet process; the above-described chemical vapor deposition method; or the above-described physical vapor deposition method.
~ here the surfaces to be coated of the structural material aforesaid category ~f), the structural material may be in the form of tubes, plates or any other members, as is the case with the metallic materials belonging to the aforesaid categories (a) to (e). When such a non-metallic material is used, a coating layer having a thickness of not less than 10 microns is required. However, the thickness of the coating layer is desirably not greater than 1 millimeter.
This is because, when an apparatus having a unduly thick coating layer is subjected to a heating step or the like, the coating layer not only reduces the overall coefficient of heat transfer to interfere with the flow of heat therethrough but also is liable to spall off owing to the difference in thermal expan on coefficient between he structural material and the I
il4V16Z
coating material.
Among various members made of the above-described structural material and coated with the above-described coating material, tubes are particularly important because they are often used as reactors, heat exchangers and the li~e and, therefore, have abundant opportunities of being exposed to a hot hydrocarbon-containing material. Accordingly, depending on the pathway by which a hydrocarbon-containing material flows through a reactor or heat exchanger, it may often be necessary to coat not only one surface of the tube but both surfaces thereof.
No particular limitation is placed on the hydrocarbon which is treated in the practice of the present invention.
Specific examples of the hydrocarbon can range from hydrocarbons having a small number of carbon atoms, such as methane, ethane, etc., to hydrocarbons having a large number of carbon atoms, such as heavy oil obtained as a distillate by subjecting reduced crude to vacuum distillation Generally speaking, the hydrocarbon which is treated in the practice of the present invention has an H/C atomic ratio of 2.0 to 4Ø The present invention is significantly effective when it is applied to the treatment of the aforesaid heavy oil.
The above-described hydrocarbon may be used alone in the form of a gas or liquid. Alternatively, it may be used in admixture with steam and/or an oxygen-containing gas, or in admixture with hydrogen, carbon monoxide, carbon dioxide and/or olefins (they may represent a product gas obtained by treating a hydrocarbon or a mixture of a hydrocarbon and steam 114V~62 I
and/or an oxygen-containing gas). The content of the hydrocarbon in such mixtures are usually in the range of 10 to 60% by weight.
The term "treat" as used herein means not only to subject a hydrocarbon-containing material to a chemical reaction such as thermal cracking, steam reforming, partial oxidation, etc., but also to handle a feed stream and a product stream before and after this chemical reaction.
In the practice of the present invention, the hydrocarbon-containing material is treated at temperatures of 500C or above. Moreover, this treatment is preferably carried out at a pressure of 6 to 100 kg/cm2G. As the structural material of apparatus for treatment under such severe conditions, nickel-containing materials such as nickel-containing heat-resistant steels are used in ordinary cases.
In accordance with one feature of the present invention, when a hydrocarbon-containing material is treated at temperatures of 500C or above and especially when it is subjected to a chemical reaction, such as thermal cracking, steam reforming, partial oxidation, etc., in the presence or absence of a catalyst, the deposition and accumulation of solid carbon on the surfaces of the reactor that are exposed to the hydrocarbon-containing material can be decreased significantly. If the deposited and accumulated solid carbon is left as it is, it interferes with the passage of a fluid containing the hydrocarbon and causes an increase in pressure loss. Moreover, in cases where it is necessary to remove or supply the heat of reaction for the purpose of effecting the 11~0~L62 aforesaid chemical reaction, the deposited and accumulated solid carbon also causes a marked decrease in overall coefficient of heat transfer and thus makes it difficult to continue the operation. As a countermeasure, therefore, it is necessary to shut down the large-scale system at regular intervals and remove the deposited carbon by any of the well- `
known means. If the present invention is applied, the frequency of this carbon-removing operation can be reduced to 2/3 less of that required in the prior art.
Another feature of the present invention is that the carburization of the nickel-containing structural material can be diminished greatly. It is well known that, when a carbon steel or an alloy steel containing nickel, chromium, iron and the like are exposed to carbon-containing substances, such as hydrocarbons, carbon oxides, etc., at temperatures of 700C or above, the so-called carburi~ation phenomenon occurs. That is, their carbon component infiltrates and diffuses into the microstructure of the steel and thereby reduces its strength to such a degree that the steel is no longer fit for use. It is said that such carburization is not only due to the infiltration and diffusion of the deposited carbon into the microstructure of the steel but also attributable to the presence of a gaseous carbon-containing substance. Thus, the present invention makes it possible to prolong the service lives of members, such as reactor tubes, pipings, etc~, which would otherwise have to be replaced at intervals of 2 or 3 years.
