Processes for producing carbon black from low-yield raw materials and products manufactured from them

Abstract

The invention describes processes for producing carbon black from low-yield carbon black raw materials. It further describes carbon blacks produced from these carbon black raw materials. It also describes the advantages obtained with the processes.

Description

Title of the invention: Processes for producing carbon blacks from low-yield raw materials and products manufactured from them

[0001] The present invention relates to methods for producing carbon black from alternative carbon black-producing feedstocks, which in many cases may include gaseous and / or low-yield feedstocks. The present invention further relates to carbon blacks formed from alternative carbon black-producing feedstocks that include gaseous and / or low-yield carbon black feedstocks.

[0002] Carbon black is used to modify the mechanical, electrical, and optical properties of compositions. Carbon blacks and other fillers are used as pigments, fillers, and / or reinforcing agents in the compounding and preparation of compositions used in rubber, plastic, paper, or textile applications. The properties of carbon black or other fillers are important factors in determining the various performance characteristics of these compositions. Significant uses of elastomeric compositions are associated with tire manufacturing, and additional ingredients are often added to impart specific properties to the finished product or its components.Carbon blacks are used to modify the functional properties, electrical conductivity, rheology, surface properties, viscosity, appearance and other properties in elastomeric and other types of compositions.

[0003] The classic and most common process for the industrial production of carbon black is the furnace process. In this process, a first liquid feedstock containing carbon, such as decantation oil, is injected into a stream of hot, fuel-poor combustion or burnt gases. Part of the feedstock pyrolyzes to produce carbon black and by-products (mainly hydrogen); the remainder oxidizes to produce CO, CO2, and H2O. The classic or traditional feedstock is decantation oil, oily sludge, coking oil, a coal tar derivative, or a heavy liquid residue from an ethylene cracking process.These carbon black raw materials are simultaneously heavy (relative density > 1.02), have a maximum atomic H:C ratio of 1.23, are rich in aromatics (Mines Bureau Correlation Index (BMCI) > 100), and are liquid at ambient temperature and pressure (e.g., 25 °C at 1 atm). They are all, in principle, derived from fossil fuels.

[0004] The furnace blackening process differs from the tunnel blackening process and the thermal blackening process, both of which use natural gas as a feedstock. The tunnel blackening process uses thousands of small natural gas diffusion flames to produce small quantities of carbon black. The carbon black is collected on water-cooled metal tunnels or drums. The tunnel blackening process had extremely low yields of about 0.05 kg C / kg of charge, which led to its abandonment in the mid-20th century. The thermal blackening process produces a particular type of carbon black with a very low structure by passing the natural gas charge over preheated bricks.Natural gas undergoes endothermic pyrolysis to carbon black above the hot bricks; these bricks cool rapidly, however, and must be periodically reheated by burning hydrogen by-products and natural gas. The thermal blackening process produces only niche grades of carbon black with very low structure and relatively low yield; it cannot produce the vast majority of carbon black surfaces and structures required for reinforcing tires, plastics, or industrial rubber compounds.

[0005] It would be both economically useful and environmentally advantageous to use low-yield, renewable, recycled, and / or sustainable feedstocks in an existing carbon black furnace process. These feedstocks would not necessarily be fossil fuel-based. Examples include ethylene, which can be produced from ethane cracking or from bioethanol. Another example is natural gas, which can be of fossil origin or produced from landfills or the decomposition of organic matter. Other examples include vegetable oil, oils derived from the pyrolysis of recycled tires, plastics, municipal waste, or biomass, or natural gas produced from landfills.

[0006] Unfortunately, these low-yield carbon black feedstocks generally result in poor yields, low surface areas, and / or poor structures in a furnace process, compared to traditionally used furnace carbon black feedstocks. The performance of these feedstocks in a furnace process can be so poor that it may be impossible to produce the structure required for most ASTM grades. The maximum structure achievable at a given surface area for a feedstock helps define the feedstock's quality capability.

[0007] Thus, there is a need in industry to provide a solution to be able to use (to allow the use of) large quantities of low-yield carbon black-forming raw materials (for example, where at least a major part of the total raw material used is a carbon black raw material) low-yield) in an existing carbon black furnace process, and yet produce carbon blacks that are comparable to carbon blacks formed from traditional furnace carbon black feedstocks (e.g., producing carbon blacks with acceptable yields and / or with large surface areas and / or large structures). Using an existing furnace process to utilize these low-yield feedstocks, instead of developing, designing, and constructing a new process to utilize them, results in significant savings of capital and development resources. SUMMARY OF THE PRESENT INVENTION

[0008] A feature of the present invention is to provide processes for preparing or producing carbon black from raw materials which include low-yield carbon black raw material(s).

[0009] Another feature of the present invention is to provide processes for preparing or producing carbon black from raw materials which include gaseous carbon black raw materials.

[0010] An additional feature of the present invention is to provide carbon blacks manufactured from raw materials which include low-yield carbon black raw materials.

[0011] Another feature of the present invention is to provide carbon blacks made from gaseous carbon black raw materials.

[0012] An additional feature consists of providing processes for using carbon black feedstocks in which at least a major part or more of the total quantity of feedstock is a low-yield carbon black feedstock.

[0013] Another feature is to provide a process for producing carbon blacks from low-yield carbon black raw materials such that the resulting carbon black has an acceptable yield (e.g., good), an acceptable surface area (e.g., large) and / or an acceptable structure (e.g., high).

[0014] To achieve these and other advantages, and according to the aims of the present invention, as indicated in the embodiments and extensively described herein, the present invention relates in part to a process for producing carbon black. The process includes the step of introducing a heated gas stream into a carbon black reactor (for example, a furnace carbon black reactor) and combining at least one first carbon black feedstock with the heated gas stream to form a reaction stream. The process further includes the downstream step of combining at least one low-yield carbon black feedstock with an existing reaction stream to form the carbon black. The process further includes the recovery of carbon black from the reaction stream. In the process, at least one low-yield carbon black feedstock comprises a major portion, or at least 60% by weight, of the total feedstock (based on total weight). The first carbon black feedstock is preferably a liquid at ambient temperature and pressure (e.g., 25 °C at 1 atm).

[0015] Furthermore, the present invention relates in part to a carbon black(s) wherein at least a major part of the raw material used to form the carbon black is a low-yield carbon black raw material.

[0016] The present invention further relates to products and / or articles such as, but not limited to, elastomeric composites formed from any or more of the carbon blacks of the present invention.

[0017] It must be understood that the preceding general description and the following detailed description are both given by way of example and explanation only and are intended to provide an alternative explanation of the present invention according to the claims.

[0018] The accompanying drawings, which are incorporated into and form part of this application, illustrate various features of the present invention, and together with the description, serve to explain the principles of the present invention. Brief description of the drawings

[0019] Fig. 1 is a graph illustrating the H:C (hydrogen atom to carbon atom) atomic ratio for traditional carbon black raw materials, compared to the low-yield raw materials used, in part, in the present invention.

[0020] Fig. 2 is a graph illustrating the relative density of traditional carbon black raw materials, compared to the low-yield raw materials that are used, in part, in the present invention.

[0021] Fig. 3 is a graph illustrating the BMCI value for traditional raw materials, compared to low-yield raw materials which are used, in part, in the present invention.

[0022] Fig. 4A is a cross-sectional view of an example of a reactor suitable for preparing carbon black of the present invention.

[0023] Fig. 4B is a cross-sectional view of another example of a reactor suitable for preparing carbon black of the present invention.

[0024] Fig. 5 is a cross-sectional view of a further example of a reactor suitable for preparing carbon black of the present invention.

[0025] Fig. 6A and Fig. 6B illustrate schematic injectors used in some of the comparative examples on a side view.

[0026] Figures 7 and 8 illustrate the dimensionless yield and the STSA (in m² / g) for certain examples and comparative examples of the present invention. The numbering labels refer to the example numbers in Tables 6 to 9.

[0027] Figures 9 and 10 are graphs illustrating the NAO and STSA (in m² / g) for certain examples and comparative examples of the present invention. The labels with whole numbers denote the example numbers in Tables 6 to 9. The numbered "N" labels on the empty diamond-shaped dots indicate data for the specified ASTM carbon black grade; for example, the dot "N330" indicates the typical surface and structure for N330 grade carbon black.

[0028] Figures 11, 12, and 13 illustrate the NAV and STSA (in m² / g) for certain examples and comparative examples of the present invention. Labels with whole numbers refer to example numbers in Tables 10, 13, and 15.

[0029] Figure 14 is a graph illustrating the yield that can be obtained for a given area for the examples and comparative examples of the present invention. The labels bearing whole numbers designate the example numbers in Table 15. DETAILED DESCRIPTION OF THE PRESENT INVENTION

[0030] The present invention relates to processes for producing carbon blacks that use a low-yield carbon black feedstock, as defined and described herein. The present invention further relates to carbon blacks produced by one or more of these processes. With the processes of the present invention, at least a major portion of the total carbon black feedstock used can be one or more low-yield carbon black feedstocks. With the processes of the present invention, large quantities of low-yield carbon black feedstocks can be used without sacrificing the quality of the carbon black produced.Thus, the processes of the present invention use carbon black raw materials that are more desirable to use for ecological and / or other reasons, and which nevertheless produce carbon blacks that are comparable to carbon blacks produced using traditional carbon black raw materials used in furnace carbon black processes.

[0031] A carbon black production process of the present invention comprises, essentially consists of, consists of, or includes the introduction of a gas stream heated in a carbon black reactor (e.g., a furnace carbon black reactor); combining at least one first carbon black feedstock with the heated gas stream to form a reaction stream; combining downstream at least one low-yield carbon black feedstock with the existing reaction stream to form carbon black; and recovering the carbon black from the reaction stream. In the process, preferably, at least one low-yield carbon black feedstock constitutes a major portion by weight of the total feedstock, and more preferably may constitute at least 60% by weight of the total feedstock.

[0032] For the purposes of the present invention, "a low-yield carbon black raw material" is a carbon black raw material having at least one of the following properties: 1. A Bureau of Mines Correlation Index (BMCI) < 100 (which provides an indication of low aromatic content for liquid feedstocks) (e.g., a BMCI below 99, below 95, below 90, below 85, below 80, below 75, below 70, such as a BMCI of 50 to 99 or 60 to 99, or 70 to 99, or 50 to 95 or 50 to 90), and / or 2. a carbon-containing material that is a gas at ambient temperature (e.g., 25 °C) and pressure (1 atm), and / or 3. an H:C atomic ratio greater than 1.23 (for example, an H:C ratio greater than 1.24 or more, 1.25 or more, 1.26 or more, 1.27 or more, 1.28 or more, 1.29 or more, 1.30 or more, 1.35 or more, 1.40 or more, 1.45 or more, 1.50 or more, such as from 1.235 to 1.5, or from 1.235 to 1.45, or from 1.235 to 1.4, or from 1.235 to 1.35, or from 1.235 to 1.3, or from 1.235 to 1.29, or from 1.235 to 1.28, or from 1.235 to 1.27, or from 1.24 to 1.5, or 1.25 to 1.5 or 1.26 to 1.5 or 1.27 to 1.5 or 1.28 to 1.5 or 1.29 to 1.5 or 1.3 to 1.5), and / or 4. a relative density of at most 1.02 (for example, at most 1.015, at most 1.01, at most 1.005, at most 1.01, at most 1.00, at most 0.99, at most 0.95, such as from 0.80 to 1.019, or from 0.80 to 1.015, or from 0.80 to 1.01, or from 0.80 to 1.005, or from 0.80 to 1.00, or from 0.80 to 0.95, or from 0.80 to 0.9, or from 0.80 to 1.015, or from 0.90 to 1.01, or from 0.90 to 1.005, or from 1.005 to 1.015).

[0033] The low-yield carbon black raw material may only exhibit the BMCI property. The low-yield carbon black raw material may only exhibit the H:C atomic ratio property. The low-yield carbon black raw material may only exhibit the relative density property. The low-yield carbon black raw material may only exhibit the gaseous property.

[0034] The low-yield carbon black raw material may exhibit the BMCI property and the H:C atomic ratio property.

[0035] The low-yield carbon black raw material may exhibit the BMCI property and the relative density property.

[0036] The low-yield carbon black raw material may exhibit the property of BMCI and the property of gas.

[0037] The low-yield carbon black raw material may exhibit the BMCI property, the H:C atomic ratio property and the relative density property.

[0038] The low-yield carbon black raw material may exhibit the BMCI property, the H:C atomic ratio property and the gaseous property.

[0039] The low-yield carbon black raw material may exhibit the BMCI property, the H:C atomic ratio property, the relative density property and the gaseous property.

[0040] The low-yield carbon black raw material can exhibit the H:C atomic ratio property and the relative density property.

[0041] The low-yield carbon black raw material can exhibit the H:C atomic ratio property and the gaseous property.

[0042] The low-yield carbon black raw material can exhibit the H:C atomic ratio property, the relative density property and the gaseous property.

[0043] The low-yield carbon black raw material may exhibit the property of relative density and the property of gas.

[0044] A low-yield carbon black feedstock can be a feedstock derived from what are considered sustainable, biological, and / or recycled sources. For example, a low-yield carbon black feedstock can be or include ethylene, a gas at ambient temperature and pressure. Ethylene can be produced from bio-based ethanol, for example, from the fermentation of corn or other plant materials. Another example of a low-yield carbon black feedstock is natural gas.

