EP2376663B1 - Method for producing a gaseous atmosphere for treating metals - Google Patents

Description

The present invention relates to the field of heat treatment of metal parts.

One of the objectives of the present invention is to propose a novel method of providing an atmosphere to be injected in furnaces intended for the heat or thermochemical treatment of metal parts.

The atmospheres targeted by the present invention must make it possible on the one hand to avoid decarburization and oxidation of the parts, but on the other hand to be able to enrich the carbon parts (carburizing and carbonitriding processes). Finally, this atmosphere must be produced in economic conditions, safe, and easy to handle.

The heat treatment atmospheres meeting the above criteria generally contain, as major components of nitrogen, which has a neutral role with respect to the treatments mentioned above, hydrogen which protects against oxidation, and carbon monoxide. carbon that both protects against oxidation and decarburization and allows if necessary to achieve a carbon enrichment (cementation). These atmospheres also contain minor components such as CO ₂ and water or CH ₄ . The atmosphere can also be enriched with hydrocarbons (natural gas, propane, etc.) in order to influence the chemical equilibrium.

Among the methods traditionally used currently to produce such atmospheres include the methods listed below, well known to those skilled in the art.

First, these atmospheres can be produced by so-called "endothermic generators". These generators produce the atmosphere from a reaction between air and a fuel (usually natural gas), a reaction occurring in a catalytic reactor heated to a temperature of the order of 1000 ° C. This type of atmosphere typically contains as major components 40% nitrogen (N2), 40% hydrogen (H2), and 20% carbon monoxide (CO). Atmospheres produced by an endothermic generator are known and used for many years, but have the disadvantage of requiring for the user the investment of a dedicated production machine. In addition, the use of an endothermic generator is often not very flexible. The production capacity generally adapts with difficulty to the real need and it is then necessary to continuously produce a flow rate higher than the required flow. On the other hand, the contents of the various constituents of the mixture are fixed by the reaction occurring in the catalytic reactor: if it remains possible to reduce the contents of H ₂ and CO by dilution with nitrogen (process commonly known as "endo diluted "), it is however not industrially feasible to increase the contents of CO and H ₂ beyond 20% and 40% respectively. Indeed, to increase the majority contents it is necessary to increase the oxygen content at the expense of nitrogen, which poses problems of safety and holding materials.

Another well-known method of manufacture is described as "in situ", or "synthetic atmosphere", in that the atmosphere is obtained without intervention of an external generator, but by direct injection into the furnace a mixture of the various gaseous constituents necessary, these constituents reacting with each other in situ, in a zone adapted to the oven temperature. Among these atmospheres are in particular mixtures of nitrogen and methanol. Methanol is most often injected with a cane inserted in the heat treatment furnace by a capillary tube using an annular flow of nitrogen gas which sprays the methanol in the form of fine droplets for 'train in the oven. Under the effect of the oven temperature, which can typically rise to 900 ° C., the methanol molecule cracks to form CO and H ₂ , according to the following reaction:

CH ₃ OH -> CO + 2H ₂ .

The mixture thus formed contains twice as much hydrogen as CO.

Atmospheres formed from nitrogen and methanol thus allow in particular to synthesize an atmosphere identical to that produced by an endothermic generator. It is also possible, according to the ratio of nitrogen and methanol, to obtain an atmosphere richer in H ₂ and CO. These atmospheres will allow in particular to achieve faster cementation treatments. The inconvenients The main reasons for this solution are, firstly, its cost, which is mainly related to the prices of methanol, and secondly the toxicity of the latter, but also concerns the fact that this process is nowadays limited in speed. treatment compared to technological breakthrough processes such as low pressure carburizing. In addition, the cracking reaction of methanol is highly endothermic which results in a significant energy consumption and the formation of cold zones in the furnaces.

où
C_S représente la teneur en carbone des pièces traitées, PC représente le potentiel carbone de l'atmosphère défini comme la teneur d'un clinquant en fer exposé à l'atmosphère pendant une durée infinie, β est le coefficient de transfert de carbone qui est proportionnel au produit des teneurs en CO et H2.For carburizing or carbonitriding treatments carried out under a gaseous atmosphere of the generator atmosphere or synthetic atmosphere type, the speed of the treatment is related to the carbon transfer rate between the atmosphere and the surface of the carbon parts or fluxes φ _C , who can express himself as follows: $${\mathrm{\phi }}_{\mathrm{VS}}=\mathrm{\beta }\left(\mathrm{PC}-{\mathrm{VS}}_{\mathrm{S}}\right)$$

or
C _S represents the carbon content of the treated parts, PC represents the carbon potential of the atmosphere defined as the content of an iron foil exposed to the atmosphere for an infinite duration, β is the carbon transfer coefficient which is proportional to the product of the contents of CO and H2.

The carbon potential can be calculated according to the following relationship assuming an equilibrium atmosphere: $$\mathit{PC}=\frac{100\cdot \mathrm{VS}{O}^2/\mathrm{VS}{O}_2}{19.6\cdot \mathrm{VS}{O}^2/1.07\cdot \exp \left(4798.6/T\right)}$$

The carbon potential is therefore characteristic of the equilibrium that can be made between the part and the atmosphere, and the coefficient β characterizes the speed with which this equilibrium can be reached.