The present invention can produce marked effects when . '~
il40~62 it is applied to parts, members or apparatus made of a nickel-containing heat-resistant steel and used at temperatures of 500C or above and specifically to the surfaces thereof that are exposed to a stream of hydrocarbon-containing material.
Although these parts, members and apparatus may have any desired shapes, tubular members used as reactors are particularly important. This is because, in the reactor, the stream of hydrocarbon-containing material usually reaches a maximum temperature, the deposition of carbon is most likely to occur owing to the necessity of removing or supplying a large amount of reaction heat, and the reduction in overall coefficient of heat transfer caused by the deposited carbon leads to the greatest trouble.
The present invention is further illustrated by the following examples. However, these examples,are not to be construed to limit the scope of the invention.
Example Ethane was subjected to steam cracking in reactor tubes having an inner diameter of 27 mm and a length of 800 mm.
These reactor tubes were made of a nickel-containing steel (Fe-20% Ni-25% alloy) and had their inner surface covered with the respective covering materials shown in Table 1.
The ratio of ethane to steam was 7 : 3 and the reactor tube was maintained at a temperature of 700C or 1,100C by external heating. After the operation was continued for 10 hours at a pressure of 1 kg/cm2G and at a feed rate of 100 cc/min, the conditions of carbon deposition on theinside surface of the reactor tube were examined. The results th`us obtained are il4V162 i~
summarized in Table 1.
Table 1 I Coating Material on Inside Surface of Reactor Tube and Conditions of Carbon Deposition ~ I
Test Coating Material Testing Conditions of Carbon Deposition Tube on Inside Surface Temper- on Inside Surface of Tube No. of Tubeature . _ (C)Amount Deposited _. _ (mgicm /10 hr) Form 1 Chromium1,000 1.0 Filmy 1!2 Fe-28%Cr Alloy1,000 2.i Filmy 1!3 Ti-6%Al Alloy 700 0.3 Sootlike 4 1.5%Si Alloyl,DOO 2.1 Filmy . 5 Ti-2%Nb Alloy 700 0.3 Sootlike 6 Cu-1%Cr Ailoy 700 < 0.1 Sootlike 7 Alumina1,000 2.0 Filmy 8 Titania1,000 1.4 Filmy 9 Silica 1,000 1.6 Filmy Silicon Carbide1,000 1.2 Filmy ~,11 Silicon Nitride1,000 1.4 Filmy !!12 Boron Nitride1,000 1.4 Pilmy 13 Chromia1,000 1.0 Filmy 14 None 1,000 -3.4 .~ilmy ~1 !
! l As is evident from the data shown in Table 1, a considerable degree of carbon deposition was noted on the uncovered inside surface of a tube made of a nickel-containing steel, even in the case of steam cracking of ethane which is a i light hydrocarbon. This carbon deposition was decreased to a ;¦ substantial degree by coating that surface with a nickel-free Il metallic or non-metalllc material. Among others, chromium, ¦l a titanium-niobium alloy and a copper-chromium alloy were found to be particularly excellent coating materials.
Claims (3)
1. In a process for treating a hydrocarbon-containing material at temperatures of 500°C or above in an apparatus made of a nickel-containing heat-resistant steel, said hydrocarbon-containing material being selected from the group consisting of a hydrocarbon, a mixture of a hydrocarbon and at least one member selected from steam and an oxygen-containing gas, and a mixture of a hydrocarbon and at least one member selected from hydrogen, carbon monoxide, carbon dioxide and olefine, the improvement which comprises coating the surfaces of said apparatus that are exposed to said hydrocarbon-containing material, with (a) a member selected from titanium, cobalt, chromium, iron and alloys thereof;
(b) a member selected from titanium, cobalt, chromium, iron and alloys thereof containing aluminum or aluminum and silicon;
(c) a steel not containing nickel;
(d) an alloy steel containing aluminum or aluminum and silicon and not containing nickel;
(e) a member selected from alloys of titanium and niobium and alloys of copper and chromium; or (f) a member selected from alumina, titania, silica, silicon carbide, silicon nitride, boron nitride and chromia.
(b) a member selected from titanium, cobalt, chromium, iron and alloys thereof containing aluminum or aluminum and silicon;
(c) a steel not containing nickel;
(d) an alloy steel containing aluminum or aluminum and silicon and not containing nickel;
(e) a member selected from alloys of titanium and niobium and alloys of copper and chromium; or (f) a member selected from alumina, titania, silica, silicon carbide, silicon nitride, boron nitride and chromia.