[0045] The low-yield carbon black raw material, for the purposes of the present invention, may be a raw material that is not derived from the production of fossil fuel-based gasoline or from coal cracking, or from cracking to produce olefins. Thus, the low-yield carbon black raw material is a raw material that is other than liquid coal tar, petroleum refinery liquid, or ethylene cracking residue.

[0046] Other examples of low-yield liquid carbon black feedstocks may include, but are not limited to, the following: tire pyrolysis oil, plastic pyrolysis oil, recycled oil, a algal oil, a plant-derived oil, an oil derived from the pyrolysis of solid municipal waste, an oil derived from the pyrolysis or decomposition of biomass (e.g., animal or vegetable) or agricultural waste, an oil derived from the processing of pulp or by-products of paper production and / or another oil derived mainly from biomaterials or any combination thereof.Examples of low-yield feedstocks include, but are not limited to, vegetable or other plant-derived oils, bio-based ethanol, wax or resin of plant or animal origin, oil obtained from animal fat, algal oil, oil obtained from the pyrolysis of sewage sludge or agricultural waste, a liquid by-product from the processing of biogenic material, a liquid produced by hydrothermal liquefaction of a biomaterial, crude tall oil, tall oil rosin, tall oil pitch or tall oil fatty acid, oil produced from recycled material, oil derived from the pyrolysis of non-standard, discarded, or end-of-life tires, oil derived from the pyrolysis of discarded or recycled plastics or rubber products, oil derived from the pyrolysis of municipal solid waste, or oil derived from the pyrolysis of biomass or any combination thereof. these.These liquid feedstocks have an H:C atomic ratio greater than 1.23, or a relative density of no more than 1.02, or a BMCI value less than 100. The H:C atomic ratio can be measured according to ASTM D5291; the relative density can be measured according to ASTM D4052; the BMCI can be measured according to Smith, H.M. (1940). Correlation Index To Aid in Interpreting Crude-Oil Analyses Technical Paper 610, Washington, DC, US Department of the Interior, Bureau of Mines; the sulfur content can be measured according to IP-336 or ISO 8754. The flash point can be measured according to ISO 2719. Specific examples of low-yield liquid carbon black feedstocks are shown in Table 1 below. [Tables 1] Example of raw material: Bolder 3 50 Tyre Pyrolysis Oil, DE-Solv Delta Energy Tyre Pyrolysis Oil, Soybean Oil, Corn Oil, Peanut Oil. Atomic ratio H:C 1.32 1.5 1.87 1.87 1.87. Relative density 1.00 0.94 0.93 0.92 0.91. BMCI 94 62.5 56 54 50. Sulfur content (% by weight) 1.08 1.03 0 0 0 Table 1.

[0047] Figure 1 is a graph showing the atomic H:C ratio for traditional high-yield carbon black feedstocks, compared to tire pyrolysis oils (TPO), vegetable oils (Veg Oil), and two-phase gaseous feedstocks (natural gas and ethylene) (Gas). For traditional feedstocks, the H:C ratio is shown for a collection of approximately 1000 representative coal tar liquids, decantation oils, and ECRs used as carbon black feedstocks for the furnace black process between 2016 and 2021. The range of H:C values ​​can be compared to the three groups of low-yield carbon black feedstocks. It is evident that traditional feedstocks have a low H:C value < 1.23 (dashed line in the figure). The low-yield carbon black feedstocks in Figure 1 all have an H:C value > 1.23.

[0048] Figure 2 is a graph that presents examples of the relative density of traditional high-yield feedstocks compared with tire pyrolysis oils (TPO) and vegetable oils (Veg Oil). For traditional feedstocks, the relative density is shown for a collection of approximately 1000 representative coal tar liquids, settling oils, and ECRs used as carbon black feedstocks for the furnace black process between 2016 and 2021. The relative density ranges are compared with the two groups of low-yield carbon black feedstocks. It is clear that traditional feedstocks generally exhibit a relative density greater than 1.02 (dashed line in the figure), whereas the feedstocks of Low-yield carbon black exhibits a relative density that is less than or equal to 1.02.

[0049] Figure 3 is a graph showing examples of BMCI numbers for traditional high-yield feedstocks, compared to tire pyrolysis oils (TPO) and vegetable oils (Veg. Oil). For traditional carbon black feedstocks, the BMCI number is shown for a collection of approximately 1000 representative coal tar liquids, settling oils, and ECRs used as feedstocks for the furnace black process between 2016 and 2021. Their BMCI values ​​are compared to the two low-yield feedstock groups. Almost all traditional feedstocks have a BMCI value > 110, and all the examples shown here have a BMCI number greater than or equal to 100 (dashed line). In contrast, the TPO and vegetable oil groups have a BMCI number less than 100.

[0050] Other examples of low-yield carbon black feedstocks may include, but are not limited to, the following: a renewable feedstock, a bio-based or biologically derived feedstock, and / or another by-product of a refining process, or any combination thereof.

[0051] Other examples of low-yield carbon black feedstocks may include, but are not limited to, the following: vegetable oils or other plant-derived oils (e.g., corn oil and / or distiller's corn oil).

[0052] Other examples of low-yield carbon black feedstocks may include, but are not limited to, the following: bio-based ethanol (derived from the fermentation of corn or other fermentation products from plants, vegetables or fruits).

[0053] Other examples of low-yield carbon black raw materials may include, but are not limited to, the following materials: waxes and resins produced from plants or animals, such as lanolin or lacquer.

[0054] Other examples of low-yield carbon black raw materials may include, but are not limited to, the following: oils obtained from animal fats.

[0055] Other examples of low-yield carbon black raw materials may include, but are not limited to, the following materials: algal oils.

[0056] Other examples of low-yield carbon black raw materials may include, but are not limited to, the following: oils obtained from the pyrolysis of sewage sludge or agricultural waste.

[0057] Other examples of low-yield carbon black feedstocks may include, but are not limited to, the following: liquid by-products from the processing of biogenic materials.

[0058] Other examples of low-yield carbon black feedstocks may include, but are not limited to, the following: liquids produced by hydrothermal liquefaction of biomaterial.

[0059] Other examples of low-yield carbon black raw materials may include, but are not limited to, the following: crude tall oils, tall oil rosin, tall oil pitch or tall oil fatty acids (e.g., from papermaking processes).

[0060] Other examples of low-yield carbon black feedstocks may include, but are not limited to, the following: renewable feedstocks, such as oils produced from recycled materials.

[0061] Other examples of low-yield carbon black raw materials may include, but are not limited to, the following: oils derived from the pyrolysis of non-standard, discarded or end-of-life tires.

[0062] Other examples of low-yield carbon black feedstocks may include, but are not limited to, the following: oils derived from the pyrolysis of discarded or recycled plastic.

[0063] Other examples of low-yield carbon black feedstocks may include, but are not limited to, the following: oils derived from the pyrolysis of solid municipal waste.

[0064] Other examples of low-yield carbon black feedstocks may include, but are not limited to, the following: oils derived from biomass pyrolysis (bio-oil), for example from animals or plants (e.g., vegetables).

[0065] As indicated above, in the present invention, at least a major part (in % by weight) of the total raw material used in certain processes of the present invention is one or more low-yield carbon black raw materials. Preferably, this quantity is at least 60% by weight, or at least 65% by weight, or at least 70% by weight, or at least 75% by weight, or at least 80% by weight, or at least 85% by weight, or at least 90% by weight, such as from 51% by weight to 95% by weight, or from 60% by weight to 95% by weight, or from 65% by weight to 95% by weight, or from 70% by weight to 95% by weight, or from 75% by weight to 95% by weight, or from 60% by weight to 95% by weight, or from 60% by weight to 90% by weight, or from 60% by weight to 85% by weight, or from 60% by weight to 80% by weight, or from 60% by weight to 75% by weight. % by weight, based on the total percentage by weight of all raw materials used.

[0066] For the purposes of the present invention, a "first carbon black feedstock" or a "high-yield carbon black feedstock" is a feedstock that is not a low-yield carbon black feedstock as defined herein. The first carbon black feedstock may be considered or designated as a traditional carbon black feedstock used in furnace carbon black processes ("traditional" carbon black feedstocks). As further stated herein, the first carbon black feedstock may be a blend of feedstocks that optionally contains small amounts of a low-yield carbon black feedstock.

[0067] The primary raw materials for carbon black are usually from the family of decantation oils or oily sludges, coal tars or coal tar distillate fractions, or ethylene or phenol cracking residues. Their defining characteristics, in relation to the production of carbon black in a typical furnace process, are indicated below.

[0068] A first carbon black raw material exhibits all three of the following properties: 1. A BMCI of at least 100 (for example, at least 101, at least 102, at least 103, at least 104, at least 105, at least 110, at least 115, at least 120, at least 130, at least 140, at least 150, at least 160, at least 170, such as from 100 to 180, from 101 to 180, from 102 to 180, from 103 to 180, from 104 to 180, from 105 to 180, from 110 to 180, from 115 to 180, from 120 to 180, from 130 to 180, from 140 to 180, from 150 to 180, from 160 to 180, from 100 to 175, from 100 to 170, from 100 to 165, from 110 to 175, from 115 to 175, from 120 to 175, from 125 to 170, from 130 to 170), 2. a relative density greater than 1.02 (for example greater than 1.025, greater than 1.03, greater than 1.035, greater than 1.04, greater than 1.05, such as from 1.021 to 1.3, or from 1.025 to 1.3 or from 1.03 to 1.3, or from 1.05 to 1.3 or from 1.07 to 1.25), 3. an H:C atomic ratio of at most 1.23 (for example, of at most 1.22, of at most 1.21, of at most 1.2, of at most 1.15, of at most 1.1, of at most 1.05, of at most 1, of at most 0.9, of at most 0.8, such that from 1.225 to 0.7, from 1.225 to 0.8, from 1.225 to 0.9, from 1.225 to 1, from 1.225 to 1.1, from 1.22 to 0.7, from 1.21 to 0.7, from 1.2 to 0.7). As an option, the primary raw material for carbon black can also be a liquid at ambient temperature and pressure (e.g., 25°C and 1 atm). Despite being a liquid, the primary raw material of Carbon black can be a pitch or similar material of extremely high viscosity and does not need to exhibit any perceptible flow.

[0069] Examples of primary carbon black raw materials are given in Table 2 below and include coal tar, liquids distilled from coal tar, settling oils or oily sludges obtained from catalytic cracking, and residual oils from ethylene cracking. As shown in Table 2, these raw materials have an H:C ratio of at most 1.23, a relative density greater than 1.02, and a BMCI value of at least 100.

[0070] Table 2: [Tables 2] Example of a raw material: Ethylene vapour cracking residue, Ethylene vapour cracking residue, Settling oil A, Settling oil B, Coal tar distillate, H:C atomic ratio 0.94 0.91 0.94 1.01 0.85, Relative density 1.07 1.08 1.10 1.11 1.14, BMCI 127 146 132 134 161, Sulfur content (% by weight) 0.2 0.17 2.1 0.95 0.6, Flash point (°C) 70 86 130 90 90. Example of a raw material: Crude coal tar, Settling oil C, H:C atomic ratio 0.72 1.01 Density 1.22 1.10 BMCI 179 163 Sulfur content (% by weight) 0.38 1.36 Flash point (°C)

[0071] The first carbon black feedstock may also include a fraction derived from the refining or distillation of tire pyrolysis oil. Tire pyrolysis may be accomplished by any process known to those skilled in the art. Examples of such processes include, but are not limited to, those found in US Patents 8350105 and 20180320082. Distillation of the resulting oil may also be accomplished by any process known to those skilled in the art. Examples of such processes include, but are not limited to, those found in US Patents 9920262 and 2019236214. Tire pyrolysis oil may be distilled to provide at least one fraction that can be used as the first carbon black feedstock and at least one fraction that is a low-yield carbon black feedstock.Indeed, distillation can yield light fractions that can be used more economically in other unit processes of the carbon black production process, for example, as fuel for a carbon black dryer or for a heater to preheat either one or both of the first or second carbon black feedstock, as disclosed in document US20130039841. Thus, integrating the distillation process with the carbon black reactor can offer both economic and environmental benefits from the recycling of carbon black-filled tires.

[0072] Optionally, in the processes of the present invention, the first carbon black raw material, based on the total quantity of raw material used (in % by weight), may be used in an amount of 49% by weight or less, 45% by weight or less, 40% by weight or less, 35% by weight or less, 30% by weight or less, by 25% by weight or less, by 20% by weight or less, by 15% by weight or less, by 10% by weight or less, by 9% by weight or less, by 8% by weight or less, 7% by weight or less, 6% by weight or less, such as 5% (in weight at 49% by weight or from 5% by weight to 45% by weight, or from 10% by weight to 40% by weight, or from 10% by weight to 35% by weight, or from 10% by weight to 30% by weight).

[0073] The first carbon black raw material can be a liquid under ambient temperature (e.g., 25 °C) and atmospheric conditions (e.g., 1 atm). “Aromatic-rich species” means that the raw material has a high quantity of aromatic compounds. For example, a high quantity of aromatic compounds is when the total weight percentage of aromatics present is at least 20% by weight or has a BMCI of at least 100, or both. The first carbon black raw material can be heated so that the raw material is in vapor form and can thus be transformed into, or used in practice as, an aromatic-rich vapor.