In a search for productivity increase, we can see the interest of increasing the CO and H2 contents, in order to maximize the carbon flow through the carbon potential and the β carbon transfer coefficient. .

An atmosphere containing 50% CO and 50% H2 especially makes it possible to maximize the β carbon transfer coefficient.

The document EP0953654 A1 proposes a method of generating a carburizing atmosphere with a mixture comprising gaseous CO and ethanol injected at high temperature but does not disclose the atmosphere used at temperatures up to 800ºC.

The present invention then proposes a new process for producing an atmosphere of the type referred to above (to avoid decarburization and oxidation of the parts while being able to enrich the carbon parts), this in direct injection into the furnace of a mixture comprising carbon dioxide and ethanol, optionally supplemented with nitrogen, while injecting CO ₂ alone or optionally mixed with nitrogen in the or the phases of the treatment cycle or the zone or zones of the oven whose temperature is below 750ºC.

The subject of the invention is defined in the claims.

This mixture can possibly be enriched with additional species to control the chemical equilibrium in the atmosphere (hydrocarbons, air ...).

The atmosphere can optionally be enriched with ammonia for the carbonitriding processes.

One of the advantageous characteristics of the invention lies, however, in the possibility of using only CO ₂ and ethanol to control these chemical equilibria, where the conventional generator or synthesis atmospheres require additions of air and fuel. hydrocarbon. Depending on the CO ₂ / ethanol ratio, the residual CO ₂ content will be higher or lower, which directly conditions the carbon potential of the atmosphere.

The components intended for the synthesis of the atmosphere can for example be injected using injection equipment already known for the implementation of nitrogen-methanol atmospheres.

As is most commonly practiced, injecting the liquid phase (ethanol) through a capillary in a rod having an annular flow composed of gaseous phases (CO ₂ , nitrogen) which will thus cause ethanol and spray in the oven.

Ethanol can also be vaporized upstream of the injection of the furnace in order to be injected in gaseous form in a mixture with the other gaseous species.

Finally still for illustrative purposes ethanol can be introduced directly into the liquid phase in the oven chamber (for example deposited in a cup) so that it vaporizes under the effect of the oven temperature and can thus react with the gaseous species introduced separately into the furnace enclosure.

Inside the oven, the CO ₂ reacts with ethanol to form a mixture of hydrogen and CO according to the reaction:

CO ₂ + C ₂ H ₅ OH → 3 CO + 3 H ₂ .

However, according to a preferred embodiment of the invention, the injection is carried out during a treatment phase or in an oven zone at a temperature greater than 750 ° C, and even more preferably whose temperature is in the range of 850 ° C to 1000 ° C.

It will be understood that we can deal with continuous furnaces or not, and therefore we will discuss in the following indifferently "oven area" or "phase of treatment" where / during which is injected the mixture comprising the Ethanol (even a batch oven may have multiple zones or chambers and not all of these rooms have the same atmosphere).

It is also known that the safety constraints related to the use of the heat treatment atmospheres and described in standard NF-EN 746-3 are very rigorous, and notably require not to inject an atmosphere considered flammable (by example potentially containing more than 5% of the mixture H ₂ , CO) below 750 ° C. As a result, below 750 ° C, the processes generally inject a "substitution" gas, usually nitrogen alone.

• Le rôle de « gaz de procédé » mélangé au gaz issu du cracking du méthanol (l'azote joue le rôle de gaz porteur en « poussant le méthanol);
• Le rôle de «gaz de sécurité» (100% du débit) dans les cas suivants :
  • quand la température est inférieure à 750°C ;
  • pour la détection de chute de débit ou de pression d'azote.

It can thus be said that, in the case of nitrogen-methanol atmospheres, nitrogen performs the following functions:

• The role of "process gas" mixed with gas from methanol cracking (nitrogen acts as a carrier gas by "pushing methanol);
• The role of "safety gas" (100% of flow) in the following cases:
  • when the temperature is below 750 ° C;
  • for the detection of flow drop or nitrogen pressure.

It is then proposed according to the present invention to inject the mixture comprising ethanol above 750 ° C, and to inject below 750 ° C CO ₂ alone, or optionally mixed with nitrogen, which has Moreover, the advantage of pre-oxidation of the feed, which will accelerate the treatment by burning the organic matter (grease, cutting oil, etc.) and activating the surface for treatment in the next phase of the process. cycle.