2. In a process for reacting a hydrocarbon with steam and/or an oxygen-containing gas at high pressure in a reactor made of a nickel-containing heat-resistant steel to produce a gaseous mixture containing hydrogen and carbon monoxide, the improvement which comprises coating the surfaces of said reactor that are exposed to said hydrocarbon, with (a) a member selected from titanium, cobalt, chromium, iron and alloys thereof;
(b) a member selected from titanium, cobalt, chromium, iron and alloys thereof containing aluminum or aluminum and silicon;
(c) a steel not containing nickel;
(d) an alloy steel containing aluminum or aluminum and silicon and not containing nickel;
(e) a member selected from alloys of titanium and niobium and alloys of copper and chromium; or (f) a member selected from alumina, titania, silica, silicon carbide, silicon nitride, boron nitride and chromia.
(b) a member selected from titanium, cobalt, chromium, iron and alloys thereof containing aluminum or aluminum and silicon;
(c) a steel not containing nickel;
(d) an alloy steel containing aluminum or aluminum and silicon and not containing nickel;
(e) a member selected from alloys of titanium and niobium and alloys of copper and chromium; or (f) a member selected from alumina, titania, silica, silicon carbide, silicon nitride, boron nitride and chromia.
3. A process as claimed in claim 2 wherein the surfaces of said reactor that are exposed to said hydrocarbon are coated with a member selected from chromium, a titanium-niobium alloy and a copper-chromium alloy.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP160810/1979 | 1979-12-13 | ||
| JP16081079A JPS5684789A (en) | 1979-12-13 | 1979-12-13 | High-temperature treatment of hydrocarbon-containing material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1140162A true CA1140162A (en) | 1983-01-25 |
Family
ID=15722910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000366750A Expired CA1140162A (en) | 1979-12-13 | 1980-12-12 | High-temperature treatment of hydrocarbon-containing materials |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS5684789A (en) |
| AU (1) | AU6536780A (en) |
| BR (1) | BR8008164A (en) |
| CA (1) | CA1140162A (en) |
| CS (1) | CS226024B2 (en) |
| DD (1) | DD155140A5 (en) |
| DE (1) | DE3046412A1 (en) |
| FR (1) | FR2472035A1 (en) |
| GB (1) | GB2066696A (en) |
| IN (1) | IN153575B (en) |
| PL (1) | PL130430B1 (en) |
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| JPS5827787A (en) * | 1981-08-10 | 1983-02-18 | Matsushita Electric Ind Co Ltd | Control of carbon |
| GB2116209B (en) * | 1981-12-23 | 1985-08-29 | Toyo Engineering Corp | Composite steel tube for thermally cracking or reforming hydrocarbons |
| JPS5953590A (en) * | 1982-09-21 | 1984-03-28 | Osaka Gas Co Ltd | Heat-treatment of coal-based heavy oil |
| US4507196A (en) * | 1983-08-16 | 1985-03-26 | Phillips Petroleum Co | Antifoulants for thermal cracking processes |
| US4724064A (en) * | 1983-11-17 | 1988-02-09 | Betz Laboratories, Inc. | Composition and method for coke retardant during hydrocarbon processing |
| US4686201A (en) * | 1984-07-20 | 1987-08-11 | Phillips Petroleum Company | Antifoulants comprising tin antimony and aluminum for thermal cracking processes |
| US4599480A (en) * | 1985-07-12 | 1986-07-08 | Shell Oil Company | Sequential cracking of hydrocarbons |
| JPS6365057A (en) * | 1986-09-05 | 1988-03-23 | Kubota Ltd | Tube for thermal decomposition or reforming reaction of hydrocarbons |
| DE4002839A1 (en) * | 1990-02-01 | 1991-08-08 | Forschungszentrum Juelich Gmbh | High temp. multilayer wall structure - with iron or nickel alloy core contg. carbide formers |