[0074] With regard to the process steps of the present invention, the process includes the step of forming or introducing a stream of heated gas into a carbon black reactor (for example, a furnace carbon black reactor).

[0075] The "heated gas stream" may be a stream of hot gases or hot combustion gases. The heated gas stream may be generated by contacting a solid, liquid, and / or gaseous fuel with a suitable oxidizing stream such as, but not limited to, air, oxygen, air-oxygen mixtures, or the like. Alternatively, a preheated oxidizing stream may be passed through without the addition of a liquid or gaseous fuel. Examples of suitable fuels for use in contact with the oxidizing stream to generate the hot gases include any of the readily combustible gas, vapor, or liquid streams, such as natural gas, hydrogen, carbon monoxide, methane, acetylene, alcohol, or kerosene. Generally, it is preferable to use fuels with a high content of carbon-containing components, and in particular, hydrocarbons.The equivalence ratio (defined below) for the mixture of fuel and oxidizer used to form the hot gas can range from 10 (very fuel-rich) to approximately 0.1 (very fuel-lean), or the lowest value that still permits the generation of hot gas by means of a given combustion chamber or oxidation device. As noted, to facilitate the generation of hot gas, the oxidizer stream can be preheated. The heated gas stream is essentially created by igniting or burning the fuel and / or oxidizer. Temperatures such as approximately 1000 °C to approximately 3500 °C for the heated gas stream can be achieved.

[0076] The carbon black reactor is preferably a furnace carbon black reactor. More preferably, the carbon black reactor is a version of the furnace reactor called a staged carbon black reactor (for example, a multistage carbon black reactor or multistage reactor). “Staged” means that the feedstock is introduced or injected at more than one axial location along the long axis of the furnace.

[0077] For the purposes of the present process and the other processes described herein, it is possible to use a multi-stage carbon black reactor such as those described in US Patent No. 4,383,973, US Patent No. 7,829,057, US Patent No. 5,190,739, US Patent No. 5,877,251, US Patent No. 6,153,684 or US Patent No. 6,403,695.

[0078] The general process of forming carbon black by means of the carbon black reactor, such as a multi-stage reactor, and of obtaining suitable hot gases for forming carbon black are further described in the patents referenced and identified above and may be applied in the present invention with the changes described herein.

[0079] Figures 4A and 4B show a cross-sectional view of a carbon black reactor (50 in [Fig. 4A] and 80 in [Fig. 4B]) that can be used. In [Fig. 4A], hot combustion gases are generated in a combustion zone or combustion chamber 1 by contacting the fuel in the form of a liquid or gaseous fuel stream 9 with an oxidant stream 5, for example, air, oxygen, or mixtures of air and oxygen (also known in the art as "oxygen-enriched air"). The fuel can be any readily combustible gas, vapor, or liquid streams such as hydrocarbons (e.g., methane, natural gas, acetylene), hydrogen, alcohols, kerosene, fuel mixtures, etc. In many cases, the selected fuel has a high content of carbon-containing components.

[0080] Various gaseous or liquid fuels, for example, hydrocarbons, can be used as combustion fuel. The equivalence ratio is the ratio of the fuel to the amount of oxidizer stoichiometrically required to completely burn the fuel. Typical values ​​for the equivalence ratio in the combustion zone range from 1.2 to 0.2. To facilitate the generation of hot combustion gases, the oxidizer stream can be preheated.

[0081] In the present invention, the combustion stage can completely or almost completely consume the combustion fuel. Oxygen, fuel selection, burner design, jet velocities, mixing conditions and / or patterns, fuel-to-air ratios, oxygen-enriched air or pure oxygen, temperatures and / or other factors can be adjusted or optimized.

[0082] The hot combustion gas stream flows downstream of zones 1 and 2 into zones 3 and 4. Carbon black feedstocks are introduced at one or more locations suitable relative to other reactor components and feedstocks. Zone 2 of the combustion chamber can be the location where one or more carbon black feedstocks are introduced. In [Fig. 4A], an injector 10 and / or an injector 6 can be used to introduce the carbon black feedstock into the reactor. The injector 10, for example, can introduce or inject a first carbon black feedstock into the reactor. Alternatively, the first carbon black feedstock can also be introduced into the chamber by means of an axial pipe or a lance (represented by pipe or lance 63 in [Fig. 4B]).As another variant, the first carbon black raw material can be injected or introduced by multiple processes simultaneously. The lance or any other injector exposed to the reactor or combustion chamber may need to be cooled or protected from excessive heat in the combustion chamber, by methods known in art.

[0083] Additional carbon black feedstock, for example, low-yield carbon black feedstock, can be introduced into reactor zone 3 at the injection point 7 via injector 6. In the present invention, generally, at least some or even all of the first carbon black feedstock can be injected or introduced before the low-yield carbon black feedstock is introduced into the reactor. Preferably, a major portion (>50%) of the first carbon black feedstock used in the reactor is introduced before any low-yield carbon black feedstock is introduced. Zones 3 and 4 are reaction zones, and zone 8 is the rapid cooling zone. Q represents the length of zone 4 before the rapid cooling zone 8.

[0084] Carbon black raw materials can be injected into the combustion gas stream through one or more nozzles designed for optimal distribution of the raw material within the gas stream. These nozzles can be single-fluid or dual-fluid. Dual-fluid nozzles can use, for example, steam, air, or nitrogen to atomize the raw material. Single-fluid nozzles can atomize by pressure, or the raw material can be injected directly into the gas stream. In the latter case, atomization is produced by the force of the gas stream.

[0085] The carbon black raw material can be injected by means of an axial injection lance or a central conduit and / or one or more radial lances arranged around the circumference of the reactor in a plane perpendicular to the flow direction. A reactor can contain several planes with radial lances along the flow direction. Spraying or injection nozzles can be arranged on the lance heads by means of which the raw material is mixed into the flow of the heated gas stream.

[0086] Figure 4B illustrates a cross-section of another example of a carbon black reactor in the furnace process, which can be used in the present invention. In this example, as in Figure 4A, an oxidizer stream 51 is combined in a combustion chamber 55 with a combustion fuel 52.

[0087] The hot, burned or partially burned gas stream prepared in chamber 55 flows in direction A toward a constriction or narrowing 64. The first carbon black feedstock is introduced into the furnace carbon black reactor 80, before the low-yield carbon black feedstock. The first carbon black feedstock can be introduced by means of an optional central conduit 63, or a lance or injector or set of lances 56, or by means of lances or injectors located at or near the constriction 64 as indicated by reference numeral 57. The first carbon black feedstock The fuel can be introduced at one of these locations, or simultaneously at two of these locations, or at all three locations simultaneously. The manner and division of the first injection of raw material, when more than one of these locations is used, can vary to modify product properties and process economy. The injectors, as well as the combustion chamber itself (or parts thereof), can be cooled according to the requirements of the processes known in art.

[0088] In [Fig. 4B], the length between the optional central conduit injector 63 and the midpoint of the constriction 64 is labeled as length 60. If this central conduit is used, this length is preferably 9 to 10 times the narrowest diameter of the first constriction 64. If the central conduit is used simultaneously with a series of injectors or lances 57 for introducing the first carbon black raw material, then the length 60 may be as above or may be only 0. Adjusting this length can allow for structural balancing and process economy. The height or diameter 54 is shown for the combustion chamber and this height is greater than the height or diameter 64 and the height or diameter 64 can be at least 20%, at least 30%, at least 40%, at least 50% smaller than the height or diameter 54.

[0089] Following the introduction of the first carbon black feedstock, the hot gas stream mixed with the feedstock enters a first reaction chamber 58. The purpose of the chamber is to ensure a residence time so that pyrolysis reactions that produce carbon black can complete an induction time and begin, eventually, to produce a population of seeding particles for subsequent structural growth as taught in US Patent No. 7,829,057. The length of this chamber 66 can ordinarily be from 9 to 20 times the narrowest diameter of the first constriction 64.

[0090] At the end of the first reaction chamber 58, the low-yield carbon black feedstock can be introduced. It can be introduced by means of an injector or a series of injectors 59 positioned inside or near a second constriction 65. Alternatively, it can be introduced with a lance substantially upstream of the constriction 65, but inside the chamber 58.

[0091] After the introduction of the low-yield carbon black feedstock, the mixture flows into a second reaction chamber 61. It is then rapidly cooled by means of a liquid or vapor cooling spray 62, as known in the art. The length from the injection point of the low-yield carbon black feedstock 59 to the rapid cooling point 62 is marked 67 in [Fig. 4B]. This length is defined to provide a residence time which controls certain properties of the product as known in the art of the furnace process.

[0092] An alternative arrangement introduces the first carbon black feedstock at locations 63 and / or 56, and then introduces the low-yield carbon black feedstock at locations 57 and / or 59, which can occur simultaneously if both locations are used. This can offer an advantageous compromise between the capacity and yield of the carbon black structure or process economy. In all the above embodiments, at least some, and preferably most (> 50%), of the first carbon black feedstock used—for example, all of the first carbon black feedstock—is introduced before and upstream of the low-yield carbon black feedstock.

[0093] In yet another example of the present invention, the first carbon black raw material may be a mixture of a high-yield carbon black raw material satisfying the BMCI, relative density, and H:C ratio parameters indicated above and a low-yield carbon black raw material, provided that the mixture satisfies the BMCI, relative density, and H:C ratio parameters indicated above for the first carbon black raw material. The mixture may contain more than 50% of the high-yield carbon black raw material by mass (for example, 50.5% to 99.5% by weight of the high-yield carbon black raw material, or 60% to 99% by weight).

[0094] Similarly, the low-yield carbon black feedstock may optionally be a mixture of a high-yield carbon black feedstock and a low-yield carbon black feedstock that does not meet at least one of the BMCI, H:C ratio, and relative density parameters required for the first carbon black feedstock, provided that the mixture also does not meet at least one of the BMCI, H:C ratio, and relative density parameters required for the first carbon black feedstock. The low-yield carbon black feedstock may be present in an amount exceeding 50% of the total feedstock of this optional mixture, by mass (for example, 50.5% by weight to 99.5% by weight of the low-yield carbon black feedstock, such as 60% by weight to 99% by weight).Furthermore, the total quantity of the first carbon black feedstock introduced into the reactor through the sum of all injection points is less than 50% by weight of the total quantity of carbon black feedstock used throughout the reactor. The total quantity of feedstock. low-yield carbon black is greater than 50% by weight based on the total raw material.

[0095] Optionally, in a process of the present invention, the process includes the step of introducing at least one first carbon black feedstock with the heated gas stream into the carbon black reactor to form a reaction stream. The first carbon black feedstock may be one or a combination of two or more different first carbon black feedstocks. When more than one type of feedstock is used as the first carbon black feedstock, multiple first carbon black feedstocks may be mixed together and injected as a blended feedstock through one or more multiple locations, or each feedstock may be injected separately into the combustion chamber at the same or different locations.

[0096] Optionally, in a process of the present invention, the process includes the step of introducing at least one low-yield carbon black feedstock into a reaction stream. The low-yield carbon black feedstock may be one or a combination of two or more different low-yield carbon black feedstocks. When more than one type of feedstock is used as the low-yield carbon black feedstock, the multiple low-yield carbon black feedstocks may be mixed together and injected as a blended feedstock through one or more locations, or each feedstock may be injected separately into the combustion chamber at the same or different locations.

[0097] In general, any of the carbon black feedstocks used in any of the processes of the present invention can be injected into a reactor by a single stream or a plurality of streams by means of injectors, which penetrate the internal regions of the hot combustion gas stream. An injector can better ensure a high degree of mixing and shearing of the hot combustion gases and the carbon black feedstock(s). It ensures that the feedstock pyrolyzes, preferably at a rapid rate and / or with a high yield, to form the carbon black of the present invention.

[0098] Fig. 5 illustrates a specific example of a reactor that can be used to implement the invention, and has been used to produce examples 1 to 13 described below.

[0099] The first carbon black raw material can be introduced at one location in the reactor or at multiple locations in the reactor. The introduction of this raw material can be carried out with a central pipe or a lance 73 located in the combustion chamber 74 having a largest diameter Dchamber 75, in the reactor 90 as shown, for example, in [Fig. 5]. The central pipe can be positioned approximately on the longitudinal axis of the reactor (central axis). The central pipe can have an injector head 77 or a spray head on the nozzle. The injector on the nozzle can have, for example, one or multiple holes (2, 3, 4, or more) around the nozzle (for example, multiple holes generally evenly spaced as shown in [Fig. 6A], where one of the multiple holes 610 is shown). This injection point can be achieved with a central pipe or can be obtained by means of other injection devices.

[0100] In one embodiment of the present invention, the low-yield carbon black feedstock can be introduced at one or more locations in the reactor. As shown, in this method of the present invention, the location or locations in the reactor are downstream of the location(s) where the first carbon black feedstock is injected or introduced. The introduction of the low-yield carbon black feedstock can be accomplished with one or more injectors (for example, one or more metal pipes located on the reactor wall) that introduce the feedstock into the reactor combustion chamber, as shown, for example, in Figures 4A and 4B. The injector may have an injector head or spray head on the nozzle.The injector on the nozzle may have, for example, one or multiple holes (2 or 3 or 4 or more) around the nozzle (multiple holes usually evenly spaced).

