Catalyst, method for producing catalyst and method for producing product

Abstract

The application relates to a catalyst, a method for producing the catalyst, and a method for producing a carbon product. The catalyst for a chemical reaction forming the carbon product is formed from Fe-based material, in which the Fe-based material is treated by an activation treatment to form a catalyst material, and the catalyst is formed from the catalyst material.

Description

[0001] CATALYST, METHOD FOR PRODUCING CATALYST AND METHOD FOR PRODUCING PRODUCT

[0002] FIELD

[0003] The application relates to a catalyst for a chemical reaction forming at least a carbon product defined in claim 1. Further, the application relates to a method defined in claim 8 for producing a catalyst. Further, the application relates to a method defined in claim 17 for producing a product, preferably at least a carbon product, by a chemical reaction with the catalyst.

[0004] BACKGROUND

[0005] It is known to use different catalysts for forming carbon products. Metal catalysts, such as metal supported catalysts, may be used in the reactions for forming carbon products, e.g. in a thermocatalytic conversion or pyrolysis processes.

[0006] OBJECTIVE

[0007] The objective is to disclose a novel type of catalyst for a reaction in which solid carbon products are produced. Further, the objective is to disclose a novel type of method for producing the catalyst. Further, the objective is to disclose an improved process for methane decomposition or pyrolysis. Further, the objective is to achieve an effective process for forming solid carbon products.

[0008] SUMMARY

[0009] The catalyst, method for producing the catalyst and method for producing at least a carbon product are characterized by what are presented in the claims. The catalyst for a chemical reaction, where at least a carbon product i s produced, i s formed from Fe- based material , in which the Fe-based material is treated by an activation treatment to form a catalyst material , and the catalyst is formed from the catalyst material .

[0010] The method for producing a catalyst for a chemical reaction comprises treating a Fe-based material by an activation treatment to form a catalyst material , and forming the catalyst from the catalyst material .

[0011] The method for producing at least a carbon product by a chemical reaction with the catalyst comprises arranging a reactant into contact with the catalyst for performing the chemical reaction in a reactor to form the carbon product , and performing the chemical reaction at a temperature of 550 - 1000 ° C in the reactor, and recovering at least the carbon product .

[0012] DETAILED DESCRIPTION

[0013] The catalyst for a chemical reaction is formed from Fe-based material , in which the Fe-based material is treated by an activation treatment to form a catalyst material , and the catalyst is formed from the catalyst material , and wherein the Fe-based material is selected from the group comprising s ide stream material , residual material , industrial waste material , sandblasting material , or any combination thereof . In the chemical reaction, at least a carbon product is formed by the catalyst .

[0014] The method for forming the catalyst comprises : selecting a Fe-based material , treating the Fe-based material by an activation treatment to form a catalyst material , and forming the catalyst from the catalyst material . The Fe-based material can be selected from the group comprising side stream material , residual material, industrial waste material, sandblasting material, or any combination thereof.

[0015] In this context, the Fe-based material means any Fe-based material, preferably side stream material, residual material, industrial waste material or the like which comprises at least Fe . The Fe-based material may comprise several components, and further impurities. The Fe-based material may contain 30 - 100 w-% iron, in one embodiment 30 - 99 w-%, in one embodiment 55 - 95 w-%, in one embodiment 60 - 90 w-%, and in one embodiment 80 - 100 w-%. Typically, the Fe-based material does not comprise iron oxides, and iron in the Fe-based material is in an inert form.

[0016] In one embodiment, the Fe-based material is selected from the group consisting of Fe-based sandblasting material, i.e. sand blast material, Fe-based flakes of sandblasting, Fe-based balls of sandblasting, Fe- based scale of sandblasting, Fe-based abrasive blasting material, Fe-based grit material, Fe-based shot blasting material, Fe-slag, Fe-containing slag, Fe-based scrap, Fe-based ore material, Fe-based industrial side stream material, e.g. red mud from aluminium production, Fe- based sludge or other industrial side stream, or any combination thereof. In one embodiment, the Fe-based material is selected from the group consisting of Fe- based sandblasting material, Fe-based flakes of sandblasting, Fe-based balls of sandblasting, Fe-based scale of sandblasting, Fe-based abrasive blasting material, Fe-based grit material, Fe-based shot blasting material, Fe-slag, Fe-containing slag, Fe-based scrap, Fe-based industrial side stream material, or any combination thereof. In one embodiment, the Fe-based material is selected from the group consisting of Fe-based sandblasting material, Fe-based abrasive blasting material, Fe-based grit material, Fe-based shot blasting material, Fe-based flakes of sandblasting, Fe-based scale of sandblasting, Fe-based balls of sandblasting, or any combination thereof . In one embodiment , the Fe-based material is Fe-based scale of sandblasting or Fe-based balls of sandblasting . In the sandblasting, rust patches and scratches are removed from the metal surfaces . In one embodiment , iron based sandblasted material and also residue materials from metal processes are a used material or waste material . In one embodiment, the iron based sandblasted material is a fresh material .