• dans le cas d'utilisation de mélanges de CO₂ et d'éthanol sans azote, on obtient un mélange H₂/CO contenant 50% de chaque constituant. Ce mélange est connu pour donner une efficacité et une rapidité de traitement optimales pour la cémentation (hors cémentation basse pression). Par rapport aux atmosphères conventionnelles de générateur endothermique ou azote-méthanol, on obtient ainsi un gain de productivité pouvant aller jusqu'à 30% ;
• par ailleurs l'éthanol présente un coût relativement similaire à celui du méthanol, tout en donnant lieu à la formation d'un volume d'atmosphère plus important. En effet, 1 litre de méthanol donne lieu à la formation de 1,67 Nm³ de gaz craqué (H₂ + CO), alors que la même quantité d'éthanol donne lieu à la formation de 1.95 Nm³ d'atmosphère ;
• l'éthanol est un produit non-toxique contrairement au méthanol ;
• il est disponible à la fois de sources de production à base d'énergies fossiles ou à base de produits de l'agriculture, alors que le méthanol est issu exclusivement de procédés de production basés sur des produits pétroliers ;
• le procédé conforme à l'invention s'adapte facilement sur les fours aujourd'hui alimentés par des mélanges traditionnels d'azote et de méthanol, il permet en effet d'utiliser tel que l'ensemble des circuits d'injection d'azote et de méthanol existants ;
• au besoin, le mélange H₂/CO ainsi généré peut être dilué à l'azote de façon à régler de façon très flexible la composition et donc l'activité de l'atmosphère ;
• il permet la pré-oxydation des charges sans nécessité de disposer d'un four spécifique pour cette opération.

The process according to the invention has many advantages over existing processes among which the following aspects can be mentioned:

• in the case of using mixtures of CO ₂ and ethanol without nitrogen, an H ₂ / CO mixture containing 50% of each constituent is obtained. This mixture is known to give optimum efficiency and speed of treatment for carburizing (excluding low pressure cementation). Compared to the conventional atmospheres of endothermic generator or nitrogen-methanol, a productivity gain of up to 30% is thus obtained;
• Moreover, ethanol has a relatively similar cost to that of methanol, while giving rise to the formation of a larger volume of atmosphere. In fact, 1 liter of methanol gives rise to the formation of 1.67 Nm ³ of cracked gas (H ₂ + CO), whereas the same quantity of ethanol gives rise to the formation of 1.95 Nm ³ of atmosphere;
• ethanol is a non-toxic product unlike methanol;
• it is available from both fossil-fuel and agricultural-based production sources, whereas methanol comes exclusively from production processes based on petroleum products;
• the process according to the invention is easily adapted to the furnaces now fed by conventional mixtures of nitrogen and methanol, it makes it possible to use such as the set of nitrogen injection circuits and existing methanol;
• if necessary, the mixture H ₂ / CO thus generated can be diluted with nitrogen so as to adjust very flexibly the composition and therefore the activity of the atmosphere;
• it allows pre-oxidation of the charges without the need for a specific furnace for this operation.

The present invention thus relates to a method for generating an atmosphere for the heat treatment of metal parts in an oven, according to which the introduction, in at least one phase of the treatment cycle or at least one zone of the furnace of heat treatment of a mixture comprising gaseous CO ₂ and ethanol in the form of fine droplets or of steam, so as to carry out inside the furnace the reaction between the CO ₂ and the ethanol to form a mixture of hydrogen and CO according to the reaction:

CO ₂ + C ₂ H ₅ OH → 3 CO + 3 H ₂ .

and characterized in that the injection is carried out in a phase of the treatment cycle or an area of the heat treatment furnace whose temperature is greater than 750 ° C, and even more preferably in the range of 850 ° C to 1000 ° C, while injecting into the phase or phases of the treatment cycle or the zone or zones of the oven whose temperature is below 750 ° C, CO ₂ alone or optionally mixed with nitrogen.

• le mélange injecté comporte également de l'azote gazeux,
• l'éthanol est réchauffé et/ou vaporisé avant injection dans le four.

The present invention may furthermore adopt one or more of the following technical characteristics:

• the injected mixture also comprises nitrogen gas,
• the ethanol is heated and / or vaporized before injection into the oven.

Claims (4)

1. Method for generating an atmosphere configured for heat treating metal parts in a furnace, which includes inserting, in at least one phase of the treatment cycle or at least one area of the heat treatment furnace, a mixture comprising gaseous CO₂ and ethanol in the form of fine droplets or vapour, so as to carry out the reaction between the CO₂ and the ethanol inside the furnace to form a mixture of hydrogen and CO according to the reaction:
   
           CO₂ + C₂H₅OH --> 3 CO + 3 H₂
   
   and being characterised in that the injection is performed in a phase of the treatment cycle or in an area of the heat treatment furnace of which the temperature is higher than 750°C, while CO₂ alone or optionally mixed with nitrogen is injected in the phase or phases of the treatment cycle or the area or areas of the furnace of which the temperature is lower than 750°C.
2. Method according to claim 1, characterised in that said mixture injected into a phase of the treatment cycle or an area of the heat treatment furnace of which the temperature is higher than 750°C also comprises gaseous nitrogen.
3. Method according to one of the preceding claims, characterised in that the ethanol is heated and/or vaporised before injection into the furnace.
4. Method according to one of the preceding claims, characterised in that the injection of the mixture comprising gaseous CO₂ and ethanol in the form of fine droplets or vapour is performed in a phase of the treatment cycle or an area of the heat treatment furnace of which the temperature is located in the interval between 850°C and 1000°C.