[0101] Optionally, the introduction of the low-yield carbon black feedstock into the reactor and the reaction stream can be such that the feedstock is introduced perpendicular to the lateral flow of the reaction stream through the reactor, as shown for example in Figures 4A and 4B. Perpendicular can mean within ±15 degrees of a true perpendicular injection of the feedstock into the reaction stream.

[0102] Optionally, the introduction of the low-yield carbon black feedstock into the reactor can take place at a location that has a narrower diameter than the reactor diameter at the point where the first carbon black feedstock was previously introduced. This location can be considered a "choke" in certain carbon black reactors. Figures 4A and 4B provide an example of this choke or constriction zone in a reactor. This narrower diameter can be at least 10% smaller, at least 20% smaller, or at least 30% larger. small, or 10% to 40% smaller than the diameter of the reactor where the first carbon black raw material was previously introduced. In [Fig. 5], this is Chamber 75 in relation to Disturbance 76.

[0103] Optionally, the introduction of the low-yield carbon black feedstock into the reactor and the reaction stream can be made at a location which is at a distance DA (on [Fig.5], this distance is indicated by Lconduit, 78) from the location where the first carbon black feedstock is introduced or injected into the reactor, and this DA is at least 1 or at least 2 times the narrowest diameter of the reactor combustion chamber (or is at least 2 times the diameter of the reactor where the first carbon black feedstock was introduced or injected).This distance may be at least 2.25, at least 2.5, at least 2.75, at least 3, at least 3.25, at least 3.5, at least 3.75, or at least 4 times the diameter of the reactor combustion chamber (or is at least 2.25, at least 2.5, at least 2.75, at least 3, at least 3.25, at least 3.5, at least 3.75, or at least 4 times the diameter of the reactor where the first carbon black was introduced or injected).

[0104] The low-yield carbon black raw material can be introduced at location 83 through one or more injectors.

[0105] Once the raw materials (primary carbon black raw material and low-yield carbon black raw material) are combined with the reaction stream, the processes of the present invention generally include a rapid cooling step for the reaction. In [Fig. 5], this is the rapid cooling spray 81. The reaction zone, after the throttling 76, is represented by the marker 80 having the largest diameter of the reactor. The cooling length represents the distance from where the low-yield carbon black raw material is introduced to the point where the rapid cooling occurs.

[0106] The reaction is stopped in the rapid cooling zone of the reactor (see zone 8 in [Fig. 4A]). As shown in [Fig. 4A], the rapid cooling zone 8 is located downstream of the reaction zone 4 and sprays a rapid cooling fluid, such as water, into the stream of newly formed carbon black particles. In general, rapid cooling serves to cool the carbon black particles and reduce the temperature of the gas stream and decrease the reaction rate. Q is the distance from the start of the reaction zone 4 to the rapid cooling point 8, and will vary depending on the position of the rapid cooling. Optionally, rapid cooling may be staged or occur at several points in the reactor. Pressure spraying, gas atomized spraying, or other rapid cooling techniques may also be used. to be used. Regarding the rapid and complete cooling of the reactions to form carbon black, any method known to those skilled in the art for rapidly cooling reactions downstream of the point of introduction of the raw materials producing carbon black may be used. For example, a rapid cooling fluid, which may be water or other suitable fluids, may be injected to stop the chemical reaction.

[0107] After rapid cooling, the gases and the cooled carbon black pass downstream through any conventional cooling and separation means by which the product is recovered. The separation of the carbon black from the gas stream is easily accomplished by conventional means such as a precipitator, a cyclone separator, a bag filter, or other means known to those skilled in the art. After the carbon black is separated from the gas stream, it may optionally undergo a granulation step.

[0108] For any one of the processes of the present invention, optionally, the carbon black produced is not a carbon black with a core and a coating.

[0109] For any one of the processes of the present invention, optionally, the carbon black is entirely formed on site in the reactor.

[0110] Optionally, any one or more of the raw materials or other components used in the processes of the present invention may be preheated before introduction into the reactor. Appropriate preheating temperatures and / or preheating techniques may be used in the present invention as stated, for example, in US Patent No. 3,095,273 issued June 25, 1963, in Austin; US Patent No. 3,288,696 issued November 29, 1966, in Orbach; US Patent No. 3,984,528 issued October 5, 1973, to Cheng et al.; US Patent No. 4,315,901 issued February 16, 1982, to Cheng et al.; US Patent No. 4,765,964 issued August 23, 1988, to Gravley et al.; US patent no. 5,997,837 issued on December 7, 1999 to Lynum et al., US patent no. 7,097,822 issued on August 29, 2006 to Godai et al.; US patent no. 8,871,173B2, issued on October 28, 2014 to Nester et al. or document CA 682982.Alternatively, or in addition, the low-yield carbon black feedstock can be preheated to a temperature higher than is typical for a higher-yield feedstock. For example, the low-yield carbon black feedstock can be heated to a temperature exceeding 600 °C, for example, from 600 to 800 °C, including at ambient pressure. Because the low-yield carbon black feedstock has a low asphaltene concentration, heating to such a high temperature does not generate significant amounts of coke or other non-solid carbon black species. Alternatively, or in addition, any or more of the carbon black feedstocks may... can be combined with a dilution fluid before introduction into the reactor, for example, as described in US patent no. 10 829 642.

[0111] Optionally, the process is carried out in the absence of at least one substance which is or which contains at least one element of Group IA or Group IIA (or ion thereof) of the periodic table.

[0112] Optionally, in any of the processes of the present invention, the process may include the step of introducing at least one substance that is or contains at least one element of Group IA or Group IIA (or an ion thereof) of the periodic table. Preferably, the substance contains at least one alkali metal or alkaline earth metal. Examples include lithium, sodium, potassium, rubidium, cesium, francium, calcium, barium, strontium, or radium, or combinations thereof. Any mixtures of one or more of these components may be present in the substance. The substance may be a solid, a solution, a dispersion, a gas, or any combination thereof. More than one substance having the same Group IA or Group IIA metal or a different metal from these groups may be used.If multiple substances are used, the substances can be added together, separately, sequentially, or at different reaction sites. For the purposes of the present invention, the substance can be the metal (or metal ion) itself, a compound containing one or more of these elements, including a salt containing one or more of these elements, and the like. Preferably, the substance is capable of introducing a metal or metal ion into the ongoing reaction to form the carbon black product. For the purposes of the present invention, preferably, the substance is introduced before the complete rapid cooling as described above.For example, the substance may be added at any point before complete rapid cooling, including before the introduction of one or both of the carbon black-producing raw materials; during the introduction of either or both of the carbon black-producing raw materials; after the introduction of one or all of the carbon black-producing raw materials; or after the introduction of all of the raw materials but before complete rapid cooling. More than one point of introduction of the substance may be used. The amount of the substance containing the Group IA or Group IIA metal may be any amount as long as a carbon black product can be formed. For example, the amount of the substance may be added in such a quantity that 200 ppm or more of the Group IA or Group IIA element is present in the final carbon black product.Other quantities include from about 200 ppm to about 5000 ppm or more or other ranges may be from about 300 ppm to about 1000 ppm, or from about 500 ppm to about 1000 ppm of the Group IA or Group IIA element present in the . The carbon black product that is formed. These levels may be related to the concentration of metal ions. As stated, these quantities of the Group IA or Group IIA element present in the carbon black product that is formed may be related to one or more elements of Group IA or Group IIA and would therefore be a combined quantity of the Group IA or Group IIA elements present in the carbon black product that is formed. The substance may be added in any way, including by any conventional means. In other words, the substance may be added in the same way that a carbon black-producing raw material is introduced. The substance may be added as a gas, a liquid, or a solid, or any combination thereof. The substance may be added at one or more points and may be added as a single stream or a plurality of streams.The substance can be mixed with the raw material, fuel and / or oxidizer before or during their introduction.

[0113] With regard to the carbon black formed by any of the processes of the present invention, the carbon black formed or produced may be any grade of strengthening or non-strengthening carbon black. Examples of strengthening grades are N10, N121, N220, N231, N234, N299, N326, N330, N339, N347, N351, N358, and N375. Examples of semi-strengthening grades are N539, N550, N650, N660, N683, N762, N765, N774, N787, and / or N990.

[0114] Carbon black can be furnace black.

[0115] Carbon black can be characterized by a specific surface, structure, size of aggregate, shape, and distribution; and / or chemical and physical surface properties. Carbon black properties are determined analytically by tests known in the art. For example, nitrogen adsorption surface area and surface area by statistical thickness (STSA), another measure of surface area, are determined by nitrogen adsorption according to test procedure ASTM D6556. Iodine value can be measured using procedure ASTM D-1510. The "structure" of carbon black illustrates the size and complexity of carbon black aggregates formed by the fusion of primary carbon black particles. As used here, carbon black structure can be measured as the oil absorption index (OAN) for uncrushed carbon black, expressed in millimeters of oil per 100 grams of carbon black, according to the procedure set forth in ASTM D-2414.The oil absorption index of the compressed sample (COAN) measures that part of the carbon black structure that is not easily altered by the application of mechanical stress. COAN is measured according to T ATSM D3493. Aggregate size distribution (ASD) is measured according to the ISO 15825 method using [method missing]. centrifugal disk photosedimentometry with a BI-DCP model manufactured by Brookhaven Instruments.

[0116] Carbon black materials having properties suitable for a specific application can be selected and defined by ASTM standards (see, for example, ASTM D 1765 Standard Classification System for Carbon Blacks Used in Rubber Products), for example, N100, N200, N300, N500, N600, N700; N800 or N900 series carbon blacks, for example, N110, N121, N220, N231, N234, N299, N326, N330, N339, N347, N351, N358, N375, N539, N550, N650, N660, N683, N762, N765, N774, N787 or N990 carbon blacks, or other commercial grade specifications.

[0117] Carbon black may exhibit any STSA such as ranging from 5 m2 / g to 250 m2 / g, 11 m2 / g to 250 m2 / g, 20 m2 / g to 250 m2 / g or more, for example, at least 70 m2 / g, such as from 70 m2 / g to 250 m2 / g, or 80 m2 / g to 200 m2 / g or from 90 m2 / g to 200 m2 / g, or from 100 m2 / g to 180 m2 / g, from 110 m2 / g to 150 m2 / g, from 120 m2 / g to 150 m2 / g and similar. Optionally, carbon black may have an iodine value (No. 12) of about 5 to about 35 mg I2 / g of carbon black (according to ASTM D1510).

[0118] The carbon black particles disclosed herein may have a BET surface area, measured by the Brunauer / Emmett / Teller (BET) technique according to the procedure in ASTM D6556, of 5 m² / g to 300 m² / g, for example, between 50 m² / g and 300 m² / g, for example, between 100 m² / g and 300 m² / g. The BET surface area may be from approximately 100 m² / g to approximately 200 m² / g or from approximately 200 m² / g to approximately 300 m² / g.

[0119] The oil absorption index (OAN) may be from 40 mL / 100 g to 200 mL / 100 g, for example between 60 mL / 100 g and 200 mL / 100 g, such as between 80 mL / 100 g and 200 mL / 100 g, for example between 100 mL / 100 g and 200 mL / 100 g or between 120 mL / 100 g and 200 mL / 100 g, between 140 mL / 100 g and 200 mL / 100 g, between 160 and 200 mL / 100 g or such as between 40 mL / 100 g and 150 mL / 100 g or 40 mL / 100 g and 150 mL / 100 g.

[0120] The CO AN can be in the range of about 40 mL / 100 g to about 150 mL / 100 g, for example between 55 mL / 100 g and about 150 mL / 100 g, such as between about 80 mL / 100 g and about 150 mL / 100 g, or between about 80 mL / 100 g and about 120 mL / 100 g.

[0121] Carbon black can be a carbonaceous product containing silicon-containing species and / or metal-containing species and the like, which can be obtained by including the additional step of introducing such species jointly or in addition to one or both of the carbon black-producing raw materials. For the purposes of the present invention, carbon black can be a multiphase aggregate comprising at least one carbon phase and at least one metal-containing species phase or one silicon-containing species phase (also known as the name of silicon-treated carbon black, such as ECOBLAK™ materials from Cabot Corporation).

[0122] As stated, carbon black can be a rubber black, and in particular a carbon black reinforcement grade or a carbon black semi-reinforcement grade.

[0123] Optionally, the carbon black of the present invention may have functional groups or chemical groups (for example, derived from small molecules or polymers, either ionic or non-ionic) that are directly attached to the carbon surface (for example, covalently attached). Examples of functional groups that can be directly attached (for example, covalently) to the surface of the carbon black particles and of methods for carrying out the surface modification are described, for example, in US Patent No. 5,554,739 issued to Belmont on September 10, 1996, and US Patent No. 5,922,118 issued to Johnson et al. July 13, 1999. As an illustration, a surface-modified carbon black that can be used here is obtained by treating carbon black with diazonium salts formed by the reaction of sulfanilic acid or para-aminobenzoic acid (PABA) with HCl and NaNO2.Surface modification by processes using sulfanilic or para-aminobenzoic acid with diazonium salts, for example, results in a carbon black exhibiting effective amounts of hydrophilic characteristic groups on the carbon coating.

[0124] Carbon black can be surface modified according to US patent no. 8,975,316 issued to Belmont et al.

[0125] Other techniques that can be used to provide functional groups attached to the surface of carbon black are described in US patent No. 7,300,964 issued to Niedermeier et al. on November 27, 2007.