[0017] In one embodiment , the Fe-based material is arranged into the form of particles , balls , flakes , or any combination thereof , preferably before the activation treatment .

[0018] In one embodiment , the Fe-based material is treated by a chemical and / or physical activation treatment . In one embodiment , the Fe-based material is treated by the chemical and / or physical activation treatment , which is selected from the group consisting of an acid treatment, alkali treatment, steam activation, air activation, carbon dioxide activation, e . g . in supercritical conditions , calcination, reduction, sintering, mechanical treatment, or any combination thereof . In one embodiment, the activation treatment or its one step is selected from the acid treatment, steam activation, air activation, mechanical treatment, or any combination thereof . In one embodiment , the Fe-based material is activated using the chemical and / or physical activation treatment, such as the acid treatment , steam activation, air activation, mechanical treatment, or any combination thereof . In one embodiment , the Fe-based material is treated using a mechanical treatment, e . g . milling, ball milling or other suitable treatment . In one embodiment , the ball milling is carried out with balls . In one embodiment , the Fe-based material is activated using at least acid treatment, steam activation and / or air activation to form the catalyst material . In one embodiment , the Fe-based material is treated using an alkali treatment, e.g. with NaOH, Ca(OH)2, KOH or other suitable alkali agent. In one embodiment, heat is used during the activation treatment. Preferably, iron is oxidized, at least partially oxidized, during the activation treatment to convert an inert form of iron to catalytic form. In one embodiment, a core of the catalyst material, e.g. a core of the catalyst particle, comprises Fe after the activation, and the surface of the catalyst material, e.g. catalyst particle, has been modified to form an active surface, and optionally also a porous surface. Then, the core of the catalyst is solid and / or hard, and carbon may be separated and / or removed more easily from the surface of the catalyst, e.g. mechanically, by rubbing the catalyst particles against each other and / or by other suitable treating. The catalyst core may then be reactivated and reused.

[0019] In one embodiment, the Fe-based material is treated by an acid treatment. In one embodiment, the Fe- based material is treated by the acid treatment, which is selected from the group consisting of acid digestion, acid dissolution, precipitation, and any combination thereof. In one embodiment, the Fe-based material is treated by the acid digestion. In one embodiment, the Fe- based material is treated by the acid dissolution. In one embodiment, the Fe-based material is treated by the acid dissolution and precipitation. In one embodiment, the Fe-based material is treated by the acid digestion and acid dissolution. In one embodiment, HNO3, HC1, HCOOH, H2SO4 or other suitable acid is used as an acid in the acid treatment in the acid treatment. In one embodiment, HNO3, HC1 or HCOOH is used as the acid. In one embodiment, HNO3 is used as the acid in the acid digestion. In one embodiment, HC1 is used as the acid in the acid dissolution. In one embodiment, HCOOH is used as the acid in the acid dissolution. In one embodiment, the Fe-based material is dried before the acid-treatment . In one embodiment, the Fe-based material is calcined before the acid-treatment . In one embodiment , the Fe-based material is dried and calcined before the acid-treatment . Preferably, the acid treatment is a purification leaching process wherein some of impurities are removed . In one embodiment, there may be a partial oxidation of iron-to-iron oxides during the acid treatment, and further possible impurities , such as metal nitrates , may be leached .

[0020] In one embodiment, the acid digestion is carried out at a temperature of 80 - 130 °C, in one embodiment at a temperature of 90 - 125 ° C, and in one embodiment at a temperature of 110 - 120 °C .

[0021] In one embodiment, the acid dissolution is carried out at a temperature of 50 - 80 °C, in one embodiment at a temperature of 50 - 70 ° C, and in one embodiment at a temperature of 55 - 65 °C . In one embodiment, the acid dissolution and precipitation are carried out at a temperature of 50 - 80 °C, in one embodiment at a temperature of 50 - 70 ° C, and in one embodiment at a temperature of 55 - 65 °C .

[0022] In one embodiment, the Fe-based material is stirred during and / or after the acid treatment . In one embodiment, the Fe-based material is stirred during the acid treatment . In one embodiment, the Fe-based material is stirred after the acid treatment . In one embodiment , a pH is adj usted during and / or after the acid treatment, e . g . by an acid addition . In one embodiment , the Fe-based material is stirred, and the pH is adj usted during and / or after the acid treatment . In one embodiment , the Fe-based material is stirred at a temperature of 50 - 70 ° C, e . g . about 60 ° C, and simultaneously the pH is adj usted . In one embodiment, pH is adj usted to a level of 7 - 9 . In one embodiment, the method further comprises stirring the Fe-based material and / or adj usting a pH during and / or after the acid treatment .