| US5015358A (en) * | 1990-08-30 | 1991-05-14 | Phillips Petroleum Company | Antifoulants comprising titanium for thermal cracking processes |
| SA05260056B1 (en) | 1991-03-08 | 2008-03-26 | شيفرون فيليبس كيميكال كمبني ال بي | Hydrocarbon processing device |
| 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 |
| CA2105188A1 (en) * | 1992-09-22 | 1994-03-23 | George A. Coffinberry | Coated article for hot hydrocarbon fluid and method of preventing fuel thermal degradation deposits |
| DE4242099A1 (en) * | 1992-12-14 | 1994-06-16 | Abb Patent Gmbh | Appts., esp. gas turbine appts. - having coating on its operating parts in contact with fuel gas or waste gas to reduce pollutant emissions |
| CN1043037C (en) * | 1993-01-04 | 1999-04-21 | 切夫里昂化学公司 | Hydrodealkylation processes |
| USRE38532E1 (en) | 1993-01-04 | 2004-06-08 | Chevron Phillips Chemical Company Lp | Hydrodealkylation processes |
| JP3471017B2 (en) * | 1993-01-04 | 2003-11-25 | シェブロン ケミカル カンパニー | Dehydrogenation process and equipment therefor |
| EP0645472A1 (en) * | 1993-09-23 | 1995-03-29 | General Electric Company | Coated article for hot hydrocarbon fluid and method of preventing fuel thermal degradation deposits |
| US5575902A (en) * | 1994-01-04 | 1996-11-19 | Chevron Chemical Company | Cracking processes |
| US6258256B1 (en) | 1994-01-04 | 2001-07-10 | Chevron Phillips Chemical Company Lp | Cracking processes |
| US6274113B1 (en) | 1994-01-04 | 2001-08-14 | Chevron Phillips Chemical Company Lp | Increasing production in hydrocarbon conversion processes |
| GB9414415D0 (en) * | 1994-07-16 | 1994-09-07 | Oxford Appl Res Ltd | Cracking feedstocks |
| US5807616A (en) * | 1995-04-24 | 1998-09-15 | Corning Incorporated | Thermal cracking process and furnace elements |
| US6071563A (en) * | 1995-04-24 | 2000-06-06 | Corning Incorporated | Method of protecting metal |
| GB2306510B (en) * | 1995-11-02 | 1999-06-23 | Univ Surrey | Modification of metal surfaces |
| US6503347B1 (en) * | 1996-04-30 | 2003-01-07 | Surface Engineered Products Corporation | Surface alloyed high temperature alloys |
| US6419986B1 (en) | 1997-01-10 | 2002-07-16 | Chevron Phillips Chemical Company Ip | Method for removing reactive metal from a reactor system |
| US6440895B1 (en) | 1998-07-27 | 2002-08-27 | Battelle Memorial Institute | Catalyst, method of making, and reactions using the catalyst |
| US6258330B1 (en) * | 1998-11-10 | 2001-07-10 | International Fuel Cells, Llc | Inhibition of carbon deposition on fuel gas steam reformer walls |
| US6358618B1 (en) | 1999-09-22 | 2002-03-19 | Corning Incorporated | Protective coating on metal |
| KR20030024685A (en) * | 2000-06-08 | 2003-03-26 | 서피스 엔지니어드 프로덕츠 코포레이션 | Coating system for high temperature stainless steel |
| AU6784601A (en) * | 2000-06-28 | 2002-01-08 | Sanyo Electric Co., Ltd. | Fuel reforming reactor and method for manufacture thereof |
| US6737175B2 (en) * | 2001-08-03 | 2004-05-18 | Exxonmobil Research And Engineering Company | Metal dusting resistant copper based alloy surfaces |
| SE525460C2 (en) * | 2002-02-28 | 2005-02-22 | Sandvik Ab | Use of a copper alloy in carburizing environments |
| ES2224003T3 (en) * | 2002-07-31 | 2005-03-01 | Itn Nanovation Gmbh | CERAMIC COATING FOR COMBUSTION BOILERS. |
| SE526448C2 (en) * | 2003-08-28 | 2005-09-20 | Sandvik Intellectual Property | Copper base alloy and its use in boiling environments |
| SE526673C2 (en) * | 2003-08-28 | 2005-10-25 | Sandvik Intellectual Property | Use of a metal sputtering resistant copper alloy |
| US7422804B2 (en) | 2004-02-03 | 2008-09-09 | Exxonmobil Research And Engineering Company | Metal dusting resistant stable-carbide forming alloy surfaces |