[0126] Modified oxidized carbon black can be prepared in a manner similar to that used for carbon black, as described, for example, in US Patent No. 7,922,805 issued to Kowalski et al. on April 12, 2011, and in US Patent No. 6,471,763 issued to Karl on October 29, 2002. Oxidized carbon black is black that has been oxidized by means of an oxidizing agent in order to introduce ionic and / or ionizable groups onto the surface. Such particles may have a higher degree of oxygen-containing groups on the surface.Oxidizing agents include, but are not limited to, oxygen gas, ozone, peroxides such as hydrogen peroxide, persulfates, including sodium and potassium persulfate, hypohalites such as sodium hypochlorite, oxidizing acids such as nitric acid, and transition metal oxidants such as permanganate salts, osmium tetroxide, chromium oxides, or ceric ammonium nitrate. Oxidizing mixtures may also be used. In particular, mixtures of gaseous oxidizers such as oxygen and ozone. Other surface modification processes, such as chlorination or sulfonylation, can also be used to introduce ionic or ionizable groups. Carbon black can be surface modified by any process known to those skilled in the art. For example, carbon black can be heat-treated as described in US patent 10767028.

[0127] Carbon black can be used in various applications, such as, for example, as reinforcement in rubber products, for example, tire components.

[0128] Carbon black can be incorporated into rubber articles, being used, for example, for tire treads, in particular in the treads of passenger car, light vehicle, truck and bus tires, all-terrain tires, aircraft tires and the like; for the underlayer; the corded gum layer; sidewalls; the foot rubber for retreaded tires and other tire uses.

[0129] In other applications, the particles can be used in industrial rubber articles, such as engine mounts, hydraulic mounts, bridge bearings and seismic isolators, tank tracks or treads, mining belts, flexible hoses, trims, seals, caulking bead type articles, bumpers, anti-vibration parts and other articles.

[0130] Carbon black can be added as an alternative to, or in addition to, primary reinforcing agents for tire components and / or other end uses of industrial rubber. Carbon black can be combined with natural and / or synthetic rubber in a suitable dry or wet mixing process based on an internal batch mixer, a continuous mixer, or a rolling mill.

[0131] Alternatively, carbon black can be mixed into rubber by means of a liquid masterbatch process. For example, a slurry containing the particles described herein can also be combined with elastomeric latex in a tank and then coagulated by the addition of a coagulant, such as an acid, using the techniques described in US Patent No. 6,841,606.

[0132] Carbon black may be introduced according to US Patent No. 6,048,923; issued to Mabry et al. on April 11, 2000. For example, a process for preparing an elastomer masterbatch may involve the simultaneous supply of a particulate filler fluid and an elastomeric latex fluid to a mixing zone of a coagulum reactor. A coagulum zone extends from the mixing zone, preferably widening gradually in cross-section in the downstream direction from an inlet end to a discharge end. The elastomeric latex may be either natural or synthetic, and the particulate filler comprises, consists of essentially consists of the material as described above. The particulate charge is supplied to the mixing zone preferably as a continuous, high-velocity jet of injected fluid, while the latex fluid is supplied at a low velocity. The velocity, flow rate, and particulate concentration of the particulate charge fluid are sufficient to induce high-shear mixing of the latex fluid and flow turbulence of the mixture within at least a portion upstream of the coagulum zone, so as to substantially coagulate the elastomeric latex with the particulate charge before the discharge end. Substantially complete coagulation can occur without the need for acid or salt-based coagulating agents. As disclosed in US Patent No. 6,075,084, additional elastomer can be added to the material emerging from the discharge end of the coagulum reactor.As disclosed in US patent no. 6,929,783, the coagulum can then be supplied to a dehydration extruder. Other examples of suitable masterbatch processes are disclosed in US patent no. 6,929,783 granted to Chung et al.; US application 2012 / 0264875A1 by Berriot et al.; US application 2003 / 0088006A1 by Yanagisawa et al.; and EP 1,834,985 B1 granted to Yamada et al.

[0133] Carbon black can be evaluated in a suitable rubber formulation, using natural and synthetic rubber. Appropriate quantities of carbon black to be used can be determined by routine experimentation and calculations, taking into account factors such as typical ASTM standard furnace black loadings in comparable manufacturing processes, parameters specific to the techniques and / or equipment used, the presence or absence of other additives, desired properties of the final product, etc.

[0134] The performance of carbon black as a reinforcing agent for rubber compounds can be evaluated by determining, for example, the performance of a rubber composition using the particles compared to the performance of a similar rubber composition that is comparable in all respects except for the use of a grade of carbon black appropriate for the given application. In other approaches, the values ​​obtained for compositions prepared according to the invention can be compared to values ​​known in the art as being associated with desired parameters in a given application.

[0135] Appropriate tests include green rubber tests, curing tests, and cured rubber tests. As green rubber tests, ASTM D4483 specifies a test procedure for the Mooney ML1+4 viscosity test at 100°C. The roasting time is measured according to ASTM D4818.

[0136] The hardening curve is obtained by the rubber treatment analyzer (RPA2000) 0.5°, 100 cpm and 150C (NR) - 160C (SBR) according to ASTM D5289.

[0137] The performance characteristics of cured samples can be determined by a series of appropriate tests. Tensile strength, elongation at break, and strain at various tensions (e.g., 100% and 300%) are all obtained by Method A of ASTM D412. Dynamic mechanical properties, including storage modulus, loss modulus, and tan[3], are obtained by strain sweep testing at 10 Hz, 60°C, and various strain amplitudes from 0.1% to 63%. Shore A hardness is measured according to ASTM D2240. The tear strength of die-type B rubber samples is measured according to ASTM D624.

[0138] The undispersed area is calculated by analyzing images obtained by optical microscopy in reflection mode for hardened rubber compounds with a truncated cross-section according to various reported methods. Dispersion can also be represented by the Z value (measured, after cross-linking, according to the method described by S. Otto et al. in Kautschuk Gummi Kuntstoffe, 58th year, NR 7-8 / 2005, article entitled "New Reference value for the description of Filler Dispersion with the Dispergrader 1000NT"). ISO 11345 highlights visual methods for the rapid and comparative estimation of the degree of macrodispersion of carbon black and carbon black / silica in rubber.

[0139] Abrasion resistance is quantified as an index based on the abrasion loss of hardened rubber by the Cabot (Lambourn type) abrader. Attractive abrasion resistance results may be indicative of advantageous wear properties. Good hysteresis results may be associated with low rolling resistance (and consequently higher fuel economy) for motor vehicle tire applications, heat buildup, tire durability, reduced tread life and casing life, improved fuel economy characteristics for the motor vehicle, etc.

[0140] The iodine value (No. 12) is determined according to test procedure ASTM D1510. The STSA (statistical thickness surface area) is determined based on test procedure ASTM D-5816 (measured by nitrogen adsorption). The OAN is determined based on ASTM D2414. The CO AN is determined based on ASTM D3493 (for example, D3493-20).

[0141] Unless otherwise stated, all proportions of material indicated by a percentage herein are percentages by weight.

[0142] The present invention will be further clarified by the following examples, which are intended to be purely illustrative.

[0143] EXAMPLES

[0144] For the purposes of the present invention and the examples presented here, we will provide an explanation of certain terms.

[0145] Equivalence ratios: the overall equivalence ratio <e>The μ₀ for a partial oxidation process is the ratio of the molar flow of oxidant required for the stoichiometric combustion of all input fuels and raw materials, divided by the actual molar flow of oxidant. Thus, when μ₀ > 1, the mixture is fuel-rich, and when it is < 1, it is fuel-poor. Carbon black production occurs preferentially when<F0 est sensiblement riche en combustible, d’ordinaire > 1.6.

[0146] The overall equivalence ratio ¢^, for the combustion chamber that produces the hot burnt gas, is defined by the quantity of fuel and burner oxidizer delivered. is usually fuel-poor, if values ​​of 0.33 to 0.9 are taken.

[0147] The equivalence ratio ¢7 is the equivalence ratio for the combustion chamber plus any additional fuel or charge introduced into the central conduit illustrated in [Fig.5], but leaving aside the charge introduced at the choke.

[0148] Yield: The yield Y is the mass of solid carbon obtained per total mass of feedstock injected into the carbon black reactor, excluding the natural gas used for the combustion chamber in [Fig. 5], and the units are [kg C / kg feedstock]. Y is equal to the total mass flow rate of solid carbon produced in the reactor, divided by the total mass flow rate of the feedstock, and this is measured in the examples herein by measuring the inlet flow rates of the feedstock, burner fuel, and all oxidizers, as well as the composition of the waste gas produced.

[0149] Carbon content: The carbon content [C] is the mass-averaged carbon content of all carbon black feedstocks introduced into the reactor, in units of [kg C / kg feedstock], and is equal to the total mass flow rate of carbon atoms entering the reactor via feedstocks, divided by the total mass flow rate of the feedstock. This value is calculated based on the measured flow rates of decanted oil and ethylene feedstocks, and their measured elemental compositions.

[0150] Dimensionless yield: The dimensionless yield Y / [C] is the above yield divided by the carbon content. It represents the fraction of the maximum possible yield that has been obtained. If Y / [C] = 0.5, for example, this means that / 2 of the The carbon raw material entering the reactor was converted into solid carbon. The remainder was lost as gaseous species.

[0151] Substances extractable by toluene, I2, STSA, OAN and CO AN

[0152] The OAN and CO AN are analyzed on dry pellets and comply with the ASTM standards identified above. The I2 index and STSA are analyzed on dry pellets using the ASTM methods identified above.

[0153] Reactor configuration and operation.

[0154] In the examples, decantation oil was used as a primary carbon black feedstock (Table 5), and ethylene gas was used as a low-yield carbon black feedstock or as a gaseous carbon black feedstock.

[0155] For a carbon black furnace process, natural gas and hot air are combined in a combustion chamber to provide a hot burnt gas stream, as shown in [Fig. 5]. This burnt gas was fuel-poor (oxidizer-rich), with a Cbp equivalence ratio typically between 0.32 and 0.8. The combustion chamber was refractory-lined, and its internal diameter is shown in Table 3.

[0156] In some of the examples, part of the raw material was introduced using a central pipe 73, as shown in [Fig. 5]. This pipe was positioned approximately on the longitudinal axis of the constriction, and horizontally. The pipe had an external diameter of 5.4 cm. When the raw material through the pipe was liquid decantation oil, a full cone sprayer or a pressure sprayer with six regularly spaced orifices perpendicular to the long axis of the central pipe was used.

[0157] When the raw material in the central line was low-yield ethylene-type carbon black raw material, a gas injector 77 as shown in [Fig. 5] was used, with the dimensions indicated in the example tables. This gas injector (Figures 6A (showing one hole 610 of three holes in total, radially spaced at regular intervals around the tip) or 6B (coaxial gas injector with a single hole 611)) was mounted on the end of the central line. When no raw material was injected in this manner, the central line was removed.

[0158] Next, the burnt gas from the chamber, along with the feed material introduced into the central line (see [Fig. 5]), if applicable, was forced into a constriction so that it entered a narrower bottleneck (76 in [Fig. 5]). At the bottleneck, the low-yield ethylene-type carbon black feed material was injected using three gas injectors spaced evenly around the inner perimeter of the bottleneck. The injectors were straight metal tubes, with an internal diameter of approximately 2 cm. These were positioned perpendicular to the direction of flow, as illustrated in [Fig.5].

[0159] The choke was attached to a refractory-lined reactor chamber. The reactor chamber provided a residence time for the feedstock to complete its pyrolysis into carbon black particles. At a rapid cooling distance downstream of the injection plane shown in [Fig. 5], a water spray was used to ensure rapid cooling, as is standard practice for furnace carbon black processes. Downstream of the rapid cooling, a filter was used to separate the carbon black particles from the waste gas stream. The carbon black at the filter was sampled for I2 absorption and toluene extractable substances (S2O). The carbon black was then granulated and dried for STSA, OAN, and COAN measurements.

[0160] The filtered residual gas was sampled and its composition was measured for each condition and the yields determined. [Tables 3] Dimension Description Units Value Combustion chamber diameter (cm) 20.3 Throat diameter (cm) 11.4 Reactor Reactor diameter (cm) Between 68.6 and 91.4 Piping As shown in examples Rapid cooling As shown in examples Table 3. Dimensions in the reactor shown in [Fig.5]

[0161] The natural gas supplied to the combustion chamber in [Fig. 5] had a measured average composition as shown in Table 4 for examples. The components were measured by gas chromatography. [Tables 4] Component % mole Nitrogen % 2.97 Oxygen % 0.00 Carbon dioxide % 0.06 Methane % 92.2 Ethane % 4.40 Propane % 0.32 Isobutane % 0.01 n-Butane % 0.01 Isopentane % 0.00 n-Pentane % 0.00 Hexanes % 0.00 Hydrogen % 0.00 Ethylene % 0.00 Table 4. Average composition of natural gas for experimental data.

[0162] The ethylene used in the examples was 99% (by weight) pure ethylene and was not subsequently analyzed.