[0023] In one embodiment, the Fe-based material is calcined and / or reduced . In one embodiment , the Fe-based is reduced . In one embodiment, the Fe-based is reduced under suitable gas flow, e . g . H2 flow . In one embodiment , the Fe-based material is calcined and / or reduced, preferably after the activation treatment or at least one step of the activation treatment . In one embodiment , an activation-treated Fe-based material is calcined and / or reduced . In one embodiment, the Fe-based material is calcined . In one embodiment, the Fe-based material is calcined and reduced . In one embodiment, the Fe-based material is reduced after the calcination . In one embodiment , an acid-treated Fe-based material is calcined and / or reduced, preferably after the acid-treatment . In one embodiment, the acid-treated Fe-based material is calcined . In one embodiment, the acid-treated Fe-based material is reduced . In one embodiment, the acid-treated Fe-based material is calcined and reduced . In one embodiment, the acid-treated Fe-based material is reduced after the calcination, e . g . under suitable gas flow, e . g . H2 flow . In one embodiment, the acid-treated Fe-based material is heated, e . g . to a temperature of 750 - 900 ° C, and reduced after the calcination . In one embodiment, the method further comprises : calcining and / or reducing the Fe-based material , preferably the activation-treated Fe-based material . In one embodiment, the method further comprises : calcining the Fe-based material at a temperature of 550 - 950 °C, in one embodiment at a temperature of 700 - 900 °C . In one embodiment, the method further comprises : reducing the Fe-based material at a temperature of 500 - 900 °C, in one at a temperature of 550 - 900 ° C, and in one embodiment at a temperature of 700 - 900 °C . In one embodiment, Fe oxides may be reduced to form Fe metal or metallic crystals in the reduction . Then, the catalyst has an unique crystal structure to enable graphitic carbon growth .

[0024] In one embodiment, the Fe-based material is dried before the calcination . In one embodiment , the Fe- based material is dried during the calcination or in the beginning of the calcination . In one embodiment , the method further comprises drying the Fe-based material before the calcination . In one embodiment , the drying is carried out at a temperature of 70 - 100 °C, in one embodiment 80 - 95 °C, e . g . about 90 ° C .

[0025] In one embodiment, the catalyst is produced from a Fe-based material comprising Fe- f lakes . The Fe- based material is treated by an acid digestion to form a catalyst material at a temperature of 90 - 120 °C . HNO3 may be used as an acid, or alternatively other suitable acid may be used as an acid . The Fe-based catalyst material is calcined and reduced at a temperature of 500 - 700 ° C after the acid treatment . In one embodiment , catalytic agent may be added to the catalyst material to form the catalyst .

[0026] In one embodiment, the catalyst is produced from a Fe-based scale of sandblasting, in which the Fe- based material is treated by an acid digestion and dissolution to form a catalyst material at a temperature of 100 - 140 ° C, or alternatively at a temperature of 70 - 120 °C . HNO3 may be used as an acid, or alternatively HCOOH or other suitable acid may be used as an acid . Optionally, the Fe-based material is stirred and / or pH is adj usted during the acid treatment or after the acid treatment . The catalyst material is calcined after the acid treatment . The calcination may be performed at a temperature of 700 - 900 °C, or alternatively at a temperature of 550 - 900 °C . Further, the calcined material may be heated, e . g . to 700 - 900 °C, and reduced under suitable gas flow, e . g . H2 flow . In one embodiment , catalytic agent, e . g . Ni , Cu, Ni-Cu, Mo, Co, Pd, Pt, Mg, Zn, Al , Ti , Mn, Si , B, or an oxide thereof or any combinations thereof , may be added to the catalyst material to form the final catalyst . In one embodiment, MgO, ZnO, B (OH)3, CeO2 , Al2O3-SiO2, aluminosilicate , or any combinations thereof may be added to the catalyst material .

[0027] In one embodiment, the catalyst is produced from a Fe-based sandblasting material , for example , comprising rough and sharp edges , dust and small balls . The Fe-based material is treated by an acid digestion to form a catalyst material at a temperature of about 100 - 140 °C, or alternatively at a temperature of 70 - 120 °C . HNO3may be used as an acid, or alternatively other suitable acid may be used as an acid . The catalyst material is calcined after the acid treatment . The calcination may be performed at temperatures of 700 - 900 ° C, or alternatively at a temperature of 550 - 950 °C . Further, the catalyst material may be reduced, e . g . at low temperature . The catalyst can be formed from the catalyst material . In one embodiment, catalytic agent may be added to the catalyst material to form the catalyst .