| SE528984C2 (en) * | 2005-08-19 | 2007-04-03 | Sandvik Intellectual Property | Composite material comprising a load carrying part and a corrosion resistant part |
| DE102006029790A1 (en) | 2006-06-27 | 2008-01-03 | Basf Ag | Continuous heterogeneously catalyzed partial dehydrogenation of hydrocarbon involves dehydrogenation through catalyst bed disposed in reaction chamber and with generation of product gas |
| ES2549704B1 (en) * | 2014-04-30 | 2016-09-08 | Abengoa Hidrógeno, S.A. | Water vapor reforming reactor tube |
| EP3336055B1 (en) | 2016-12-19 | 2019-05-22 | L'air Liquide, Société Anonyme Pour L'Étude Et L'exploitation Des Procédés Georges Claude | Corrosion protected reformer tube with internal heat exchanger |
| KR102428962B1 (en) * | 2020-07-07 | 2022-08-04 | 한국과학기술연구원 | Lightweight hydrogen generating reactor comprising composite materials with high efficiency |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1988873A (en) * | 1930-07-02 | 1935-01-22 | Ig Farbenindustrie Ag | Thermal treatment of hydrocarbons |
| US1995647A (en) * | 1930-07-24 | 1935-03-26 | Ig Farbenindustrie Ag | Apparatus for and improvement in carrying out chemical processes at elevated temperatures |
| GB361856A (en) * | 1930-07-25 | 1931-11-25 | Ig Farbenindustrie Ag | Improvements in carrying out reactions in the presence of hydrogen |
| GB403647A (en) * | 1932-06-18 | 1933-12-18 | Ig Farbenindustrie Ag | Improvements in the thermal treatment of hydrocarbons |
| GB1149163A (en) * | 1966-03-22 | 1969-04-16 | Ici Ltd | Protection against carburisation |
| US3507929A (en) * | 1966-11-30 | 1970-04-21 | John Happel | Decoking process for a pyrolysis reactor |
| US3536776A (en) * | 1967-08-24 | 1970-10-27 | Mobil Oil Corp | Hydrocarbon pyrolysis |
| US3704333A (en) * | 1970-08-20 | 1972-11-28 | Continental Oil Co | Thermal decomposition of organic compounds |
| FR2165263A5 (en) * | 1971-12-23 | 1973-08-03 | Onera (Off Nat Aerospatiale) | Refractory alloy tubing - for high temp hydrocarbon vapour transport |
| US3865634A (en) * | 1973-08-13 | 1975-02-11 | Exxon Research Engineering Co | Heat resistant alloy for carburization resistance |
| US3827967A (en) * | 1973-08-30 | 1974-08-06 | Shell Oil Co | Thermal cracking of hydrocarbons |
| JPS5832229B2 (en) * | 1978-09-22 | 1983-07-12 | 日本真空技術株式会社 | Vacuum containers and vacuum equipment parts coated with metal nitride |
| US4297150A (en) * | 1979-07-07 | 1981-10-27 | The British Petroleum Company Limited | Protective metal oxide films on metal or alloy substrate surfaces susceptible to coking, corrosion or catalytic activity |
-
1979
- 1979-12-13 JP JP16081079A patent/JPS5684789A/en active Pending
-
1980
- 1980-11-25 IN IN1312/CAL/80A patent/IN153575B/en unknown
- 1980-11-27 GB GB8038064A patent/GB2066696A/en not_active Withdrawn
- 1980-12-10 DE DE19803046412 patent/DE3046412A1/en not_active Withdrawn
- 1980-12-11 FR FR8026344A patent/FR2472035A1/en active Granted
- 1980-12-12 AU AU65367/80A patent/AU6536780A/en not_active Abandoned
- 1980-12-12 BR BR8008164A patent/BR8008164A/en unknown
- 1980-12-12 DD DD22602780A patent/DD155140A5/en unknown
- 1980-12-12 CS CS879480A patent/CS226024B2/en unknown
- 1980-12-12 PL PL22842580A patent/PL130430B1/en unknown
- 1980-12-12 CA CA000366750A patent/CA1140162A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| BR8008164A (en) | 1981-06-30 |
| AU6536780A (en) | 1981-06-18 |
| IN153575B (en) | 1984-07-28 |
| CS226024B2 (en) | 1984-03-19 |
| DE3046412A1 (en) | 1981-09-10 |
| DD155140A5 (en) | 1982-05-19 |
| PL130430B1 (en) | 1984-08-31 |
| FR2472035A1 (en) | 1981-06-26 |
| GB2066696A (en) | 1981-07-15 |
| PL228425A1 (en) | 1981-08-07 |
| JPS5684789A (en) | 1981-07-10 |
| FR2472035B1 (en) | 1984-04-27 |
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