[0163] The liquid decanting oil in these examples was the raw material G in Table 2 and exhibited the properties listed here, as well as the properties indicated in Table 5 below. [Tables 5] Process Property Units Value ASTM D-4052 Relative Density None 1.0978 ASTM D-5291-02 Carbon by weight % 90.32 ASTM D-5291-02 Hydrogen by weight % 0.63 IP-336 Sulfur by weight % 1.36 ASTM D-3228 Nitrogen by weight % 0.19 ASTM D- PCS MJ / kg 40.64 Table 5. Properties of raw material decantation oil.

[0164] Results

[0165] Tables 6 to 9 present examples of carbon black production in the furnace process of [Fig. 5]. Examples 1 to 5 and 11 to 13 show what This occurs when low-yield ethylene-type carbon black feedstock is used alone in the furnace, either in the choke, in the center line, or with a staggered injection of some of the ethylene into the center line followed by the injection of the remainder into the choke. Examples 6 to 10 and 14 to 18 illustrate the advantages of the present invention compared to the case of ethylene alone. In the present invention, a minority of the total feedstock was the first carbon black feedstock, injected via the center line, with the low-yield ethylene-type carbon black feedstock injected into the choke.

[0166] As the results show, the use of the low-yield carbon black feedstock alone produced poor yields for a given area (Figures 7-8), and a structural capacity (as indicated by the OAN or COAN) too low to match most ASTM carbon black grades (Figures 9-10). Without wishing to be bound by any theory, these results can be attributed, at least in part, to the low aromatic content of the low-yield carbon black feedstock, compared to the first carbon black feedstocks.

[0167] Several advantages are obtained with the present invention, as shown, at least in part, by the examples herein. First, the dimensionless yield is greatly improved when the present invention is put into practice, compared to using low-yield carbon black raw material alone. Second, the ability to achieve a superior structure increases greatly with the use of the processes of the present invention. The scaling of low-yield carbon black raw material (Example 4 and Example 5) alone does not allow this performance to be achieved. [Tableauxô] Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Air flow to burner N / m³ / h 1613 1411 1409 1410 1408 Air temperature °C 498 499 500 498 499 Natural gas flow N / m³ / h 74 64 65 65 65 Natural gas temperature °C 15 15 15 15 15 Central line injector type Name None Coaxial Coaxial Radial Radial Ethylene flow to throttle injectors Kg / h 335 0 0 196 152 Ethylene flow to central line Kg / h 0 303 284 108 154 Ethylene temperature °C 60 60 60 60 60 Oil flow Settling to central line Kg / h 0 0 0 0 0 Settling oil temperature °C Fraction of raw material to central line fr 0.00 1.00 1.00 0.35 0.50 Central line location L line m 0.76 0.48 0.48 Rapid cooling length L rapid cooling m 14.3 14.3 17.4 17.4 17.4 FP - 0.44 0.43 0.45 0.45 0.45 Fo - 2.81 2.89 2.74 2.91 2.93 Carbon yield Kg / h 0.149 0.203 0.174 0.219 0.213 Average carbon content by mass Kg / h 0.856 0.856 0.856 0.856 0,856 Dimensionless yield 0.175 0.237 0.203 0.256 0.249 Surface area per STSA m2 / g 32.3 21.8 28.8 27.7 29.8 Absorption I2 g / 100g 33.6 26.9 25.6 28.4 31.4 , OAN ml / 100 g 34.9 39.3 39.1 COAN ml / 100 g 32.5 35.8 Table 6. Table of examples of carbon black produced with ethylene alone, for <e>p ~ 0.45 [Paintings?] Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Air flow to burner N / m³ / h 1409 1411 1409 1408 1410 Air temperature °C 501 500 499 500 497 Natural gas flow N / m³ / h 65 65 67 65 64 Natural gas temperature °C 15 15 15 15 15 Central line injector type Name Solid cone sprayer Solid cone sprayer Pressure sprayer Solid cone sprayer Solid cone sprayer Ethylene flow to throttling injectors Kg / h 312 328 225 199 228 Ethylene flow rate to central line Kg / h 0 0 0 0 0 Ethylene temperature °C 60 60 60 60 60 Settling oil flow rate to central line Kg / h 98 102 155 136 155 Settling oil temperature °C 154 161 167 160 170 Raw material fraction to central line 0.24 0.24 0.41 0.41 0.40 Central pipe location T 1C / pipe m 0.66 0.66 0.76 0.66 0.66 Rapid cooling length L Rapid cooling m 17.4 17.4 17.4 17.4 17.4 F? - 0.44 0.44 0.46 0.44 0.44 Fo - 3.66 3.82 3.39 3.03 3.39 Carbon yield Kg / h 0.410 0.433 0.391 0.332 0.407 Average mass carbon content Kg / h 0.867 0.867 0.875 0.875 0.875 Dimensional yield 0.472 0.499 0.447 0.379 0.465 Surface area per STSA m2 / g 36.3 35.5 64.9 77.9 57.5 I2 absorption g / 100 g 39.8 40.0 66.6 81.2 63.7 OAN ml / 100 g 109 110 158 155 123 COAN ml / 100 g 75.3 98.7 107.5 89.3 Table 7. Carbon black production in which settling oil is introduced into the central line, with most of the raw material introduced at the constriction as shown in [Fig.5]. [Tables 8] Ex. 11 Ex. 12 Ex. 13 Air flow rate to burner N / m³ / h 1407 1408 1411 Air temperature °C 501 501 504 Natural gas flow rate N / m³ / h 111 112 112 Natural gas temperature °C 15 15 15 Center line injector type Name None None Coaxial Ethylene flow rate to throttling injectors Kg / h 311 276 0 Ethylene flow rate to center line Kg / h 0 0 311 Ethylene temperature °C 60 60 60 Settling oil flow rate to center line Kg / h 0 0 0 Settling oil temperature °C Raw material fraction to center line 0.00 0.00 1.00 Center line location L conduit m 0.76 Cooling length ra pîdc L rapid cooling m 14.3 14.3 14.3 FP - 0.76 0.77 0.76 Fo - 3.28 3.01 3.27 Carbon yield Kg / h 0.373 0.296 0.416 Average carbon content by mass Kg / h 0.856 0.856 0.856 Dimensionless yield 0.436 0.346 0.486 Surface area per STSA m2 / g 32.01 16.9 Absorption I2 g / 100g 21.8 31.1 14.6 OAN ml / 100 g 27 40 45 COAN ml / 100 g 35.7 Table 8. Table of examples of carbon black produced with ethylene alone, for <e>p ~ 0.75. [Tables 9] Ex. 14 Ex. 15 Ex. 16 Ex. 17 Ex. 18 Air flow to burner N / m³ / h 1410 1410 1408 1411 1402 Air temperature °C 500 500 504 498 496 Natural gas flow rate N / m³ / h 112 112 111 111 111 Natural gas temperature °C 15 15 15 15 15 Central duct injector type Name Solid cone sprayer Solid cone sprayer Solid cone sprayer Solid cone sprayer Solid cone sprayer Ethylene flow rate to throttle injectors Kg / h 174 171 199 218 258 Ethylene flow rate to central line Kg / h 0 0 0 0 0 Ethylene temperature °C 60 60 60 60 60 Settling oil flow rate to central line Kg / h 121 118 140 67 81 Settling oil temperature °C 156 156 162 127 140 Raw material fraction to central line 0.41 0.41 0.41 0.23 0.24 Central pipe location T 1C / pipe m 0.66 0.66 0.66 0.66 0.66 Rapid cooling length L rapid cooling m 17.4 17.4 17.4 17.4 17.4 FP - 0.77 0.77 0.76 0.75 0.76 Fo - 3.04 2.99 3.37 3.00 3.44 Carbon yield Kg / h 0.404 0.388 0.464 0.347 0.445 Average carbon content by mass Kg / h 0.876 0.875 0.876 0.867 0.868 Ad dimensional yield 0.462 0.444 0.530 0.400 0.513 Surface area per STSA m2 / g 66.9 69.2 57.8 58.5 43.3 Absorption I2 g / 100 g 76.9 76.6 64.3 66.5 49.7 OAN ml / 100 g 167 155 166 121 128 COAN ml / 100 g 103.9 100.5 101.0 93.3 85.5 Table 9: Carbon black production in which settling oil is introduced into the central line, with a major part of the raw material introduced at the constriction as shown in [Fig.5].

[0168] Improved yield.

[0169] Figure 7 illustrates the dimensionless yields obtained from Examples 1 to 5 and 6 to 10, with respect to the area. The numbering labels on the data points refer to the example numbers in Tables 6 to 9. In Examples 1 to 5, ethylene is the only feedstock used. In Example 1, ethylene is injected only in the choke. In Examples 2 and 3, ethylene is injected using only the center line, using the coaxial injector (Fig. 6B). In examples 4 and 5, part of the ethylene feedstock is staggered in the central line (35 and 50% by mass), the remainder being injected using the throttling.

[0170] Examples 6 to 10 in the diagram show the effect of the present invention when compared with Examples 1 to 5. In Examples 6 to 10, a portion of the raw material (25 or 40% by mass) was settling oil, injected through the central line as shown in Table 7. The dimensionless yields for these examples were all well above those achieved with the low-yield carbon black raw material alone. In particular, compare Examples 1, 3, 4, and 5 in [Fig. 7] with Examples 6 and 7. The use of a relatively small amount (25%) of the primary carbon black raw material significantly increased the yield obtained, over a given surface area range of 30 to 35 m² / g of STSA.

[0171] In general, the dimensionless yield decreases with increasing surface area in a furnace carbon black process, all other conditions being held constant. This is because larger surface areas require higher temperatures, leading to greater oxidation and a lower yield for solid carbon. Thus, a dimensionless yield versus surface area scheme will roughly show a decreasing trend with increasing surface area. This effect is highlighted by the ovals in [Fig. 7]. The group of carbon blacks produced with the present invention (Examples 6 to 10) is on a trend line with a yield significantly higher than those produced from ethylene alone (Examples 1 to 5).

[0172] It should also be noted that scaling the feedstock of ethylene alone (examples 4 and 5) has little effect on improving the yield obtained at a given surface. The first feedstock of carbon black or material with a high aromatic content appears to be necessary in the first phase to produce the effect.

[0173] Tables 8 and 9 present a similar set of examples, in which <Fpa une valeur plus élevée. Les résultats sont illustrés sur la [Fig.8]. Les exemples 11 et 12 représentent un fonctionnement sans les aspects de la présente invention, puisque de l’éthylène seul a été injecté soit dans l’étranglement, soit dans la conduite centrale ; Les exemples 14 à 18 montrent l’avantage de la présente invention, puisqu’une petite quantité d’huile de décantation a été fournie via la conduite centrale. Une fois encore, comme sur la [Fig.7], la présente invention a beaucoup augmenté le rendement pouvant être obtenu au niveau d’une surface donnée, et ce niveau est maintenu indépendamment de <FP. Une fois encore, le groupage de noirs de carbone manufactured with the present invention (examples 14 to 18) was on a trend line whose yield is much higher than those manufactured from ethylene alone (examples 11 and 12).

[0174] Without being bound by any specific theory, it is hypothesized that the production of seeding particles from the first carbon black feedstock introduced in the first phase is either insignificant or not the sole factor contributing to the increased yield effect with the present invention. The value of dh for Examples 6 and 7 was < 1.6, suggesting that very few carbon black particles were produced from the oil in the central line; nevertheless, the yield advantage was achieved. Therefore, the effect can be at least partially attributed to the aromatic content of the settling oil.

[0175] Structural improvement at the level of a fixed surface.

[0176] The second advantage of the present invention is that it allows a significant increase in the structure that can be obtained at a given surface, as shown in [Fig. 9]. In this figure, the numbering labels on data points denote the example numbers in Tables 6 to 9; the "N" labels on empty diamond-shaped points refer to ASTM quality requirements for a particle structure at a given surface. All the examples shown here were without the use of an alkali metal additive, so that they represent the maximum structure that can be obtained for the described operating configuration. As can be seen, the aromatic-deficient, low-yield carbon black feedstock alone (Examples 1, 3, and 5) produced carbon black grades with very low structure.The use of the present invention has produced significantly higher maximum structures (examples 6 to 10).

[0177] It is also noted that the scaling of the ethylene-only feedstock, as shown in Example 3, did little to improve the structure obtainable from the low-yield carbon black feedstock. Instead, it would appear that the aromatic-rich feedstock, or the first carbon black feedstock, should be injected into the first phase.

[0178] Dots representing typical structures for common ASTM-listed grades of carbon black (empty diamonds) are included in [Fig. 9]. This helps to illustrate how the present invention can use a raw material that is incapable of producing common grades of carbon black, on its own, and provide a process using such a raw material to produce these grades.

[0179] Similarly, [Fig. 10] shows the structure versus the surface from Tables 8 and 9. Once again, the present invention shows that by injecting an aromatic-rich feedstock upstream of the low-yield carbon black feedstock, a structure and surface can be obtained as required. for common grades of carbon black, whereas with low-yield carbon black raw material alone, this is not possible in a conventional furnace carbon black process.