[0028] In one embodiment , the catalyst is produced from a Fe-based scale of sandblasting . The Fe-based material is treated by an acid digestion and dissolution to form a catalyst material at a temperature of 100 - 140 °C, or alternatively at a temperature of 70 - 120 ° C . HNO3, and alternatively HCOOH or other suitable acid, may be used as an acid . Optionally, the Fe-based material may be stirred at 50 - 70 ° C and / or pH may be adj usted . After that , the catalyst material may be dried at a temperature of 70 - 100 ° C, and calcined at 700 °C - 900 °C . In one embodiment, catalytic agent may be added to the catalyst material to form the catalyst .

[0029] In one embodiment, the catalyst is produced from a Fe-based residue material . The Fe-based material is treated by an acid dissolution and precipitation to form a catalyst material at a temperature of about 60 ° C . HC1, and alternatively other suitable acid, is used as an acid. Optionally, the Fe-based material is stirred at 50 - 70 °C and / or pH is adjusted. After that, the catalyst material is dried at a temperature of 70 - 100 °C and calcined at 700 °C - 900 °C. In one embodiment, catalytic agent may be added to the catalyst material to form the catalyst .

[0030] In one embodiment, the catalyst is produced from the Fe-based material. The Fe-based material is treated by an acid, and after the acid-treatment, the material is reduced.

[0031] In one embodiment, a catalytic agent, e.g. a promoter, is added to the catalyst material to form the catalyst. The catalytic agent may be formed of one or more components. In one embodiment, the catalytic agent contains a catalytically active agent, e.g. metal or metals, and a carrier material, e.g. Mg-, A1-, Zn-based carrier material. In one embodiment, the catalytic agent is the catalytically active agent, e.g. Ni, Cu, Ni-Cu. In one embodiment, the catalytic agent is selected from the group consisting of nickel, copper, molybdenum, magnesium, zinc, aluminium, titanium, cobalt, manganese, chromium, silicon, boron, cobolt, platinum, palladium, carbon, and an oxide thereof, and any combination thereof. In one embodiment, the catalytic agent or catalytically active agent is selected from Ni, Cu, Ni-Cu, Mo, Mg, Zn, Co, Pt, Pd, Mn, B, Al, Ti, Si, or oxide thereof, aluminosilicate, or any combination thereof. In one embodiment, the catalytic agent is selected from MgO, ZnO, B(OH)3, CeO2, A12O3-S1O2, aluminosilicate or any combinations thereof. In one embodiment, the catalytic agent or catalytically active agent is selected from nickel, copper, Ni-Cu alloy, molybdenum, or any combination thereof. In one embodiment, the catalytic agent or catalytically active agent contains Ni-Cu metals. In one embodiment, the method further comprises: adding the catalytic agent to the catalyst material to form the catalyst .

[0032] In one embodiment , the catalytic agent contains at least metal as a catalytically active agent . In one embodiment , the metal is selected from nickel and / or copper . In one embodiment , the catalytic agent comprises one or more catalytically active agents . In one embodiment , the catalytic agent contains at least two metals . In one embodiment , the catalytic agent is formed of one or more catalytically active agent .

[0033] In one embodiment , the catalytic agent is arranged to a surface of the catalyst material , where the chemical reaction can be carried out . In one embodiment , the catalytic agent is arranged to form a catalyst surface onto the catalyst . In one embodiment , the catalytic agent is impregnated to the Fe-based material to form the catalyst material . In one embodiment , the catalytic agent is impregnated to the catalyst material to form the catalyst .

[0034] In one embodiment , the catalytic agent , promoter, additive and / or secondary metal-based material are added to the Fe-based material . In one embodiment , the catalytic agent, promoter and / or additive are added to the catalyst material .

[0035] The catalyst may comprise a desired shape or structure . The catalyst is formed of the catalyst material , preferably without a support or a support material , i . e . the catalyst is a non-supported catalyst . In one embodiment , the catalyst or its surface may be pretreated by modi fying for improving the activity of the catalyst . In one embodiment , the catalyst is pre-treated at least by an acid, heat or their combination .

[0036] In the method embodiment for producing at least a carbon product by a chemical reaction with the catalyst , as defined, a reactant is arranged into contact with the catalyst for performing the chemical reaction in a reactor to form the carbon product; the chemical reaction is performed at a temperature of 550 - 1000 °C in the reactor, and at least the carbon product is recovered .

[0037] The carbon product comprises at least carbon, especially an allotrope of carbon. Preferably, the carbon product is formed as the reaction product in the solid form. In one embodiment, the allotrope of the carbon product is formed, and the allotrope comprises carbon nanofibers, carbon nanotubes, single wall carbon nanotubes, multiwalled carbon nanotubes, carbon nano onions, carbon nano shells, carbon micro shells, carbon coils, amorphous carbon, graphene, graphite fibers, graphite, or any combination thereof. In one embodiment, the allotrope of the carbon product is formed, and the allotrope comprises graphite fibers and / or graphite, e.g. any graphite, turbostratic graphite, any graphite fibers, filamentous graphite fibers or the like. In one embodiment, the allotrope of the carbon product is a mixture of the allotropes. The allotrope of the carbon product may contain also other graphitic type carbon and / or metal or metal oxide impurities.

[0038] In one embodiment, the chemical reaction is selected from the group consisting of a methane splitting, catalysed methane splitting, catalysed pyrolysis, catalysed hydrocarbon pyrolysis, catalysed methane pyrolysis, catalytic hydrocarbon decomposition, catalytic methane decomposition, thermocatalytic decomposition, thermocatalytic methane decomposition, chemical vapor deposition, other reaction, or any combination thereof. In one embodiment, the chemical reaction is the thermocatalytic decomposition.

[0039] In one embodiment, the method further comprising producing hydrogen in the reactor. The hydrogen is formed by the chemical reaction, and the hydrogen is recovered from the reactor. Preferably, the chemical reaction is carried out by the catalyst in the reactor, preferably inside the reactor. In this context, the reactor may be any reactor, chamber or space where the chemical reaction can be carried out. In one embodiment, the reactor is selected from the group consisting of a pyrolysis reactor, fluidized reactor, fixed reactor, fixed bed reactor, rotary kiln reactor or any combination thereof. In one embodiment, the reactor is a fluid bed reactor or a rotary kiln reactor.

[0040] In one embodiment, the chemical reaction is performed at a pressure between 0 - 5 bars and / or at a temperature between 550 - 1000 °C, e.g. 600 - 900 °C. In one embodiment, the chemical reaction is performed at a reaction temperature of between 600 - 900 °C, in one embodiment 750 - 850 °C. In one embodiment, the chemical reaction is performed under the atmospheric pressure. In one embodiment, the chemical reaction is performed under the pressure of between 0 - 5 bars. In one embodiment, the contact time of the reactant with the catalyst is selected based on the reactant and the catalyst. In one embodiment, the chemical reaction is the reaction, in which the hydrocarbon is treated, and the hydrocarbon is selected from the group of Ci-io-al- kanes, such as methane and ethane, C2-io_alkenes and C2- 10-alkynes, or a mixture of hydrocarbons. Preferably, the reactant is fed to the reactor and the chemical reaction is performed in the reactor, and at least carbon is formed, and it can be recovered. Preferably, the reactant is arranged to contact with the catalyst in the reactor. In this context, the reactant means any suitable reactant, which can be treated in the process. In one embodiment, the reactant is a hydrocarbon selected from the group of Ci-10-alkanes , such as methane and ethane, C2-io_alkenes , and C2-io_alkynes , or any combination thereof . In one embodiment , the reactant comprises at least methane .

[0041] In one embodiment , the reactant is arranged to flow from top to bottom in the reactor . The reactant flow direction from top to bottom enables easier carbon recovery from the bottom . In one embodiment , the reactant is arranged to flow from bottom to top in the reactor, especially i f a fluidi zed reactor i s used . In one embodiment , the reactant i s arranged to flow horizontally .

[0042] In one embodiment , the catalyst is used in a methane splitting, catalysed methane splitting, catalysed pyrolysis , catalysed hydrocarbon pyrolysis , catalysed methane pyrolysis , catalytic hydrocarbon decomposition, catalytic methane decomposition, thermocata- lytic decomposition, thermocatalytic methane decomposition, chemical vapor deposition, other reaction, or any combination thereof . In one embodiment , the catalyst i s used in a reactor, vertical reactor, tube reactor, fixed reactor, fixed bed reactor, pyrolysis reactor, fluidi zed reactor, rotary kiln reactor or any combination thereof . The reactor may be a batch reactor or a continuous reactor . In one embodiment, the reactor is a batch rotary kiln reactor or a continuous rotary kiln reactor .

[0043] Thanks to the invention an ef fective process can be provided to produce solid carbon products and hydrogen . When the Fe-based raw material is treated by the activation treatment , the activity of the catalyst can be increased, and the catalyst is active already at a temperature of 750 - 850 ° C . The carbon yield and methane conversion can be increased . Further, the carbon formation and allotropes may be modi fied . The carbon product having high purity may be achieved . For example , the carbon and / or the allotropes of the carbon may have purity of 80 - 99 % . Further, the acid treatment modi fies the structure of the Fe-based material and / or physical properties , e . g . surface area, reduction profile and other properties . The Fe-rich catalysts are cheap, environmentally friendly and sustainable . Further, the catalysts may be regenerated, recycled and / or reused .

[0044] The invention of fers a possibility to achieve the carbon product and hydrogen with good properties easily . Further, ef ficiency can be improved in the ther- mocatalytic decomposition process , e . g . methane splitting .