[0180] Examples 19 to 26 in Tables 10A and 10B, and the figures based thereon, illustrate examples where the low-yield carbon black feedstock was heavy tire pyrolysis oil, or HTPO. HTPO is a recycled oil produced by the pyrolysis of used tire chips. The oil is then distilled to produce a "heavy" or higher-density oil fraction. The HTPO used in these examples had properties shown in Table 11; the conventional feedstock for these examples was decantation oil, also shown. [Tables 10] Example number 19 20 21 22 Air flow to burner N / m³ / h 2000 2000 2000 2000 Air temperature °C 500 500 500 500 Natural gas flow rate N / m³ / h 160 160 159 159 Natural gas temperature °C 25.0 25.0 25.0 25.0 Reactor configuration name Figure 5 Figure 5 Figure 5 Figure 5 Central line injector type name BETE 1 / 2 BETE 1 / 2 BETE 1 / 2 BETE 1 / 2 Potassium acetate solution concentration g / L 5 5 5 5 Average feed material temperature °C 150 151 139 144 Total feed material flow rate to central line Kg / h 0 0 0 0 Fraction of tire pyrolysis oil in the central drive charge fr 0.0 0.0 0.0 0.0 Total raw material flow rate to first choke Kg / h 449 398 417 492 Fraction of tire pyrolysis oil in the choke charge fr 1.0 1.0 0.7 0.7 Potassium acetate solution flow rate Kg / h 3.4 3.4 3.1 3.7 Total raw material flow rate to second choke (kg / h) — — — — Fraction of tire pyrolysis oil in the choke charge (fr) — -- — — Potassium acetate solution flow rate (kg / h) — — — — , Fraction of tire pyrolysis oil in total charge fr 1.0 1.0 0.7 0.7 Central line location L line m 0.71 0.71 0.71 0.71 Rapid cooling length L rapid cooling m 7.6 4.0 4.9 4.9 O 0.77 0.77 0.76 0.76 ¢0 3.15 2.88 2.95 3.34 Carbon yield Kg / kg 0.48 0.43 0.46 0.53 Dimensionless yield 0.54 0.48 0.51 0.59 Surface area per STSA m2 / g 73.9 94.1 91.6 69.4 Absorption I2 g / 100g 82.7 94.3 94.5 67.8 OAN ml / 100 g 65.5 64.1 82.8 73.5 COAN ml / 100 g 62.7 63.0 72.0 63.5 Table 10A Example number 23 24 25 26 Air flow to burner N / m³ / h 2000 2000 2000 2000 Air temperature °C 500 500 500 500 Natural gas flow rate N / m³ / h 160 160 160 160 Natural gas temperature °C 25.0 25.0 25.0 25.0 Reactor configuration Figure 5 Figure 5 Figure 5 Figure 5 Central line injector type BETE 1 / 2 BETE 1 / 2 BETE 1 / 2 BETE 1 / 2 Potassium acetate solution concentration g / L 5 5 5 5 Average feed material temperature °C 138 133 140 140 Total feed material flow rate to central line Kg / h 147 126 148 125 Fraction of tire pyrolysis oil in the central feed fr 0.3 0.3 1.0 1.0 Total raw material flow rate to first choke kg / h 344 292 344 292 Fraction of tire pyrolysis oil in the choke feed fr 0.7 0.7 1.0 1.0 Potassium acetate solution flow rate kg / h 3.6 3.0 3.5 3.1 Total raw material flow rate to second choke kg / h — — — — Fraction of tire pyrolysis oil in the throttling load fr -- — — -- Potassium acetate solution flow rate kg / h — — — — Fraction of tire pyrolysis oil in the total load fr 0.7 0.7 0.7 0.7 Central line location L line m 0.71 0.71 0.71 0.71 Rapid cooling length L rapid cooling m 4.9 4.9 4.9 4.9 0.77 0.77 0.77 0.77 ¢0 3.34 2.96 3.35 2.95 Carbon yield kg / kg 0.53 0.46 0.53 0.46 Dimensionless yield 0.58 0.52 0.59 0.51 Area per STSA m2 / g 70.7 89.1 72.0 87.0 Absorption I2 g / 100g 72.5 92.7 71.1 91.7 OAN ml / 100 g 84.1 88.1 88.7 89.3 COAN ml / 100 g 80.9 84.7 82.9 86.4 Table 10B [Tables II] Process Property Units Heavy TPO Settling Oil Distillery Corn Oil ASTM D-4052 Relative Density None 1.07 0.96 0.92 H:C Atomic Ratio None 1.04 1.40 1.46 BMCI None 137 90 55* ASTM D-529 1-02 wt% Carbon % 90.8 88.3 87.9 ASTM D-529 1-02 wt% Hydrogen % 7.9 10.4 10.8 IP-336 wt% Sulfur % 0.62 0.83 0.04 ASTM D-3228 wt% Nitrogen % 0.25 0.46 0.08 ASTM D-240 PCS MJ / kg 40.4 43.1 39.5 * Estimated from an average boiling point of 375°C for corn oils Table 11.

[0181] The reactor configuration for Examples 19 to 26 is illustrated in [Fig. 5]. The key dimensions for this configuration are given in Table 12. In these examples, a portion of the total feed material, whether settling oil or a mixture of settling oil and HTPO, was sometimes injected into the central line 73 using the injector shown in Table 12. The remainder of the total feed material was injected into the choke 76 in [Fig. 5]. The choke injectors were a set of four small tubes with diameters of 0.7 to 1.5 mm, evenly spaced around the circumference of the choke, installed so as to be oriented perpendicular to the crossflow. The sizes of the choke injectors were chosen so that the liquid feed material sufficiently penetrates the crossflow of the choke. [Tables 12] Dimension Description Units Value Combustion chamber diameter (cm) 20.3 Throat diameter (cm) 11.4 Reactor diameter (cm) between 22.9 and 9 1.4 Piping As shown in examples Rapid cooling As shown in examples Table 12

[0182] As shown in [Fig. 1 1], when pure HTPO was used in a single injection location, the structure as measured by the NAO was low (Examples 19 and 20). In Examples 21 and 22, a mixture of 30% settling oil and 70% HTPO is used in the throttling, and the structure increases. In Examples 23 and 24, this same mixture was used, except that 30% of the total raw material quantity was injected into the central line, with the remainder injected into the throttling. In examples 25 and 26, decantation oil was injected as pure feedstock into the central line, while HTPO was injected as pure feedstock into the choke, such that decantation oil constituted 30% of the total feedstock injected and HTPO constituted 70% of it.It was this process – in which the first carbon black raw material was a traditional raw material, while the low-yield raw material was injected downstream – that generated the greatest structural capacity.

[0183] Examples 27 and 28 in Table 13 illustrate instances in which a configuration such as that shown in [Fig. 4B] was used. Table 14 gives the dimensions of the reactor used in these examples. [Fig. 12] illustrates these examples as well as Examples 21 and 22. [Tables 13] Example number 27 28 Air flow to burner N / m³ / h 2000 2000 Air temperature °C 500 500 Natural gas flow rate N / m³ / h 160 160 Natural gas temperature °C 25.0 25.0 Reactor configuration name Figure 4B Figure 4B Center line injector type name None None Potassium acetate solution concentration g / L 1 1 Average feed material temperature °C 139 139 Total feed material flow rate to first choke Kg / h 250 250 Fraction of tire pyrolysis oil in center line charge 0.5 0.7 Potassium acetate solution flow rate Kg / h 2 2 Total feed material flow rate to second choke Kg / h 167 168 Fraction of tire pyrolysis oil in the c Throat load fr 1 0.7 Potassium acetate solution flow rate Kg / h — — Fraction of tire pyrolysis oil in total load fr 0.7 0.7 Rapid cooling length L rapid cooling m 6.7 6.7 O 0.77 0.77 ¢0 2.95 2.95 Carbon yield Kg / kg 0,435 0.444 Adimensional yield num 0.484 0.494 Surface area per STSA m2 / g 111 104 Absorption I2 g / 100g 109 115 OAN ml / 100 g 176 157, Table 13 [Tables 14] Dimension Description Units Value Chamber diameter 55 Combustion chamber diameter cm 20.3 Restriction diameter 64 First restriction diameter cm 11.4 Section diameter 58 First reactor chamber diameter cm 16 Section length 66 First reactor chamber length cm 61 Restriction diameter 65 Second restriction diameter cm 16 Rapid cooling e 67 As shown in the examples Table 14. The numbers in the Dimension column refer to [Fig.4B].

[0184] All the examples in [Fig. 12] used an overall raw material mixture of 30% decantation oil and 70% HTPO. When this mixture was injected into a single choke with the configuration of [Fig. 5], a relatively weak structure was obtained (Examples 21 and 22). Although this weak structure was partly the result of a relatively high alkali additive compared to Examples 27 and 28, Examples 21 and 22 would be the weakest structures even if no alkali were used. When the same mixture was injected into two choke locations, a superior structure was obtained (Example 28).However, when all of the first raw material, or traditional raw material, was injected into the first constriction, with the low-yield raw material used exclusively in the second constriction, then a superior structure was obtained at a given surface (Example 27). The dashed line indications on the data points, whose slope corresponds to that between Example 22 and Example 21, are given for illustrative purposes.

[0185] Examples 29 to 33 in Table 15 illustrate instances where the low-yield raw material was a vegetable oil, in this case, distiller's corn oil. Table 11 gives the properties of this vegetable oil as used in the experiment. The reactor configuration for these examples is shown in [Fig. 4B] with dimensions as given in Table 12. [Tables 15] Example number 29 30 31 32 33 Air flow to burner N / m³ / h 2000 2000 2000 2000 2000 Air temperature °C 500 500 500 500 500 Natural gas flow rate N / m³ / h 160 160 160 160 160 Natural gas temperature °C 25 25 25 25 25 Reactor configuration name Figure 4B Figure 4B Figure 4B Figure 4B Figure 4B Central duct injector type name None None None None None Potassium acetate solution concentration g / L 1 1 1 1 1 Average feed material temperature °C 160 160 145 166 151 Total feed material flow rate to first choke Kg / h 360 400 277 244 226 Fraction of corn oil from dist. in the choke charge fr 0.7 0.7 0.7 0.5 0.5 Flow rate of potassium acetate solution Kg / h 1.75 1.86 2.0 2.2 1.9 Flow rate of total raw material to the second choke Kg / h 0 0 152 157 151 Fraction of corn oil from dist.in the strain charge fr -- — 0.7 1.0 1.0 Potassium acetate solution flow rate Kg / h — — — — — Fraction of corn oil of dist. in the total charge fr 0.7 0.7 0.7 0.7 0.7 . Rapid cooling length (L) rapid cooling m 4.4 5.7 7.3 6.7 6.7 num 0.76 0.76 0.76 0.76 0.76 ¢0 num 2.63 2.84 2.73 2.86 2.72 Carbon yield Kg / kg 0.336 0.387 0.358 0.362 0.333 Dimensionless yield num 0.375 0.432 0.399 0.404 0.376 Surface area per STSA m² / g 109.5 90.5 108.3 133.1 137 I² absorption g / 100g 112.4 98.8 113.1 136.9 137 OAN Ml / 100 g 79.9 83.3 113.8 174.9 168.4 COAN Ml / 100 g 71 67.40.3 95.2 120.6 120.2 Table 15

[0186] Figure 13 illustrates the ability of exemplary embodiments to improve the structural capacity of the brittle feedstock. All of these examples used 30% decantation oil and 70% distiller's corn oil as the carbon black feedstock. In Examples 29 and 30, these two feedstocks were mixed directly and injected into a single reactor choke. This resulted in a weak structure, with an OAN of less than 90 ml / 100 g. When two chokes were used, as in Example 31, but the feedstocks were mixed directly, the structure improved modestly but remained weak.

[0187] However, in an exemplary embodiment where all the decantation oil went exclusively into the first constriction, the structure increased significantly, as shown in Examples 32 and 33. To achieve this, a mixture of 50% decantation oil and 50% corn oil was injected into the first constriction, while 100% corn oil was injected into the second constriction. The overall raw material usage in these examples was the same as in Examples 29 to 33: 30% of the total raw material used was decantation oil and 70% was distiller's corn oil.

[0188] The use of the embodiments provided herein has also improved the yield achievable on a given surface, as shown in [Fig. 14]. A direct mixture of 30% decantation oil and 70% corn oil in a single choke gave low yields (Examples 29 and 30), while the use of a double choke only slightly improved it (Example 21). However, when all of the decantation oil was injected exclusively in the first constriction (50% decantation oil and 50% corn oil in the first constriction, 100% corn oil in the second constriction), the dimensionless yield improved considerably (Examples 32 and 33). The dashed line in [Fig. 14] represents the yield slope with the area observed in Examples 29 and 30; this type of negative slope is typical of furnace carbon black processes.