[0045] BRIEF DESCRIPTION OF THE DRAWINGS

[0046] The accompanying drawing, which is included to provide a further understanding of the invention and constitute a part of this speci fication, illustrates some embodiments of the invention and together with the description help to explain the principle of the invention . In the drawing :

[0047] Figs . 1 , 2 and 3 show the test results o f the catalysts .

[0048] EXAMPLES

[0049] The catalyst is produced from a Fe-based material . The Fe-based material is treated by an activation treatment to form a catalyst material , and the catalyst is formed from the catalyst material . For example , Fe- based scale of sandblasting or Fe-based balls of sandblasting may be used as the Fe-based material . Alternatively other suitable Fe-based material may be used as the Fe-based material .

[0050] The Fe-based material is treated by a chemical and / or physical activation treatment, which may be selected from the group consisting of an acid treatment , steam activation, air activation, reduction, mechanical treatment, or any combination thereof . According to an example , the Fe-based material may be stirred during and / or after the activation treatment , e . g . acid treatment. Further, according to an example, a pH may be adjusted during and / or after the activation treatment, e.g. acid treatment.

[0051] The Fe-based material is at least calcined, and optionally reduced, after the activation treatment. Alternatively, the Fe-based material is at least reduced. The Fe-based material may be calcined at a temperature of 700 - 900 °C. The Fe-based material may be reduced at a temperature of 500 - 900 °C. According to an example, the Fe-based material may be dried before the calcination or during the calcination.

[0052] The catalyst is formed from the catalyst material. The catalyst can be used in the chemical reaction for forming a solid carbon product, preferably comprising an allotrope or allotropes of the carbon. A hydrocarbon reactant, e.g. methane or other hydrocarbon, is arranged into contact with the catalyst for performing the chemical reaction in a reactor, e.g. fluid bed reactor, to form the carbon product. The chemical reaction is performed at a temperature of 750 - 850 °C in the reactor, and at least the carbon product is recovered.

[0053] According to an example, a catalytic agent is added to the catalyst material to form the catalyst. The catalyst agent comprises metal, e.g. nickel and copper metals or Ni-Cu alloy.

[0054] Example 1

[0055] In this example, the catalyst was produced from a Fe-based material comprising Fe-f lakes. The Fe-based material was treated by an acid digestion to form a catalyst material at a temperature of 90 - 120 °C for 2 - 16 hours. 1 M HNO3 was used as an acid. In the acidtreatment, iron is, at least partially, oxidized and thus the Fe-based material is converted from an inert form to catalytic active material, and possibly metal nitrates are leached. The Fe-based catalyst material was calcined and reduced at a temperature of about 550-900 °C after the acid treatment. Then, Fe-oxides are reduced to form Fe metallic crystals.

[0056] Example 2

[0057] In this example, the catalyst was produced from a Fe-based scale of sandblasting. The Fe-based material was treated by an acid digestion and dissolution to form a catalyst material at a temperature of about 120 °C. In the first tests (A) HNO3 was used as an acid, and in the second tests (B) HCOOH was used as an acid. Further, in both tests concentrations of the acids were 1 M (Al, Bl) and 2 M (A2, B2) . In tests B, pH was adjusted during the acid treatment to 7 - 11. The catalyst material was calcined after the acid treatment. The calcination was performed at two different temperatures, i.e. at 700 °C and 900 °C, for 1 hour. The calcined samples were heated to 800 °C and reduced under pure H2 flow for 2 hours.

[0058] Further, catalytic agents, such as Ni, Cu, Ni- Cu and Mo, were added to the catalyst material. The catalyst was formed from the catalyst material. The catalysts were tested in the process conditions, such as at 750 - 800 °C, to form carbon product in the methane decomposition reactor.

[0059] It was observed from the tests that the Fe- based raw material, without treating, is inactive at 750 - 800 °C temperature. The carbon yield and methane conversion increased clearly after the acid treatment. Further, it was observed that the acid treatment enriches the iron oxides, leaches out the impurities or trace elements. Further, the acid treatment modifies the structure of the Fe-based material, i.e. textural properties are enhanced, and makes more surface reactivity, and modifies physical properties, e.g. surface area, reduction profile and other properties. Even the carbon formation was different than the untreated samples. When the treated Fe-based sandblasting scale material was used in the catalyst, the significant amount of multiwalled carbon nanotubes were grown besides graphitic carbon nano onions and flakes.

[0060] Example 3

[0061] In this example, the catalyst was produced from a Fe-based sandblasting material comprising rough and sharp edges and dust. The Fe-based material comprised about 94.5 w-% iron. The Fe-based material was treated by an acid digestion to form a catalyst material at a temperature of about 40 - 120 °C. HNO3 was used as an acid. The catalyst material was calcined after the acid treatment. The calcination was performed at two different temperatures, i.e. at 700 °C and 900 °C. Further, the catalyst material was reduced at low temperature, e.g. 650 - 800 °C.

[0062] The catalyst was formed from the catalyst material. The catalysts were tested in the process conditions, such as at 750 - 850 °C, to form carbon product in a mid-scale reactor of the methane splitting.

[0063] The acid-treated Fe-based material was compared to the raw Fe-based sandblasting material, prepared without the acid treatment.

[0064] It was observed from the tests that the raw Fe- based sandblasting material, without treating, is low in activity at 750 - 850 °C temperature. The carbon yield and methane conversion increased after the acid treatment. The acid-treated sandblast material was highly active and selective in the production, where high yield of graphitic carbon was achieved, compared to the raw Fe-based sandblasting material. With the acid-treated sandblast material, almost 5 times carbon yield was achieved compared to the raw Fe-based sandblasting material. Further, it was observed that the physiochemical properties of the acid treated sandblast material can be modified, and surface properties and reducibility may be improved.

[0065] Example 4

[0066] According to this example, the catalyst is produced from a Fe-based scale of sandblasting material. The Fe-based material is treated by an acid digestion and dissolution to form a catalyst material at a temperature of about 120 °C. HNO3, and alternatively HCOOH or other suitable acid, is used as an acid. Optionally, the Fe-based material is stirred at 60 °C and pH is adjusted. After that, the catalyst material is dried at 90 °C and calcined at 700 °C - 900 °C.

[0067] Example 5

[0068] In this example, the catalyst was produced from Fe-based balls of sandblasting, such as spherical sandblasting material. The Fe-based material was treated by an acid digestion to form a catalyst material at a temperature of 90 - 120 °C for 2 - 16 hours. 1 M HNO3 was used as an acid. In the acid-treatment, iron is, at least partially, oxidized and thus the Fe-based material is converted from an inert form to catalytic material, and possibly metal nitrates are leached. The Fe-based catalyst material was calcined and reduced at a temperature of about 550-900 °C after the acid treatment. Then, Fe- oxides are reduced to form Fe metallic crystals.

[0069] Example 6

[0070] According to this example, the catalysts were formed from Fe-based material, and the catalysts were compared with the comparative catalysts.

[0071] The samples (catalysts) and comparative samples (comparative catalysts) , as presented in table 1, were formed from Fe-based material, i.e. Fe-based balls of sandblasting (SBX) and Fe-based scale of sandblasting (SFX) .

[0072] The Fe-based material was treated by an acid digestion using HNO3 and by a calcination to form the catalysts (samples) . In the acid-treatment, undiluted HNO3 or IM HNO3 were used as the acid. The calcination was performed at two different temperatures, i.e. at 700 °C and 900 °C.

[0073] The comparative samples (catalysts) were not treated by an acid nor calcined.

[0074] The catalysts were tested in the process conditions, i.e. at a temperature of 750 - 850 °C, to form carbon .

[0075] Further, table 1 shows the results, such as total carbon (g) and yield (g carbon / g catalyst) . Further, the results are shown in Fig. 1.

[0076] Table 1 where undil. means undiluted, pure HNO3concentrated (more than 86 % HNO3or highly concentrated HNO3)

[0077] It was observed from the tests that the comparative catalyst, without treating, is low in activity. The catalysts, with the acid-treatment and calcination, have better carbon yield. Thus, the improved carbon yield can be achieved, when the catalyst is treated with acid and calcined.

[0078] Example 7

[0079] In this example, the catalyst was produced from Fe-based balls of sandblasting, such as spherical sandblasting material. The Fe-based material was treated by a reduction to form a catalyst material at a temperature of 650 - 900 °C for 120 minutes under H2 flow. The size of the particles was 0.3 - 1.5 mm. Fig. 2 shows the reduction with H2 flow for three samples.

[0080] The formed catalysts were tested in the process conditions to form carbon product in the thermocatalytic decomposition reactor, where methane was treated at 750 - 900 °C. Fig. 3 shows carbon yield (gC / h) in the test.

[0081] It was observed from the tests that good carbon yield can be achieved when the treated catalysts are used in the thermocatalytic decomposition.

[0082] The catalyst and method are suitable in different embodiments for using in different processes where carbon is formed. Further, the invention is suitable in different embodiments for producing carbon products and other products, such as hydrogen.

[0083] The invention is not limited merely to the examples referred to above; instead, many variations are possible within the scope of the inventive idea defined by the claims.