[0189] The present invention includes the following aspects / embodyments / features in any order and / or in any combination: A process for producing carbon black comprising: introducing a stream of heated gas into a furnace carbon black reactor; the combination of at least one first raw material of carbon black with said heated gas stream to form a reaction stream; the downstream combination of at least one low-yield carbon black feedstock with said reaction stream present to form carbon black, wherein the at least one low-yield carbon black feedstock comprises at least 60% by weight of the total feedstock; and the recovery of carbon black in the reaction stream, in which the first raw material of carbon black is a liquid at ambient temperature and pressure, and has the following properties: - a correlation index from the Bureau des Mines (BMCI) > 100, - an H:C atomic ratio < 1.23 and - a relative density > 1.02; and in which the low-yield carbon black raw material exhibits at least one of the following properties: a correlation index from the Bureau des Mines (BMCI) < 100, or an H:C atomic ratio > 1.23 or a relative density < 1.02 or is a gas at ambient temperature and pressure. 2. The process according to any one of the preceding or following embodiments / features / aspects, wherein the low-yield carbon black raw material has at least one of the following properties: a) said Bureau of Mines correlation index (BMCI) < 95 or b) said gas at ambient temperature and pressure, or c) said H:C atomic ratio > 1.3 or d) said relative density < 1.0. 3. The process, in which the raw material for low-yield carbon black is ethylene. 4. The process according to any one of the preceding or following embodiments / features / aspects, wherein the low-yield carbon black feedstock is natural gas. 5. The process according to any one of the preceding or following embodiments / features / aspects, wherein the low-yield carbon black raw material has said relative density less than 1.02. 6. The process according to any one of the preceding or following embodiments / features / aspects, wherein the low-yield carbon black raw material is a tire pyrolysis oil, or an oil derived from the distillation or fractionation of tire pyrolysis oil. 7. The process according to any one of the preceding or following embodiments / features / aspects, wherein the low-yield carbon black feedstock is a feedstock other than liquid coal tar, petroleum refinery liquid, ethylene cracking residue, or phenol cracking residue. 8. The process according to any one of the preceding or following embodiments / features / aspects, wherein the low-yield carbon black feedstock is a plastic pyrolysis oil, a high H:C ratio settling oil, a renewable feedstock, a bio-based feedstock or other by-product of a refining process, or any combination thereof. 9. The process according to any one of the preceding or following embodiments / features / aspects, wherein said low-yield carbon black feedstock comprises at least one of the following materials: a vegetable oil or oil derived from other plants, a bio-based ethanol, a wax or resin of vegetable or animal origin, an oil obtained from animal fat, an algal oil, an oil obtained from the pyrolysis of sewage sludge or agricultural waste, a by-product liquid from the processing of a biogenic material, a liquid produced by hydrothermal liquefaction of a biomaterial, crude tall oil, tall oil rosin, tall oil pitch or tall oil fatty acid, an oil produced from recycled material, an oil derived from the pyrolysis of non-standard, discarded or end-of-life tires,an oil derived from the pyrolysis of discarded or recycled plastics or rubber products, an oil derived from the pyrolysis of solid municipal waste, or an oil derived from the pyrolysis of biomass, or any combination thereof. 10. The process according to any one of the preceding or following embodiments / characteristics / aspects, wherein the at least first raw material of carbon black comprises one or more of a settling oil, an oily sludge, coal tar, a coal tar derivative, an ethylene cracking residue or a phenol cracking residue. 11. The process according to any one of the preceding or following embodiments / features / aspects, wherein the first carbon black raw material comprises a fraction obtained from the distillation of pyrolysis oil from tyres. 12. The process according to any one of the preceding or following embodiments / features / aspects, wherein the low-yield carbon black feedstock constitutes 65 to 90 percent by weight of a total feedstock input into said process. 13. The process according to any one of the preceding or following embodiments / features / aspects, wherein the low-yield carbon black feedstock constitutes 70 to 90 percent by weight of a total feedstock input into said process. 14. The process according to any one of the preceding or following embodiments / features / aspects, wherein the furnace carbon black reactor has a combustion chamber and a choke downstream of the combustion chamber and a reaction chamber downstream of the choke and a rapid cooling zone downstream of the reaction chamber, and wherein the first carbon black feedstock is injected into a combustion chamber of the furnace carbon black reactor and the low-yield carbon black feedstock is injected into the choke. 15. The process according to any one of the preceding or following embodiments / features / aspects, wherein the furnace carbon black reactor has a combustion chamber and a choke downstream of the combustion chamber and a reaction chamber downstream of the choke and a rapid cooling zone downstream of the reaction chamber, and wherein the first carbon black feedstock is injected into said choke and the low-yield carbon black feedstock is injected after said choke. 16. The process according to any one of the preceding or following embodiments / features / aspects, wherein the furnace carbon black reactor includes a second choke downstream of said combustion chamber and before said rapid cooling zone, and said low-yield carbon black feedstock is injected into said second choke. 17. The process according to any one of the preceding or following embodiments / features / aspects, wherein said at least one first carbon black raw material is introduced into said carbon black reactor of furnace in at least one location upstream of a location where at least one low-yield carbon black feedstock is injected and at least one separate location downstream of the location of said at least one low-yield carbon black feedstock. 18. The process according to any one of the preceding or following embodiments / features / aspects, wherein the quantity of the first carbon black feedstock introduced before the location where at least one low-yield feedstock is injected is greater than 50% of the total quantity of the first carbon black feedstock. 19. The process according to any one of the preceding or following embodiments / features / aspects, wherein said at least one low-yield carbon black feedstock is introduced into said furnace carbon black reactor in at least two separate locations, one of the separate locations being downstream of the other. 20. The process according to any one of the preceding or following embodiments / features / aspects, wherein said at least one first carbon black feedstock is a mixture which comprises less than 50% by weight of a non-high yield carbon black feedstock on the basis of the total weight of said first carbon black feedstock. 21. The process according to any one of the preceding or following embodiments / features / aspects, wherein said at least one first carbon black raw material comprises from 95% by weight to 100% by weight of a high-yield carbon black raw material on the basis of the total weight of said first carbon black raw material. 22. The process according to any one of the preceding or following embodiments / features / aspects, wherein said at least one low-yield carbon black feedstock is a mixture comprising less than 50% by weight of a high-yield carbon black feedstock on the basis of the total weight of said low-yield carbon black feedstock. 23. The process according to any one of the preceding or following embodiments / features / aspects, wherein said low-yield carbon black raw material has said BMCI < 100. 24. The process according to any one of the preceding or following embodiments / features / aspects, wherein said low-yield carbon black raw material has said atomic H:C ratio > 1.23 25. The process according to any one of the preceding or following embodiments / features / aspects, wherein said low-yield carbon black raw material is said gas at ambient temperature and pressure. 26. The process according to any one of the preceding or following embodiments / features / aspects, wherein said recovered carbon black is a carbon black of NI 10, N121, N220, N231, N234, N299, N326, N330, N339, N347, N351, N358, N375, N539, N550, N650, N660, N683, N762, N765, N774, N787 or N990 quality. 27. Carbon black resulting from any preceding or following embodiment / characteristic / appearance.

[0190] The present invention may include any combination of the various features or embodiments above and / or below as stated in any sentences and / or paragraphs herein. Any combination of features disclosed herein shall be considered as forming part of the present invention, and no limit is envisaged as to the features that may be combined.

[0191] Furthermore, when a quantity, concentration, or other value or parameter is indicated as a range, preferred range, or list of upper and lower preferred values, it shall be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether the ranges are disclosed separately or not. When a range of numerical values ​​is stated herein, unless otherwise specified, the range is deemed to include its endpoints and all whole numbers and fractions within the range. The scope of the invention is not intended to be limited to the specific values ​​stated in the definition of a range.

[0192] Other embodiments of the present invention will become clear to those skilled in the art upon consideration of this document and implementation of the invention disclosed herein. It is understood that the document and the present examples are considered by way of example only, the true scope and spirit of the invention being indicated by the following claims and their equivalents.< / e> < / e> < / e>

Claims

Demands

1. A process for producing carbon black comprising: introducing a heated gas stream into a furnace carbon black reactor; combining at least one first carbon black feedstock with said heated gas stream to form a reaction stream; combining downstream at least one low-yield carbon black feedstock with said reaction stream present to form the carbon black, wherein the at least one low-yield carbon black feedstock comprises at least 60% by weight of the total feedstock; and recovering the carbon black from the reaction stream, wherein the first carbon black feedstock is a liquid at ambient temperature and pressure, for example, 25 °C at 1 atm, and has the following properties: - a Bureau des Mines correlation index (BMCI) > 100, - an H:C atomic ratio < 1.23 and - a relative density > 1.02;and in which the low-yield carbon black raw material exhibits at least one of the following properties: a Bureau of Mines correlation index (BMCI) < 100 or an H:C atomic ratio > 1.23 or a relative density < 1.02 or is a gas at ambient temperature and pressure, e.g., 25 °C at 1 atm.;

2. A process according to claim 1, wherein the low-yield carbon black feedstock is at least one of the following: a) said Bureau des Mines correlation index (BMCI) < 95 or b) said gas at ambient temperature and pressure, e.g., 25 °C at 1 atm or c) said H:C atomic ratio > 1.3 or d) said relative density < 1.

0.

3. A process according to claim 1, wherein the low-yield carbon black raw material is ethylene.

4. A process according to claim 1, wherein the low-yield carbon black feedstock is natural gas.

5. A process according to claim 1, wherein the low-yield carbon black raw material has said relative density less than 1.

02.

6. A process according to claim 1, wherein the low-yield carbon black feedstock is a tire pyrolysis oil, or an oil derived from the distillation or fractionation of tire pyrolysis oil.

7. A process according to claim 1, wherein the low-yield carbon black feedstock is a feedstock other than liquid coal tar, petroleum refinery liquid, ethylene cracking residue, or phenol cracking residue.

8. A process according to claim 1, wherein the low-yield carbon black feedstock is a plastic pyrolysis oil, a high H:C ratio settling oil, a renewable feedstock, a bio-based feedstock or other by-product of a refining process, or any combination thereof.

9. A process according to claim 8, wherein said low-yield carbon black feedstock comprises at least one of the following: a vegetable oil or oil derived from other plants, a bio-based ethanol, a wax or resin of vegetable or animal origin, an oil obtained from animal fat, an algal oil, an oil obtained from the pyrolysis of sewage sludge or agricultural waste, a by-product liquid from the processing of a biogenic material, a liquid produced by hydrothermal liquefaction of a biomaterial, crude tall oil, tall oil rosin, tall oil pitch or tall oil fatty acid, an oil produced from recycled material, an oil derived from the pyrolysis of non-standard, discarded or end-of-life tires, an oil derived from the pyrolysis of discarded or recycled plastics or rubber products,an oil derived from the pyrolysis of solid municipal waste or an oil derived from the pyrolysis of biomass, or any combination thereof,

10. Cl. A process according to any one of the preceding claims, wherein the at least first carbon black raw material comprises one or more of a settling oil, a sludge oily, coal tar, a coal tar derivative, an ethylene cracking residue or a phenol cracking residue.

11. A process according to any one of the preceding claims, wherein the first carbon black raw material comprises a fraction obtained from the distillation of tire pyrolysis oil.

12. A process according to claim 1, wherein the low-yield carbon black feedstock is from 65 to 90% by weight of a total feedstock input into said process.

13. A process according to claim 1, wherein the low-yield carbon black feedstock ranges from 70 to 90 percent by weight of a total feedstock input into said process.

14. A method according to claim 1, wherein the furnace carbon black reactor (80) has a combustion chamber (55) and a choke (64) downstream of the combustion chamber (55) and a reaction chamber (58) downstream of the choke (64) and a rapid cooling zone (62) downstream of the reaction chamber (58), and wherein the first carbon black feedstock is injected into the combustion chamber (55) of the furnace carbon black reactor (80) and the low-yield carbon black feedstock is injected into the choke (64).

15. A method according to claim 1, wherein the furnace carbon black reactor (80) has a combustion chamber (55) and a choke (64) downstream of the combustion chamber (55) and a reaction chamber (58) downstream of the choke (64) and a rapid cooling zone (62) downstream of the reaction chamber (58), and wherein the first carbon black feedstock is injected into said choke (64) and the low-yield carbon black feedstock is injected after said choke (64).

16. A method according to claim 15, wherein the furnace carbon black reactor (80) comprises a second choke (65) downstream of said combustion chamber (55) and before said rapid cooling zone (62), and said low-yield carbon black feedstock is injected into said second choke (65).

17. A method according to claim 1, wherein said at least one first carbon black raw material is introduced into said furnace carbon black reactor in at least one location upstream of a location where at least one low-yield carbon black feedstock is injected and at least one separate location downstream of said at least one low-yield carbon black feedstock location.

18. A method according to claim 17, wherein the quantity of the first carbon black feedstock introduced before the location where at least one low-yield feedstock is injected is greater than 50% of the total quantity of the first carbon black feedstock.

19. A method according to claim 1, wherein said at least one low-yield carbon black feedstock is introduced into said furnace carbon black reactor in at least two separate locations, one of the separate locations being downstream of the other.

20. A process according to claim 1, wherein said at least one first carbon black feedstock is a mixture comprising less than 50% by weight of a low-yield carbon black feedstock on the basis of the total weight of said first carbon black feedstock.

21. A process according to claim 1, wherein said at least one first carbon black raw material comprises 95% by weight to 100% by weight of a high-yield carbon black raw material based on the total weight of said first carbon black raw material.

22. A process according to claim 1, wherein said at least one low-yield carbon black feedstock is a mixture comprising less than 50% by weight of a high-yield carbon black feedstock on the basis of the total weight of said low-yield carbon black feedstock.

23. A process according to claim 1, wherein said low-yield carbon black raw material has said BMCI < 100.

24. A process according to claim 1, wherein said low-yield carbon black raw material has said atomic ratio H:C> 1.

23.

25. The method according to claim 1, wherein said raw material low-yield carbon black is said gas at ambient temperature and pressure, e.g., 25 °C at 1 atm.

26. The method according to claim 1, wherein said carbon black recovered is a grade carbon black of N110, N121, N220, N231, N234, N299, N326, N330, N339, N347, N351, N358, N375, N539, N550, N650, N660, N683, N762, N765, N774, N787 or N990.

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