Claims

CLAIMS1 . A catalyst for a chemical reaction forming at least a carbon product , wherein the catalyst is formed from Fe-based material , in which the Fe-based material is treated by an activation treatment to form a catalyst material , and the catalyst is formed from the catalyst material , and wherein the Fe-based material is selected from the group comprising side stream material , residual material , industrial waste material , sandblasting material , or any combination thereof .2 . The catalyst according to claim 1 , wherein the Fe-based material is treated by a chemical or physical activation treatment, selected from the group consisting of an acid treatment, steam activation, air activation, mechanical treatment, or any combination thereof .3 . The catalyst according to claim 1 or 2 , wherein the Fe-based material is treated by an acid treatment , which is selected from the group consisting of acid digestion, acid dissolution, precipitation, and any combination thereof .4 . The catalyst according to any one of claims 1 to 3 , wherein the Fe-based material is calcined and / or reduced .5 . The catalyst according to any one of claims 1 to 4 , wherein a catalytic agent is added to the catalyst material to form the catalyst .

6. The catalyst according to claim 5 , wherein the catalytic agent is selected from the group consisting of nickel , copper, molybdenum, magnesium, zinc, aluminium, titanium, cobalt , manganese, chromium, silicon, boron, platinum, palladium, carbon, and an oxide thereof , and any combination thereof .7 . The catalyst according to any one of claims 1 to 6 , wherein the Fe-based material is selected fromthe group consisting of Fe-based sandblasting material , Fe-based flakes of sandblasting, Fe-based balls of sandblasting, Fe-based scale of sandblasting, Fe-based abrasive blasting material , Fe-based grit material , Fe-based shot blasting material , Fe-slag, Fe-containing slag, Fe- based scrap, Fe-based industrial side stream material , or any combination thereof .8 . A method for producing a catalyst for a chemical reaction forming at least a carbon product , wherein the method comprises : selecting a Fe-based material , treating the Fe-based material by an activation treatment to form a catalyst material , and forming the catalyst from the catalyst material , and wherein the Fe- based material is selected from the group comprising side stream material , residual material , industrial waste material , sandblasting material , or any combination thereof .9 . The method according to claim 8 , wherein the Fe-based material is treated by a chemical or physical activation treatment , selected from the group consisting of an acid treatment, steam activation, air activation, mechanical treatment, or any combination thereof .10 . The method according to claim 8 or 9 , wherein the Fe-based material is treated by an acid treatment, which is selected from the group consisting of acid digestion, acid dissolution, precipitation, and any combination thereof .11 . The method according to any one of claims 8 to 10 , wherein the acid digestion is carried out at a temperature of 80 - 130 °C .12 . The method according to any one of claims 8 to 11 , wherein the acid dissolution and precipitation is carried out at a temperature of 50 - 80 °C .13 . The method according to any one of claims 8 to 12 , wherein the Fe-based material is selected from the group consisting of Fe-based sandblasting material ,Fe-based flakes of sandblasting, Fe-based balls of sandblasting, Fe-based scale of sandblasting, Fe-based abrasive blasting material, Fe-based grit material, Fe-based shot blasting material, Fe-slag, Fe-containing slag, Fe- based scrap, Fe-based industrial side stream material, or any combination thereof.

14. The method according to any one of claims 8 to 13, wherein the method further comprises: calcining the Fe-based material at a temperature of 550 - 950 °C.

15. The method according to any one of claims 8 to 14, wherein the method further comprises: reducing the Fe-based material at a temperature of 500 - 900 °C.

16. The method according to any one of claims 8 to 15, wherein the method further comprises: adding a catalytic agent to the catalyst material to form the catalyst .

17. A method for producing at least a carbon product by a chemical reaction with the catalyst according to any one of claims 1 to 7, wherein the method comprises a) arranging a reactant into contact with the catalyst for performing the chemical reaction in a reactor to form the carbon product; b) performing the chemical reaction at a temperature of 550 - 1000 °C in the reactor; and c) recovering at least the carbon product.

18. The method according to claim 17, wherein the allotrope of the carbon product is formed, and the allotrope comprises carbon nanofibers, carbon nanotubes, single wall carbon nanotubes, multiwalled carbon nanotubes, carbon nano onions, carbon nano shells, carbon micro shells, carbon coils, amorphous carbon, graphene, graphite fibers, graphite, or any combination thereof .

19. The method according to claim 17 or 18, wherein the chemical reaction is selected from the groupconsisting of a methane splitting, catalysed methane splitting, catalysed pyrolysis , catalysed hydrocarbon pyrolysis , catalysed methane pyrolysis , catalytic hydrocarbon decomposition, catalytic methane decomposi- tion, thermocatalytic decomposition, thermocatalytic methane decomposition, chemical vapor deposition, other reaction, or any combination thereof .20 . The method according to any one o f claims 17 to 19 , wherein hydrogen is formed in the chemical reaction, and the hydrogen is recovered from the reactor .21 . The method according to any one of claims 17 to 20 , wherein the reactor is a fluid bed reactor or a rotary kiln reactor .

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